You are on page 1of 342

o

o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o

o
o
o
o
o
o
o
o
o
c
c
c
Canadian Cataloguing in Publication Data c
Main entry under title: c
(-
Diagenesis
(Geoscience Canada reprint series; 4) c
Includes bibliographical references.
ISBN 0-919216-40-4
c
1. Diagenesis. 2. Rocks, Sedimentary.
c
I. Mcllreath , Ian A. II. Morrow, D.W. c
III. Geological Associat ion of Canada. IV. Series. c
QE571.D43 1990 552'.03 C90-090377-5 c
c
c
c
c
c
Cover Explanation: Realms of burial dia-
genesis (mesogenesis) are colour-coded in
c
shades of yellow. Early diagenesis (eogene- c
sis) is shown in purple and post-uplift dia-
genesis (telogenesis) is shown in green. Hot c
lower lithosphere marking the boundary be- Autho rization to photocopy items for internal or personal use, or
is
c
tween diagenesis and metamorphism is indi-
cated in red. Directions of fluid movement are
the internal or personal use of specific clients , granted by the
Geological Associat ion of Canada for libraries and other users c
indicated by arrows . Black indicates open
pore space in cavities or vugs . These open
registered with the Copyright Clearance Center (CCC) Transac-
tional Reporting Service, prov ided that the base fee of $3.00 per
c
spaces are filled with diagenetic mineral ce- copy is paid directly to CCC , 21 Congress Street, Salem , Mas-
sachusetts 01970, USA. 0·919216·40·4 $3 .00 + 0.00.
c
ments during burial.
The above perm ission does not extend to other kinds of copying , c
Illustration Concept: David Morrow, Calga ry
Graphics: Design Media Ltd., Toronto
such as copy ing for general distr ibution, for advert ising or promo-
tional purposes, for creating new collective works, or -for resale. c
For such copy ing , arrangements must be made with the publisher
in advance of publ lcatlon . c
Additional copies may beobtained bywriting to: L'Association geolog ique du Canada accorde I'autorisation de c
Geological Associat ion of Canada
Publications
photocopier des documentspour un usage interne au personnel ,
ou pour I'utilisation interne ou personnelle de clients particuliers, c
Department of Earth Sciences
aux bibliotheques et autres util isateurs inscrits au Copyright Clear-
ance Center (CCC) Transactional Reporting Service, ala condition c
Memorial University of Newfoundland
St. John 's, Newfoundland A1B 3X5
que Ie tar if de base de 3$ par copie soit paye directement au
Cent re, 21 Congress Stree t, Salem, Massachusetts 01970, USA.
c
Canada 0·919216·40·4 $3 .00 + 0.00 .
La presents permission ne s'applique pas a d'autres genres de
c
© 1990 ISBN 0-919216-40-4 reproduction, notamment la reproduction en vue d'une distribu- C
tion generate, a des fins de publtcite au de promotion, pour la
Typesetting: creation de nouveaux travaux collectifs ou pour la revente . Dans E
ces cas , iI faut prendre les dispos itions qu i s'imposent en cornmu-
Geological Association of Canada
and Typeline, Mississauga. Ontario niquant en advance avec I'ed iteur de l'Association. l
C
Printing:
The Runge Press Ltd. C
Ottawa, Ontario C
C
C
C
C
(

r:

CONTENTS
(
r
Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v

Introduction .
I.A. Mcllreath and D. W Morrow
r:
Limestones - Introduction .
N.P James and P W Choquette

( Limestones - The Sea Floor Diagenetic Environment


N.P James and PW Choquette
(
Limestones - The Meteoric Diagenetic Environment @§)
N.P James and P W Choquette

Limestones - The Burial Diagenetic Environment @


P W Choquette and N.P James

Dolomite - Part 1: The Chemistry of Dolomitization and 113


c Dolomite Precipitation
D.W Morrow

Dolomite - Part 2: Dolomitization Models and Ancient Dolostones . . 125


D.W Morrow

~~1P~~~~~e;~~d ·I i<.·L~~~~~t~i~' 8
Aspects of the Diagenesis of Coarse-Grained Siliciclastic Rocks .. @
r
I.E. Hutcheon

r: Catagenesis of Argillaceous Sedimentary Rocks 177


A. E. Foscolos .
r
Chemistry and Diagenesis of Organic Matter in Sediments 189
and Fossil Fuels
M.A. Barnes, WC. Barnes and R.M. Bustin

Determining Levels of Organic Diagenesis in Sediments 205


and Fossil Fuels
R.M. Bustin, M.A. Barnes and we. Barnes

Origin of Chert: Diagenesis of Biogenic Siliceous Sediments 227


R. Hesse

Silica Diagenesis: Origin of Inorganic and Replacement Cherts .. .. 253


R. Hesse

Early Diagenetic Pore Water/Sediment Interaction: 277


Modern Offshore Basins
R. Hesse

Fluid Geothermometry in Sedimentary Systems 317


I.E. Hutcheon, H.L. Abercrombie and D. Gardner

Index 325
/

c v

Co PREFACE
r:
The articles that formed the Diagenesis series in Other new contributions to the original series have
G Geoscience Canada were initiated by the senior editor, Ian A. been provided by R. Hesse, and I.E. Hutcheon, H.J. Aber-
Mcllreath, in the March 1982 issue of Geoscience Canada. crombie and D. Gardner concerning Inorganic Chert and
C The underlying philosophy of the Diagenesis series was Fluid Geothermometry, respectively. We are grateful for
o similar to that of the Facies Models series edited by Roger G.
Walker. Like the Facies Models series, the Diagenesis series
these additional contributions. The emphasis of the latter
paper is not on the origin of a particular rock type, but rather
( has been directed toward the non-specialist, the "general on an important aspect of the subsurface diagenetic
( , purpose geologist" alluded to by Professor Walker in the environment. This paper was included to remind even the
preface to the Facies Models series, and toward research casual reader that diagenesis involves the study of pro-
r:
scientists interested in aspects of diagenesis outside their cesses that affect the physico-chemical characteristics of
normal fields of specialization. The enormous success of the the diagenetic environment and to encourage the reader to
G first review series indicated that other aspects of the geo- look beyond the geologist's natural emphasis on the " end
o sciences, such as diagenesis , would benefit from this type of
simplified approach. As with the Facies Models series,
products " of diagenesis to the conditions and processes that
formed these "end products". The paper by Hutcheon,
o authors were asked to prepare reviews dealing with aspects
of diagenesis that entailed a minimum of jargon ,but yet
Abercrombie and Gardner fulfils this need by showing how
dissolution and precipitation of minerals in the subsurface is
c covered a signif icant part of the subject. Diagenesis itself is a closely related to temperature and solution composition.
natural associate of the subject of sedimentology, the main Ian Mcllreath originated this series and invited one
focus of the Facies Models series. An appreciation of both of the authors , David W. Morrow, to later join him as co-editor
o sedimentology and diagenesis are, of course, necessary for in order to facilitate the handling of what proved to be a

o an overall comprehension of the origin of sedimentary rocks.


In this sense, the Diagenesis review series is a natural
review series of unusual length. The length of this series has
also led to the decision not to include papers dealing pri-
o
r:
complement to the Facies Models series.
Twelve of the fifteen contributions within this vol-
marily with techniques for the study of diagenesis. This has
led to the exclusion of some papers that were part of the
ume originally were published in Geoscience Canada and original Geoscience Canada series from the final Diagenesis

o have since been revised for publicat ion here. Three papers
are new to this series and have been included to broaden the
volume and to the inclusion of some addit ional papers that
were submitted after publication of the Geoscience Canada
volume coverage on the subject of diagenesis . In this regard series. This is an unfortunate, but necessary, consequence
we extend our special thanks to Dr. R.J. Spencer of the of the decision to give priority to a more cohesive series and
University of Calgary for providing us, at relatively short we extend our apprec iation to the authors of papers that

c notice , with a review paper dealing with the diagenesis of


evaporites.
have been excluded for their understanding with regard to
this decision. Revised versions of some of these techniques
This series emphasizes the role that diagenesis papers have recently been included in other compilations
plays in the origin of common sedimentary rock types or, in (see Hutcheon , 1989).
o other words, how diagenesis transforms unconsolidated Monica Easton, as Managing Editor for Geoscience
o sediments into Iithified sedimentary rocks. Most of the
papers in this volume deal with specific sedimentary rock
Canada, has been more than helpful in editing and in hand-
ling the manuscripts for the printer. We thank a succession of
o types and their diagenesis and_are segregated into groups
according to general rock type so that carbonates and
chairpersons (Glen Caldwell, John Kramers , Godfrey
Nowlan and Bob Baragar) of the Geological Association of
evaporites are grouped separately from siliciclastics. Dia- Canada publications committee for their help. Peter Russell
genesis of organic material also is discussed separately and designed the sketches that head each article. Also, thanks
not as part of other rock types because of its widespread are due to Bob McNutt and Andrew Miall, the editors-in-chief
o occurrence as a constituent in all rock types and because of
its paramount economic importance both as coals and as
of Geoscience Canada during the progress of this series.
Finally, we extend our thanks to all authors and contributors
o fluid hydrocarbons. of illustrations and photographs for their willingness to fulfil
o our requests and for their monumental patience in waiting for
final publication. We hope their patience has been rewarded.

Ian A. Mcllreath and David W. Morrow


Petro-Canada and the Institute of Sedimentary and
Petroleum Geology, 1990
General Introduction

L ! ",,, ~
11 01
cesses such as compaction, cemen- is possible to assert, in a general way,
( tat io n, solut Lo~lJ.:Ill.adlated minera) that the realm of diagenesis is charac-
recrystallization and r.eRlacement, sub- ter ized by pressures of 0.1 MPa to
surface_solutiQo:IeJiching,.coaliflcatic;>..D.. 10MPa(1.0 bar to 1kb) and by tempera-
aiidttle degradation of organic material tures ranging from 0° to 300°C (see
( and generation of h drocarbon5.""Some Bates and Jackson , 1987). This corr
au ors, part icularly Russian workers sponds to a maximum burial depth of
(e.g., Strakhov, 1956), differentiate about 10 to 15 kilometres. In other
( between the period of initial lithification words, diagenesis occurs under the
of unconsolidated sediment and later pressure-temperature conditions char-
( changes that affect already lith ified acteristic of the earth 's outer crust and
Diagenesis
( rock. Strakhov (1953, 1956) restr icted the earth's surface.
General Introduction the use of the term " diagenesis" to One natural thermodynamically de-
apply only to the initial lithification fined interface that might be consid-
stage and applied the term " cata- ered to place an absolute operational
David W. Morrow
genesis" or "metagenesis" to any and upper limit on the realm of diagenesis
Institute of Sedimentary and
all subsequent changes that affect coincides with the critical points of
Petroleum Geology
sedimentary rocks. However, in Norti ' aqueous solutions involved in diagene-
( 3303 - 33rd Street N. W
America and Europe, the term " d i ag e ~­ sis. This is the curvilinear plane in pres-
Calgary, Alberta T2L 2A 7
esis" is taken to embrace all Chang~ sure - temperature - composition
Ian A. Mcllreath that occur in sediments and sedimen space across which liquid solutions
Petro-Canada tary rocks up to the time when they and their associated vapour phases
enter the realm of metamorphism merge to become single fluid phases.
c P. O. Box 2844
Calgary, Alberta T2P 3E3 (Larsen and Chilingar, 1979; see also
Foscolos, this volume, p. 177-187).
Little is known about the effects of
supercritical fluids on sedimentary
INTRODUCTION .;;!.. The transition between diagenesis rocks except to say that recrystalliza-
In this general introduction to a review ~nd metamorphism has not been as tion is likely to be much more rapid and
of diagenesis, we want to give the rigorously defined as the transition complete under the ir influence than
reader a broad overview of the papers between sediment deposition and that experienced by rocks containing
that are gathered together in this vol- subsequent diagenesis. As discussed subcritical solutions. One problem with
ume. Also, we aim to provide insight by Larsen and Chilingar (1979), it is im- this type of demarcat ion of the diagen-
( into what constitutes the scope of dia- possible to determine a unique combi- esislmetamorphism boundary is that
genesis and comment on some practi- nation of pressure and temperature even for pure water the critical tempera-
cal if not economic reasons why we that could be taken to characterize the ture of 374°C is considerably greater
should study diagenesis. Lastly, we transition between diagenesis and than that generally assumed to coincide
hope to give the interested reader some metamorphism because of the greatly with the upper temperature limit of the
indication as to what are the directions contrasting degrees of mineralogic diagenetic realm. This natural thermo-
of modern research toward the study of stabilities that characterize different dynamic demarcation is even less realis-
diagenesis. rock types. For example, evaporites tic for the much higher critical tempera-
recrystallize at temperatures and pres- tures and pressures that apply to the
DIAGENESIS - DEFINITION AND sures that have little affect on quartz saline aqueous soutions (Crawford,
SCOPE sandstones. Most workers would pro- 1981, fig. 4.12) that predominate in the
The term "diagenesis", like the term bably concur with Fyfe at al. (1958)that subsurface (Dickey, 1969). Conse-
"facies " (e.g., Walker, 1979), has diagenesis involves minor changes in quently, the pressure-temperature
undergone continual redefinition and the rock matrix and "crystallization of boundary separating diagenetic from
discussion since its introduction to the cement minerals in the hitherto open metamorphic conditions in the subsur-
geological literature by Von Guembel pores" whereas metamorphism occurs face occurs at considerably lower tem-
(1868). Larsen and Chilingar (1979), in where "the coarse crystal grains are peratures and pressures than those
their comprehensive review of diagene- also extensively involved in reaction so which characterize the critical points of
sis in all its aspects, provide an excel- that the rock becomes substantially subsurface fluids. In other words, dia-
lent historical summary of the term recrystallized". In essence, therefore, genesis of rocks proceeds only under
"diagenesis" as it applies to the origin of the classification of a particular rock as the influence of subcritical fluids; liquids
sedimentary rocks. Broadly speaking, metamorphic indicates that the original and their associated vapour phases.
as Larsen and Chilingar (1979) have sedimentary components are no longer Important consequences of the sub-
stated, "diagenesis can be defined as discernible as might be inferred from critical chemical behaviour of diage-
the changes whi ur in the charac- the etymology of the word "metamor- netic fluids include the fractionation of
ter and com osition of sed iments~ phosis". gases, such as carbon dioxide, hydro-
ginning from the moment of de osi' Although it is not possible to assign gen SUlphide, methane and other light
and lasting until the resultin materials unique ranges to the pressure and tem- hydrocarbons between the gaseous
roc s ~eJI1QY..e.d.J.ntQ the...r.e.al!J:L..Dl perature conditions characteristic of and liquid phases (i. e., dissolved
~9J: ~_ " alJd includes ro- subsurface diagenetic environments, it gases). For example, the existence of a
c
2 Diagenesis Geoscience Canada Reprint Series 4 c
(

large subcritical H20-C02 unmixing cipitation. Exceptions to this rule occur sents a quantitative, or at least semi- c
solvus (Todheide and Franck, 1963)
controls the composition of the CO2 -
where secondary porosity is developed
with the opportunity for further signifi-
quantitative, approximation of objec-
tively measureable parameters such as
c
bearing diagenetic solutions that are
most important for the creation and
cant porosity occlusion by diagenetic
minerals precipitated during later burial
mineralogic composition and texture.
In contrast, the classification of Cho-
c
destruction of subsurface porosity episodes . The effects of telogenesis quette and Pray (1970) and other simi-
through their participation in equilibria
involving carbonate minerals (see
can, of course, be repeated many times
and are particularly important in the
lar schemes primarily are inferential
and are based on the inferred origin or
c
Hutcheon , this volume, p. 165-176). diagenesis of soluble carbonates and genesis of diagenetic features observed
In recognition of the fundamentally
different processes that affect sedimen-
evaporites. Telogenesis can totally
erase the effects of earlier diagenetic
in sedimentary rocks. It is precisely
these features and phenomena about
c
tary rocks in a variety of diagenetically events in these soluble rock types. which our knowledge is very in - c
distinctive near-surface and deeper
subsurface environments many modern
Conversely, telogenesis may have only
a minor effect on insoluble siliciclastic
complete. Rocks which have very dif-
ferent diagenetic histories can be quite c
workers have adopted classification
schemes that subdivide these settings
rocks and on organic material. similar in mineralogy and texture. Dolo-
mites (or dolostones) are perhaps the
c
into two or three diagenetic realms. THE DIAGENETIC CYCLE - prime example of a rock type for which c
Recently, the tripartite classification of
Choquette and Pray (1970) has gained
PROCESSES, CONTROLS AND
PRODUCTS
classifications such as that of Choquette
and Pray (1970) can not be used with c
in popular usage (e.g., Schmidt and
Macdonald, 1979). In this classification
Classifications, such as that of Cho-
quette and Pray (1970), are useful in
confidence even though dolostones
themselves are considered by most
c
of diagenetic realms, eogenesis is that they communicate to the reader workers to be, almost invariably, com- c
(b defined as those diagenetic changes important information in a cursory pletely diagenetic in origin (Larsen and
c
that occur at or near the sediment@.olJ manner and the reader is forced to Chilingar, 1979). Consequently, the
SUrface where the interstitial solutiollS_
are still in communication with the over-
understand the rationale that underlies
these classificat ions. However, all clas-
objective of the reviews gathered
together in this series of articles lies in
c
lying water mass. After burial has effec- sifications have a drawback in that they demonstrating the diversity of pro- c
tively sealed the pore-filling solutions
from the overlying water mass , the
are generalizations. If a classification
scheme deals with purely descriptive
cesses through which sediments are
diagenetically altered and Iithified rather
c
enclosing sediments are considered to
r ~h ave passed into the mesogenetic dia-
attributes, such as classifications of
sedimentary rock types, then it pre-
than to categorize them rigorously
within classification schemes.
c
~genetic realm of the dge~ubsurface. c
THE DIAGENETIC CYCLE
Most sediments remain in the meso-
genetic regime throughout most of their
c
c
.
diagenetic history. Diagenesis that
occurs under the direct influeMfLQf.
r?i\eteoric solutions following uplift and SEDIMENTS c
\.:::::./eroslon IS conl:1!gne.cLto..tbe..telogeaetic
diagenetic .J..Ei9.i.m_e.... Other, similar
\ c
schemes that separate early diagenesis DIAGENETIC PROCESSES
~
c
from later diagenesis during burial and
from diagenesis after uplift and erosion INCREASING
ROCK/FLUID INTERACTION
DECREAS.... c
have been proposed (Fairbridge, 1967).
Organic geochemists tend to use the
THERMODYNAMIC
GRADIENTS
THERIIIOGYNAMIC
8RADIENTS c
term catagenesis in place of "meso- ,r------,~
DIAGENETIC PRODUCTS c
genesis" to indicate the diagenetic
changes that affect organic material
ROCK AND PORE SPACE
WITH CONTAIMED FLlHDS c
during burial (see Bustin and Barnes, c
this volume, p. 000-000).
Diagenesis for most ancient sedimen- +
ROCK C
tary sequences involved the repeated
exposure of these sequences to diage-
NON-POROUS
HtGHL Y-CEMENTED
E
netic realms as these sequences under-
Figure 1 A schematic representation of burial diagenesIs. The commonly observed correla-
\.
went cycles of subsidence and uplift.
Generally, however, the imprint of the tion of porosity reduction with burial depth is accompanied by repeated departures of the rock/
water system from thermodynamic equilibrium. These departures result in mineral precip itation
C
original eogenetic and mesogenetic his-
tory is preserved because of the large
or dissolution until the pore solution becomes saturated with respect to potential mineral C
precipitates. The natural evolution of pore fluids in the direction of increasing concentration or
porosity reduction and lithification that salinity with increas ing depth of burial favours mineral precipitation and porosity reduction C
occurs during the initial episodeof burial during burial diagenesis . However, many processes can interrupt or reverse this trend and
diagenesis. This severely limits the cause the retention or secondary development of porosity in the subsurface that is necessary C
extent of subsequent mineral pre- for the emplacement of hydrocarbon accumulations and many mineral deposits.
l
'--
<.
(,
( General Introduction 3
(

c Commonly, sediments undergo mul- formities. The immense Fateh Field of crystallization from clay minerals during
o tiple stages of diagenesis in the subsur-
face reflecting a succession of epi-
the United Arab Emirates, with over on
billion barrels of ultimate recoverable oil
burial-induced clay diagenesis also has
the potential to cause mineral under-
( sodes of cementation, dissolution and reserves, is an outstanding example of saturation in pore solutions and may

c recrystallization. In a very generalized


manner, these episodes may be viewed
reservoir enhancement by secondary
porosity development during the circula-
play a significant role in the develop-
ment of subsurface "overpressured"
( as part of an overall diagenetic cycle tion of low salinity meteoric ground zones (see Foscolos, this volume,
(Figure 1) involving cyclical departures water beneath an unconformable s - p. 177-187).
( of the rock/fluid system from thermo- face (Jordan et aI., 1985).

o dynamic equilibrium. These depar-


tures from equilibrium are followed by
It can readily be appreciated then that
the occurrence of hydrocarbon accu-
SEDIMENTARY ROCKS AND FLUIDS
- DIAGENETIC END PRODUCTS
o rock/fluid interaction that may be man-
ifested as the precipitation of mineral
mulations of economic size is linked to
the preservation of original or primary
The primary focus of the articles pre-
sented in this volume is on the end pro-
o cements, as pore space creation and porosity, or to the creation of secondary ducts of diagenesis - the rocks them-

o enlargement by dissolution or by fluid-


mediated mineral replacement reac-
porosity throughout the burial range
favourable for the maturation of hydro-
selves and the processes that led to the
development of individual rock types.
o tions. These processes all reflect the carbons (see Barnes et a/., this volume,
p. 189-204). This is true also for the
The sequence of articles here is dif-
ferent from their original order of
o return to thermodynamic equilibrium of
the rock/fluid system. occurrence of many economic metal appearance in the Geoscience Canada
This type of generalization empha- deposits which, in addition, depend series. Here, there is an overall subdivi-
C- sizes the great variety of subsurface upon the generation of subsurface solu- sion between sedimentary rocks that
O chemical processes that cause dissolu- tion salinities compatible with the for- originated as chemical sediments and

o tion and precipitation in response to


departures from thermodynamic equi-
librium. However, diagenesis itself is
mation of soluble chloride metal com-
plexes favourable for the transport of
metals in solution to precipitation sites in
those that are siliceous or siliciclastic.
Papers concerned with organic material
are included in the latter part of the
often represented in terms of unidirec- porous rock (Hanor, 1979). In other volume because of their emphasis on
o tional trends of porosity reduction words, under normal conditions, burial- the maturation of organic material in sili-

o through physical compaction, pressure


solution and mineral precipitation that
dependent processes of hydrocarbon
generation and metal concentration in
ciclastic sediments.
The first four papers by James and
commonly reflect the initial cycle of bur- subsurface fluids are countered by the Choquette deal with the diagenesis of
ial of a sediment which may have en- progressive disappearance of porosity limestones from their initial deposition
dured multiple episodes of burial and and hence a reduced opportunity for the through deep burial diagenesis and

o uplift. Diagenesis during burial is


almost universally accompanied by a
entrapment of hydrocarbons or forma-
tion of ore deposits. Atypical events are
subsequent exposure to meteoric
waters. They point out that diagene-
o trend of increasing pore water salinity
that commonly, though not invariably,
necessary for the generation of en-
hanced subsurface porosity although
sis in limestones is profoundly influ-
enced by the initial sediment miner-
o is linked to a progressive approach to there is now some evidence to suggest alogy, whether it is dominantly magne-

o saturation with respect to dissolved


minerals (Hanor, 1979). Consequently,
that organic maturation itself is respon-
sible, in some cases, for the develop-
sian calcite or aragonite. They outline
the intriguing research that has increas-
o there is an overall tendency for pre-
cipitation of mineral cements to con-
ment of "aecondary porosity t1:1"Ol 19b tb~
generation of organic acids during early
ingly indicated that shallow marine car-
bonate sedimentation and associated
tinue throughout the burial history of a bur ial diagenesis (e.g., Surdam and synsedimentary cementation has not
o sedimentary rock resulting in a rock
that is highly cemented and containing
Crossey, 1985). Commonly, however,
undersaturation with respect to diage-
always been dominated by aragonite.
Early Paleozoic seas may have been t.-
o little porosity (Figure 1). netic minerals in subsurface fluids and dominated by calcite, rather than arag-LV 'f

o Reversals to the general trend of


porosity reduction occur if major mineral
consequent porosity enhancement
through mineral dissolution is accom-
onite precipitation.
The role of climate as a major control
c components of the rock become under-
saturated during diagenesis. The gener-
plished by mixing with less saline mete-
oric solutions. This can occur where
on meteoric diagenesis (i.e., telogene-
sis) and the discussion of pressure-solu-
( ation of secondary porosity in carbon- deeply buried sediments are uplifted to tion effects during burial diagenesisare
ates by subsurface carbonate mineral shallower depths so that the sedimen- emphasized. Pressure-solution, both
l dissolution during burial (Schmidt and tary pile can be infiltrated by fresh or intergranular and along stylolites, is
r MacDonald, 1979) is an excellent exam- brackish ground water. An excellent identified as the most active process in
ple of this type of reversal in which example of meteoric ground water inva- porosity reduction and as a major con-
"~ cementation is followed by dissolution sion that accompanied post-burial uplift tributor of cement during deep burial
and porosity enhancement leading to is afforded by the Mesozoic and Tertiary diagenesis. An abundance of textural,
the development of subsurface hydro- foreland basin sediments of western chemical and isotopic evidence is uti-
carbon reservoirs. Many examples of Canada that were uplifted and subaeri- lized to compare modern with ancient
hydrocarbon reservoir facies and ore ally exposed during the Tertiary Lara- examples of carbonate diagenesis or to
deposit host facies exist because of mide Orogeny (Hitchon, 1984). The re- simply infer diagenetic processes or
porosity enhancement beneath uncon- lease of interlayer water and water of conditions. Among these criteria, oath-
c
4 Diagenesis Geoscience Canada Reprint Series 4 c
c
odoluminescence of cement fabrics, is addressed through the development teins, carbohydrates, lipids and lignin c
although commonly used to infer pre-
cipitational conditions during the
of criteria for the identification of cemen-
tation and recrystallization textures. The
into hydrocarbons. Early diagenesis
ends with the synthesis of " kerogen",
c
cementation of ancient limestones,
appears to us to lack documentation in
presence of certain " high temperature
salts" in evaporites may be useful as
the ubiquitous source material for
hydrocarbons . Unlike many other dia-
c
modern examples of diagenesis. Some minimum temperature geothermom- genetic processes, maturation of hy-
key research, in our estimation, could eters and, along with fluid inclusions, drocarbons is irreversible and strictly c
be done through the systematic inves-
tigation and documentation of the cath-
provide evidence as to temperatures
and pressures that affected these evap-
temperature dependent. Plots of the
hydrogen 'to carbon ratio versus the c
odoluminescent character of modern or
near-modern calcite cements from a
orites during diagenesis.
The second half of the volume, deal-
oxygen to carbon ratio of kerogen (or
bitumen) and coals on "van Krevelen"
c
variety of diagenetic environments. This
would place inferences concerning the
ing with siliciclastic and siliceous rocks
and the diagenesis of organic material,
diagrams delineates the progressive
thermal maturation of these residual
c
significance of cathodoluminescent ce- begins with Hutcheon's paper on the organic solids during burial and gener- c
ment stratigraphy in ancient limestones
on a firmer footing. The role of organic
diagenesis of coarse-grained siliciclas-
tics. Burial diagenetic reactions, such as
ation of hydrocarbons of progressively
shorter carbon chain lengths. Their
c
maturation toward the generation of feldspar albitization and reactions second paper outlines the tremendous c
secondary porosity and late stage ce-
mentation is described in the paper
between clay minerals and carbonates
occur in many siliciclastic sequences
advances that have been made in the
quantification of stages in the thermal c
dealing with deep burial diagenesis. It is
evident that research into the interaction
and are shown to have a profound effect
on the chemistry of pore solutions and
maturation of kerogens and coal. They
discuss vitrin ite reflectance and the
c
of organic material with carbonates dur- on the potential for porosity reduction othe r, less well documented optical c
ing diagenesis has barely begun.
Two papers by Morrow discuss dolo-
through reaction-related cementation.
Some of these reactions generate CO2
methods , such as conodont colour
alteration indices (CAl), palynomorph c
mitization, one of the more elusive dia-
genetic gremlins . The first paper deals
in addition to CO2 generated by organic
maturation. This CO2 can contribute to
thermal alteration indices (TAl), and lip-
tinite fluorescence that are commonly
c
with what is known concerning the the development of secondary porosity compared to an equivalent rank of c
chemistry of dolomitization and dolo-
mite precipitation. The influence of a
or to additional carbonate cementation
and porosity reduction depending on
vitrinite reflectance . Chemical meth-
ods for evaluating source rock potential c
variety of kinetic inhibiting factors
affecting dolomite precipitation at low
whether carbonate equilibria or non-car-
bonate equilibria control the hydrogen
and for characterizing maturation rank
also are discussed. These include tech-
c
temperature is discussed and the re- ion activity (pH) of diagenetic pore solu- niques for isolating biological markers c
cent perception that the presence of
sulphate in solution strongly inhibits
tions. Hydrocarbon recovery efficien-
cies are related to the presence of pore-
or " geochemical fossils", such ho-
panes and steranes, from extractable
c
the precipitation of dolomite, even at filling diagenetic clay and carbonate organic matter (i.e., organic matter sol- c
the high temperatures typical of deep
burial, is assessed. The following paper
minerals.
Diagenes is of fine-grained argilla-
uble in standard organic solvents).
These markers provide information c
deals with the origin of ancient dolo-
stones and a wide variety of models for
ceous sediments is outlined by Fos-
colos. Here, the emphasis is on the
concerning the source rocks for par- •
ticular hydrocarbon accumulations .
c
dolomitization in synsedimentary to effects of the temperature controlled, Rock-EvaliP analysis is presented as a c
deep burial settings are described.
Emphasis is given to mass balance
dominantly isochemical clay reactions
by wh ich swelling clays (smectites)
means for the routine estimation of
both the organic source rock potential c
considerations in assessing the poten-
tial relevance of particular models for
evolve to the non-swelling iIIitic clays
that characterize most ancient basinal
and the maturation rank of most sedi-
mentary rocks in a manner that is most
c
dolomitization. Recent research con- shales. These changes are accom- accessible to petroleum exploration ists c
cerning the origins of dolomite crystal
textures and their potential application
panied by the sporadic release of water
from clay minerals to the pore solution
unfamiliar with organic geochemistry.
Modelling of thermal maturity in basins c
as diagenetic geothermometers are
discussed along with the recent
and may contribute to the development
of overpressured zones in shale se-
is also discussed using calculated time-
temperature indices (TTl) based on
c
application of fluid inclusion studies to quences and, possibly, to hydrocarbon subsidence histories. c
the problem of the origin of dolomite.
Spencer's contribution concerning
migration. The dissolution of feldspars
generates amorphous hydrous gels of
The origin of chert and siliceous sedi-
ments is discussed in two following e
the diagenesis of evaporites rounds out silica, aluminum and iron that can par- papers by Hesse. In the first paper, he
the first half of the volume series. Tex- ticipate in later stages of clay diagene- describes the origin and distribution of
tural studies and criteria for the recogni- sis, such as the growth of diagenetic siliceous sed iments in the world's <--
tion of successive episodes of evaporite chlorite in pore spaces. oceans emphasizing the important role
diagenesis are emphasized. The long Diagenesis of organic material is of water depth in relation to the calcite
C
neglected importance of diagenetic reviewed in the follOWing two papers by compensation depth. Low temperature C
cementation, inferred from the degree Barnes , Bustin and Barnes. In their first maturation of siliceous radiolarians and
of porosity reduction observed in buried paper, they outline the transformation diatoms results in their transformation C
evaporites and ancient evaporites, of initial biologic materials, such as pro- from opal-A to the opal-CT of porcel-
C
C
C
C
r:
c., General Introduction 5

C
r lanites and finally to chert composed example, externally imposed changes search toward understanding diagene-
o dominantly of quartz. The shift in the
d(101) peak position of opal-CT has
in fluid chemistry commonly exert a
strong effect on the diagenesis of car-
sis. Such summaries become dated
very quickly with respect to such a
o some potential as a maturation indicator bonate, clays and aluminosilicates and rapidly evolving subject in which re-

c in sediments less than 100 million years


old. The second paper emphasizes the
silica but has little effect on the dia-
genesis of organic material or evapo-
search efforts are proceeding in many
different directions. With this caveat in
c various modes of siliceous replace-
ments that sediments and rocks
rites. Organic material is commonly not
affected because its diagenesis is dom-
mind, certain aspects of diagenesis can
be identified as undergoing particularly
c undergo. Commonly, such replace- inated by thermal organic maturation intensive research at the present time.

c ments occur under high pH conditions


that favour silica precipitation.
whose reactions proceed relatively
rapidly to form liquid hydrocarbons that
The final paper of this volume by
Hutcheon, Abercrombie and Gardner
( The final two papers of the series, by tend to exclude other fluids from the highlights one important and very active
Hesse and Hutcheon, Abercrombie and pore space. Evaporites are little modern research direction. This is the
( Gardner depart from the main series affected by compositional changes in application of computer-based models

o theme emphasizing the "end products"


of diagenesis in that they deal instead
pore solutions because dissolution of
soluble evaporite minerals effectively
of mineral and aqueous chemistry to
simulate the thermodynamic state of
o with diagenetic conditions and pro- buffers the solution composition diagenetic systems. Figure 2 is an

o cesses. Hesse shows how the inter-


pretation of concentration profiles of
against externally imposed solution
composition changes. Temperature is,
example of a stability diagram gener-
ated by the PC-based program (PTA) of
o pore water chemistry in modern marine
basins can be used to infer rates of
of course, an important external control
on all diagenetic changes involving
Brown et al. (1988). This diagram was
used to infer the compositional changes
o sedimentation and pore water advection
with respect to ongoing sediment reac-
chemical reactions. Silica cementation
has been singled out as an exception to
of waters that participated in diagenesis
of the Clearwater Formation at Cold
tions. The role of organic material in this rule because of the greatly domi- Lake, Alberta, based on the petro-
o controlling early sediment diagenesis
because of the generation of carbon,
nant role that the pH of the solution plays
in silica diagenesis, particularly during
graphically determined sequenceof dia-
genetic minerals (Abercrombie, 1989).
nitrogen, sulphur and hydrogen as bac- early diagenesis, or eogenesis. The rate Programs such as PTA of Brown et al.

o terial metabolites is emphasized.


Hutcheon, Abercrombie and Gardner
of fluid flow has a strong effect in most
diagenetic situations, but generally not
(1988)generate phase diagrams in pres-
sure - temperature - activity space for
show how concentrations of ions, such on the diagenesis of organic material. thermodynamic systems with user-
as sodium, potassium and silica, in solu- Similar reasoning may be applied to the defined components. Other programs,
C tion can be used as geothermometers in other cited diagenetic controls in such as SOLMNEQ (Kharaka and
the presence of equilibrium mineral assessing their relative significance. Barnes, 1973) bridge the gap between
l asemblages. This table is presented merely to give the thermodynamic activities of com-
( Table 1 is meant to provide a gener- the reader an overview of the gener- ponents and their concentrations in
alized assessment of the relative degree alized diagenetic controls that apply to aqueous systems to permit the calcula-
C of importance of individual diagenetic the diagenetic end product rock types tion of mineral saturations from con-
o controls on the development of the dia-
genetic rock types that are described
discussed in this volume. centration data. Other programs, such
as PHREEQE (Parkhurst et al., 1980),
in this series. These controls are DIRECTIONS OF MODERN have been developed which permit the
envisaged as primarily being external in RESEARCH modelling of reaction pathways, which
nature and are imposed upon the rock- It is difficult to summarize in a concise may be plotted on phase diagrams, and
or sediment-pore fluid system. For manner the directions of modern re- can even give estimates of the extent of

Table 1 Dependence of diagenesis on major diagenetic controls.

Diagenetic Controls
Diagenetic Products Biologic Time Temperature Pressure Fluid Flow Fluid
Activity Chemistry
l Carbonate Cementation and Strong Weak Strong Strong Strong Strong
r
Recrystallization
Evaporite Cementation and Weak Weak Strong Strong Strong Weak
Recrystallization
Clay and Alumino-Silicate Weak Strong Strong Weak Strong Strong
Diagenesis
Organic Material Strong Strong Strong Weak Weak Weak
Silica Cementation and Strong Weak Weak Weak Strong Strong
Recrvstallization

"
'---
c
6 Diagenesis Geoscience Canada Reprint Series 4 c
c
mass transfer of chemical components c
between the solid phases and the solu-
tion during fluid-mediated chemical
c
reactions . Ultimately, this approach will
yield important quantitative estimates COMPUTER-GENERATED
c
(
of the amount of porosity loss or gain
MINERAL PHASE DIAGRAM
during successive stages of diagenesis
12
c
for a wide range of rock types .
A closely related intensive research
effort has recently been devoted toward
c
an improved understanding of the inter-
action between organic matter and min-
eraI diagenesis. The production of
organic acids and carbon dioxide as 10 Analcime c
reaction products during the diagenesis
of organic matter has been shown to
c
exert a strong influence on the satura- c
tion state of carbonate minerals and the
acidity of subsurface environments c
(Surdam and Crossey, 1985). Again the
accuracy of the assessment of values
C
for these solution parameters is depend- C
ent upon the development of accurate
models of aqueous chemistry. One Potassium
C
important aspect with regard to the
Feldspar C
improvement of these models concerns
the acquisition of more accurate ther- C
modynamic data for organic acids, such
as acetic acid, which are abundant in
C
subsurface environments. Recent ad- C
vances in the understanding of early
diagenesis of organic material have C
been made concerning the correlation
of early diagenetic mineral reactions,
C
such as the generation of pyrite by sul- C
phidic diagenesis, with the degree of
preservation and availability of organic C
material for diagenesis during later bur-
ial (Gautier, 1985).
C
The diagenetic aspects of models for C
basin development have undergone
definite changes under the impact of o C
new ideas concerning the role of
organic acids. For example, Surdam et
o 2 10 12 C
aJ. (1989) have shown that variations in C
the amounts and types of organic
material results in profound differences C
in the style of mineral diagenesis and in
the evolution of porosity during burial
C
diagenesis of many hydrocarbon-bear-
Figure 2 A computer-generated phase diagram that has been used to infer the evolution of
C
ing siliciclastic sequences .
Rapid recent advances have also fluid compositions during diagenesis of the Clearwater Formation in the Cold Lake heavy oil C
area, Alberta (Abercrombie, 1989). The succession of diagenetic minerals observed in this unit
occurred with respect to techniques that
indicate initial deposition in brackish waters of mixed marine/river composition (stage I).
provideestimates of the relative and abso-
luteagesof subsurfacediageneticevents.
Enrichment of sodium and potassium is reflected by the progression from mixed layer clays (lIa)
to the maximum diagenetic assemblage, stage lib, comprising quartz-Kspar-analcime-iIIite(?). c
Absolute ages for the precipitation of This was followed by precipitation of Kaolinite and isotopically distinct calcite reflecting Tertiary (
authigenic clay minerals and feldspars in uplift of the Clearwater, an influx of low salinity meteoric fluids, and biodegradation of oil. This
siliciclastic sediments may be obtained caused pore fluids to change composition along the path labelled 1/1. C
from the K/Ar, 4OArJ39Ar, and K/Ca iso-
topic dating techniques and from fission C
track dating with greatly improved (
C
C
/'

(
General Introduction 7
r

accuracy in recent years. Such ad- Chilingar, G.V. and Wolf, K.H., 1988, eds., Lundegarde, P.D., 1989, Temporal recon-
C vances greatly improve our ability to Diagenesis , I: Elsevier, Amsterdam , struction of sandstone diagenetic histo-
unravel the geochronological history of Developments in Sedimentology, v. 41, ries, in Hutcheon, I.E., ed., Burial Dia-
G diagenetic cements and consequently 591 p. genesis : Mineralogical Association of
( our ability to understand the history of Choquette, P.w. and Pray, L.C., 1970, Geo- Canada, Short Course Handbook, v. 15,
logic nomenclature and classification of p. 161-194.
diagenesis and its application to basin
( analysis (Lundegarde, 1989). Fission
porosity in sedimentary carbonates: Naeser, N.D., 1986, Neogene thermal his-
American Association of Petroleum Geo- tory of the northern Green River Basin,
( track dating of heavy minerals, such as logists Bulletin, v. 54, p. 207-250. Wyoming-Evidence from fission track
apatite and zircon, also gives important Crawford, M.L., 1981, Phase equilibria in dating, in Gautier, D.L., ed., Roles of
( paleotemperature infor mat ion that aqueous fluid inclusions, in Hollister, Organic Matter in Sediment Diagenesis:
spans the temperature range for oil L.S. and Crawford , M.L. , eds., Short Society of Economic Paleontologists and
( Course in Fluid Inclusions: Applications
generation (Naeser, 1986). Mineralogists, Special Publication No.
c Modern studies of diagenesis have
also moved in the direction of semi-
To Petrology: Mineralogical Association
of Canada, Short Course Handbook Vol-
38, p. 65-72.
Parkhurst, D.L., Thorstenson, D.C. and
o quantitative to quantitative modelling ume 6, p. 75·100.
Dickey, P.A., 1969, Increasing concentration
Plummer, N.L., 1980, PHREEQE - a
Computer Program for Geochemical
o of diagenetic processes from the scale
of diagenetic micro-environments to a
of subsurface brines with depth: Chemi- Calculations: United States Geological

c global scale. Chilingar and Wolf (1988)


provide a broad overview of research
cal Geology, v. 4, p. 361-370.
Fairbridge, R.W., 1967, Phases of diagenesis
and authigenesis , in Larsen, G. and
Survey, Water-Resources Investigations
80-96 (revised and reprinted in 1987),
193 p.
concerning models for diagenesis, Chilingar, G.V., eds., Diagenesis in Sedi- Schmidt, V. and McDonald, DA , 1979, The
particularly as they apply to the ori- ments: Elsevier, Amsterdam . role of secondary porosity in the course
gin of ore deposits and hydrocarbon Fyfe, W.S., Turner, F.J. and Verhoogen, J., of sandstone diagenesis, in Scholle, P.A.
o reservoirs. 1958, Metamorphic reactions and meta-
morphic facies: Geological Society of
and Schluger, P.R., eds., Aspects of
Diagenesis: Society of Economic Pale-
o It is evident that the study of diagene-
sis has expanded far beyond a purely America, Memoir 73, 259 p.
Gautier, D.L., 1985, Interpretations of early
ontologists and Mineralogists, Special
Publication No. 26, p. 209·226.
descriptive stage involving merely the
diagenesis in ancient marine sediments, Strakhov, N.M., 1953, Diagenesis of sedi-
identification of minerals or rocks of in Gautier, D.L., Kharaka, Y.F. and Sur- ments and its significance for sedimen-
diagenetic origin. This series has dam, R.C., eds., Relationship of Organic tary iron formation: Izvestia Akademia
emphasized the contribut ion of diage- Material and Mineral Diagenesis: Nauk SSSR, Series of Geology, v. 5,
netic processes to the origin of specific Society of Economic Paleontologists and p. 12-49.
o rock types. The reader will appreciate,
however, that diagenesis itself involves
Mineralog ists, Short Course No. 17,
p.6·72.
Strakhov, N.M., 1956,Towards knowledgeof
diagenesis, in Questions of Mineralogy
o the interaction of many different pro-
cesses in the lithosphere , biosphere
Hanor, J.S., 1979, The sedimentary genesis
of hydrothermal fluids, in Barnes, H.L.,
of Sedimentary Formations: L'vov Gos.
Univ., L'vov.
and hydrosphere. The complexity of ed., Hydrothermal Ore Deposits: John Surdam , R.C. and Cressey, L.J., 1985,
Wiley and Sons, New York, p. 137·169. Mechanisms of organic/inorganic inter-
some of these processes may be
Hitchon, B., 1984, Geothermal gradients, actions in sandstone/shale sequences,
glimpsed in the papers of this series. It
o is our hope that this information may be
hydrodynamics, and hydrocarbon occur-
rences: American Association of Petro-
in Gautier, D.L., Kharaka, Y.F. and Sur-
dam, RC. , eds., Relationship of Organic
o of assistance to the reader in pursuing
his or her research interests or as an aid
leum Geologists , Bulletin, v.68,
p.713·743.
Matter and Mineral Diagenesis: Society
of Economic Paleontologists and Miner-
to exploration ists involved in the search Hutcheon, I.E., 1989,ed., Burial Diagenesis: alogists, Short Course No. 17, p. 177-232.
for hydrocarbon and mineral resources. Mineralogical Association of Canada , Surdam , RC., Dunn, T.L., Heasler,H.P. and
Short Course Handbook, v. 15, 409 p. MacGowan, D.B., 1989, Porosity evolu-

o REFERENCES CITED Jordan, C.F., Jr., Connally, T.C., Jr. and Vest,
H.A., 1982, Middle Cretaceous carbon-
tion in sandstone/shale systems , in
Hutcheon, I.E., ed., Burial Diagenesis,

o Abercrombie, H.J., 1989, Water-rock inter-


action during diagenesis and thermal
ates of the Mishrif Formation, Fateh
Field, offshore Dubai, UAE., in Roehl,
Mineralogical Association of Canada,
Short Course Handbook, v. 15, p. 61-127.
( recovery, Cold Lake, Alberta, Ph.D . P.A. and Choquette , P.W. eds., Carbon- Todheide, K. and Franck, E.U., 1963, Das
thesis, Department of Geology and Geo- ate Petroleum Reservoirs: Springer-Ver- Zwe iphasengebeit und die kritische
r:
physics, The Unversity of Calgary, Cal- lag, New York, p. 425-442. Kurve im system Kohlendioxid-Wasser
gary, Alberta , 183 p. Kharaka, Y.K. and Barnes, I. , 1973, bis zu Drucken von 3500 bar: Zeitschrift
Bates, RL. and Jackson, J.A., 1987, Glos- SOLMNEQ: Solution-mineral equilib- fur Physiks und Chernie, N.F., v.37,
sary of Geology, Third Edition: American rium computations : Un ited States p.388-40t
Geological Institute, 788 p. Department of Commerce, NTIS Report Von Guernbel, C.w., 1868, Geognostische
Brown, T.H., Berman, R.G. and Perkins, PB 215-899, Springfield, Virginia, 81 p. Beschreibung des ostbayerischen
E.H., 1988, GEO-CALC: Software pack- Larsen, G. and Chilingar, G.v., 1979, eds., Grenzgebirges, I-III, 700 p.
age for calculation and display of pres- Diagenesis in Sediments and Sedimen- Walker, R.G., 1979, ed., Facies Models:
sure-temperature-composition phase tary Rocks: Elsev ier, Amsterdam, Geoscience Canada Reprint Series 1.
diagrams using an IBM or compatible Developments in Sedimentology, v.25A, 211 p.
personal computer: Computers and 579 p.
Geosciences, v. 14, p. 279-289.
c
8 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
c
c
(
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
SEM photomicrograph of sandstone in the Cretaceous Viking Formation ofthe Caroline Oil Field. Intergrown clusters of authigenic c
microquartz and chlorite (OC) are interspersed with authigenic pyrite (P) in the deeply buried, chert-rich Caroline sandstones.
Chlorite is commonly associated with late-stage burial diagenesis of siliciclastic sediments. Photograph courtesy G.E. Rein!lon
and A.E. Foscolos (Geological Survey of Canada).
c
C
E
C
(
(
C
C
(
C
C
Limestones: Introduction 9

tion is surface and subsurface fluid tation, although not ubiquitous, is the
composition. Waters most commonly in most important diagenetic process on
contact with carbonate rocks and sedi- the modern sea floor. It is manifest in the
ments are marine, meteoric or deeE f ormation of grains (i.e., ooids), the hard-
subsurface in origin ~With time, as car- ening of soft grains by intragranular pre-
bonates are deposited, precipitated, cipitat ion (i.e., peloids), and the lithifica-
buried, eroded, exposed and reburied, tion of loose carbonate sediments to
they interact with these fluids, each of form sea floor limestone. In contrast, the
which affects the sediments or rocks in main biological process is boring, by a
a special way and leaves a unique dia- variety of macro and microendoliths,
Limestones: genetic signature. Each region charac- who may destroy much depositional
terized by waters of different composi- fabric .
Introduction tion (Figure 1) can be thought of as a -1k Both of these processes, precipitation
separate diagenetic environment (Pur- and boring, take place on the shallow
dy, 1968). In this synthesis we recog- tropical sea floor. With increasing water
Noel P. James nize three major diagenetic environ- depth, accompanying increases in pres-
Department of Geological Sciences ments : (1) the sea floor and underlying sure and decreases in temperature
r: Queen's University shallow marine phreatic, characterized combine to result in some cases in ~ neo-
Kingston, Ontario K7L 3N6 by marine waters, together with the morphism ..and ultimately in complete
strandline bathed in mixed marine and dissolution. _
Philip W. Choquette fresh waters; (2) the meteoric distin- The Meteoric. If carbonate sedi-
Department of Geological Sciences guished by the freshwater vadose and ments are, through uplift, fluctuations in
University of Colorado plireatic zones and the shallow phre- sea level or simply rapid accretion,
Boulder, Colorado 80309-250 atic region of mixed fresh and marine exposed subaerially to percolating
waters ; and (3) the deep burial, where meteroic waters, dramatic changes take
INTRODUCTION pores are filled with waters that may place. Diagenesis is driven by two reac- 0'1
Limestones are among the most once have been marine but have been tions, one between the carbonates , LV
capricious of rocks. Mostly born from moderately to drastically modified by regardless of composition, and meteonc
the sea and generally biologic in origin, burial diagenesis. Changes that take waters of differing temperature andlor ~~
they possess an extremely sensitive place in each of these settings is the Peo• called water-controlled meteoric V
record of past life and conditions on topic of a separate article in the follow- diagenesis and another between miner-
earth, yet because they are lime and so ing series, but to place the whole spec- als of differing solubilities and meteoric
easily susceptible to chem ical change , trum in context we first summarize the water calledminerakontrolled meteoric
this record is commonly blurred or ren- main attributes of all the realms and diagenesis. Water-controlled alteration is
dered unreadable by diagenesis. Para- outline the diagenetic changes that reflected by the formation of caves and
doxically, this same diagenesis is eco- occur in each. Other karst features, local precipitation of
nomically beneficial because the holes The Sea Floor. Carbonate precipi- spelean carbonates ao.d_calccete-d~I-
and voids created during alteration
may be later filled by base metal pre- /VCr X,'lA..j 2.-0"~ (f,f)lAJ.. .0~ I-/t)
cipitatesor hydrocarbons. So, to under-
stand limestones for any purpose it is
'hV/Iet c-s« * c)
imperative to decipher the often com-
plex series of processes that have mod-
ified their texture and composition
through geologic time.

o
r
The following articles are an overview
and not an in-depth treatment of the
topic ; they are intended as a guide to
r current understanding and a synthesis
®
, ' h:j..
of concepts useful when interpreting the
diagenetic history of limestones. Since DEEP BURIAL
most limestones are marine, the articles
r
. ;...

...... t-- 1. / Y concentrate on these rocks. The papers


,.- '<
were originally written between 1982 (;'j~ I,
} and 1986 and have been revised and .. J7;;';;::;t? .r~"
~j -; Y-;,' \,\t. updated for this volume. l\)nD~ uO#'/ (~"
~ ./ ~ Figure 1 A sketch outlining the main diagenetic environments through which carbonate
,,,)1 \; ~v DIAGENETIC ENVIRONMENTS sediments and rocks pass in geologic history. Depending upon hydrodynamics, configuration
LV' ~\" Since rock-water jnteractionJs the pri- of the aquifer and permeability, the freshwater phreatic waters may underlie only the exposed
1\'" \ i , mary force driving carbonate diagene- area as illustrated here or may extend seaward beneath the shelf and underlie a thin shallow
l'\f'~1 Y sis, a key tactonln the diagenetic equa- ,~t IV marine phreatic zone.
'-'" v· ~ \ ' \..~( ~\ (btl I( I J.t 1 / _ tiC " 0'1 V'!f
r , i"\J~ Q M~'" ~(' '6' ~<,((}v c /)l/f()..rf~1J.0 U.lI\lvV~ l
{f.Jl.l/tl I l l , , , -( .,
~ I). j I' \1lI' >\l ~
/ \) II 1.:-......... lJY~i...,I "!~.-.:!.!!./7'oJ~ -!.-_--
~ ~ <:l \ \I\I"~V 'j \
C~ ~ ~ ~ U1u ~16'''r;j /</1(/
' I) J
,J'....f --.-/ . II i I-(JI/Y YI"'V 'I
D' o U (1'1 "'., 0 'I . I
c
10 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
~
o opment. Mineral-cQntrolled alteration
results in the transformation Qf arag-
burial environment for extended
periods. NQt all carbonates , however,
TECHNIQUES AND LITERATURE
The indispensable source of information c
onite and magnesium-calcite (high
magnesium calcite) to calcite witfi neg-
are flushed by meteor lc waters . Nev-
ertheless, it is common to see some
on the topic of carbonate diagenesis is
the text by Bathurst (1975) and the fol- c
Iigible magnesium CQntent (low magne-
sium calcite). Many components have
evidence of meteoric diagenesis, gen-
erally because in shallow-marine set-
lowup article in 1980 . For a more general
treatment of the subject the reader is
c
their microstructure altered dramat- tings they accumulate rapidly to sea referred to the books by Friedman and c
ically during this process ot mineral
transformation, while others are dis-
level. Combined with subtle fluctua-
tions in sea level, this commonly leads
Sanders (1979), Blatt et al. (1980) and
Flugel (1982). Good sourcesfor the iden- c
solved completely leading tQ new pat- to subaerial exposure and thus mete- tification of components are the vol- c
terns of porosity and permeability.
These changes are accompanied by
oric diagenesis, even if short lived.
In actual experience different dia-
umes by Scholle (1978) and Horowitz
and Potter (1971). For a parallel treat- c
widespread lithfficatlon through ce-
ment precipitation.
genetic processes vary markedly in
importance Irorn environment to en-
ment of diagenesis with a somewhat
different approaches the articles by
c
The processes and products of mete- vlronrnent (Table 1). Most sediments on Longman (1980) and Harris et al. (1985) c
oric diagenesis cannot be applied
equally tQ carbonates ot all ages
the modern sea floor are affected to
some degree by bloerosion, but ce-
are recommended. Papers treating spe-
cific aspects of cementation and neo- c
because ot changes in the biosphere
(varying skeletal mineralogy and ter-
mentat ion is facies specific and most
deposits are unlithified. Once exposed
morphism, petrography and geochem-
istry, can be found in compilations by
c
restrial vegetation) and the atmosphere to percolatinq non-marine fluids, all Schneidermann and Harris (1985) , c
(varying PC0 2) through geQIQgic time.
The rates at which mineral transforma-
sediments suffer some dissolution
toqether with variable cementation and
Schroeder and Purser (1986) and James
and Choquette (1988). c
.t ion, dissoiution, early cementation and neomorphism. The effect of organisms Since the changes that take place are
largely chemical, the study of carbonate
c
the formation of karst features occur
[ are strongly influenced by local surface
is localized to the soil zone with the
formation of calcrete and phytokarst. In <!@geoesjs requires both petrograpbk; c
temperature and rainfall.
The Deep Burial. As carbonate
the deep subsurface compaction and
cementation affect all rocks and sedi-
~Emligal an~sis . The basic
relationships are seen fr.om-stamea c
sediments undergo proqresslve burial ments and are commonly accompanied slabs and thin seJ;.tlons.or,acetate -peels
a~y' be ~lJgmented QY scanning
c
and are subjected tQ increasing temper-
ature and pressure during and after lithi-
by neomorphism. Dissolution, how-
ever, appears to be restricted to spe- electron microscopy. Especially useful c
fication, they go through a variety of
liiO'dftications. The important changes
cific situations.
The degree to which carbonate is
are the trace-element concentrations of
strontium, magnesium, iron and manga- c
which occur include mechanical and altered in any of these settings de- nese and the concentration ratios of car-
bon (13C/12C), oxygen (180/ 160) and, in
c
chemical compaction - during which
porosities may be shar ply reduced;
pends upon (1) the cornposltlon and
flux of the waters through the sediment special cases, sulphur and strontium c
cementation by carbonate, ~hate ,
~ilic.a .silicate mmerals; conversion
or rock, and. ~2) the I~ngth of tim~ t~e
rock or stabilized sediment rernams m
isotopes. Cathodoluminesence, in-
duced in carbonate minerals mainly by
c
of metastable forms of CaC03 to low-Mg
A&-
the environment. excitation of reduced manganese
(Mn2+) and allowing differentiation of
c
calcite (often accompanied by other Because cements are progressively
changes such as clay and gypsum dehy- '-added to the rock as it passes from one various zones within carbonate crystals, c
dration); decomposition, as well as bio-
chemical and thermochemical trans-
diagenetic environment to another, the
sequence of alteration can often by
has become widely used in recent years.
Finally, the nature of past fluids them-
c
formation of original organic matter. .I!!fl worked out best by examining the selves may sometimes be ascertained c
dominan tre 'n burial dia enesi::i ~
long-term rec!..Ud.ioo..af..p.Q.r..Q.s.i.tY-tbJ:gJJgh
"Cement Stratigraphy" in detail. from study of fluid inclusions.
c
tllousands of metres of burial. Under
Table 1 Relative importance of diagenetic processes in carbonates.
c
some conditions, however, porosity ap-
pears to be created anew during bur-
fz,) al di enesis through dissolution of
Diagenetic
Process Shallow Tropical
Diagenetic Environment
Deep
c
Sea Floor
Meteoric
Subsurface C
~
arbon ate grains ana-eemenrs. he de-
~ tails 0 t e 1580 litlon process are still Biogenic
Alteration
extensive localized -- E
unclear, but apparently involve the pro-
duction of CO2 by organic compounds Cementation localized extensive ubiquitous C
undergoing thermobiochemical reac-
tions in the presence of other pore
Dissolution -- ubiquitous localized C
fluids. Neomorphism -- extensive extensive (
Diagenetic Pathways. Most car-
bonates, because they sit on the sea
Compaction -- -- ubiquitous (
floor or in reef cavities for a while before
being buried, suffer some degree of syn-
• Neomorphism as used in these articles refers to the alteration of carbonate minerals in a wet
diagenetic environment through processes of polymorphic transformation (e.g., " inver-
C
sedimentary diagenesis. Similarly, most sion" of aragonite to calcite) or recrystallization (e.g., finely crystalline calcite to coarsely C
ancient limestones have been in the crystalline calcite), but not simple pore-space filling .
C
C
c./
( Limestones Introduction 11

C
f
SELECTED REFERENCES Friedman, G.M. and Ali, SA, 1981, Diagene- Milliman, J.D., 1974, Marine carbonates:
c The literature on carbonate diagenesis
is vast - the following texts and papers
sis of Carbonate Rocks: Cement-
porosity relationships: Society of Eco-
New York, Springer-Verlag, 375 p.
Good review sections on techniques and
o together, give the reader a working nomic Paleontologists and Mineralo-
gists, Reprint Series No. 10.
diagenesis of modern carbonates.
Purdy, E.G., 1968, Carbonate Diagenesis:
r overview and introduction to the topic.
A collection of 12 papers on carbonate An environment survey: Geologica

c Amieux, P., 1982, La cathodolominescence:


methode d'etude sedimentologie des
diagenesis which have appeared in the
Journal of Sedimentology Petrology.
Fuchtbauer, H., 1969, ed., Lithification of
romana, v. 7, p. 183-228.
A beautifully presented, wide-ranging
paper on diagenetic environments.
C Carbonates: Bulletins des Centres carbonate sediments, parts 1 and 2: Roeder, R.J., 1983, Carbonates: miner-
Ressources Exploration Prod. Elf Aqui- Sedimentology, v.12, p.7-159, and alogy and chemistry: Reviews in Miner-
taine, v. 6, p. 457-483. p. 163-222. alogy, v. 11, 394 p.
o An excellent overview of cathodolumi- These 2 volumes contain a suite of excel- A number of excellent short papers, with

o nescence - as applied to carbonates,


with good photographs.
lent papers on carbonate cementation.
Harris, P.M., Kendall, C.G. St.C. and Lerche,
superb, pertinent reviews on crystal
chemistry (R.J. Roeder and J.A. Speer),

o Bathurst, R.G.C., 1975, Carbonate Sedi-


ments and Their Diagenesis: Elsevier,
I., 1985, Carbonate cementation-a brief
review, in Schneidermann, N. and
Magnesian calcites (F.T. Mackenzie et
al.), Aragonite-calcite transition (W.O.

c New York, 658 p.


The authoritative text on the subject of
Harris, P.M., eds., Carbonate Cements:
Society of Economic Paleontologists and
Carlson), dissolution and precipitation
(J. W. Morse) and trace elements and
c carbonate diagenesis - very readable
with exhaustive scholarship. Any worker
Mineralogists, Special Publication No.
36, p. 79-96.
isotopes (J. Viezer).
Roehl, P.O. and Choquette, P.W, 1985,
o in the field should have this book.
Bathurst, R.G.C., 1980, Lithification of car-
A succinct overview of carbonate
cements in different settings.
Carbonate Petroleum Reservoirs:
Springer-Verlag, New York, 622 p.
( bonate sediments: Science Progress Horowitz, A.S. and Potter, P.E., 1971, Intro- A series of 35 papers on the geology of
Oxford, v. 66, p. 451-471. ductory Petrography of Fossils: carbonate reservoirs, many of which
An update on research in limestone dia- Springer-Verlag, New York, 302 p. deal extensively with diagenesis.
genesis since 1975. Good photomicrographs of wide variety Schneidermann, N. and Harris, P.M., 1985,
Blatt, H., 1982, Sedimentary Petrology: of limestones. Carbonate Cements: Society of Eco-
WH. Freeman, San Francisco, 564 p. Hudson, J.D., 1977, Stable Isotopes and nomic Paleontologists and Mineral-
A good chapter reviewing carbonate Limestone Lithification: Journal of the ogists, Special Publication No. 36,
diagenesis. Geological Society, v. 133, p. 637-660. 379 p.
Blatt, H., Middleton, G. and Murray, R., An excellent overview and good place to A collection of 21 papers on the petro-
1980,Origin of Sedimentary Rocks: Pre- start when consid~ring the application of graphic and geochemical attributes of
ntice-Hail, Englewood Cliffs, NJ, 782 p. stable isotope analysis to carbonates. cements in all diagenetic environments.
One overview chapter on carbonate James, N.P. and Choquette, P.W, 1988, Scholle, P.A., 1978, A Color Illustrated
diagenesis. Paleokarst: Springer-Verlag, New York, Guide to Carbonate Rock Constituents,
Bricker, O.P., 1971, Carbonate Cements: 421 p. Textures, Cements and Porosities:
Johns Hopkins Press, Baltimore, MD, A variety of different papers on all aspects American Association of Petroleum
376 p. of karst and paleokarst, ranging in age Geologists, Memoir 27, 241 p.
Numerous short articles which together from Precambrian to modern. An excellent reference while doing car-
illustrate the spectrum of cements in car- Longman, M.W., 1980, Carbonate diage- bonate petrography with a good
, bonate rocks, modern and fossil. netic textures from nearshore diagenetic bibliography on techniques and class-
Flugel, E., 1982, Microfacies Analysis of environments: American Association of ification.
Limestones: Springer-Verlag, New York, Petroleum Geologist, Bulletin, v. 64, Schroeder, J.H. and Purser, B.H., 1986,
633 p. p.461-487. Reef Diagenesis: Springer- Verlag, New
Although this is a general text there are A good review of the processes and pro- York, 455 p.
good reviews on diagenesis - and an ducts from nearsurface diagenetic The biological and chemical aspects of
excellent source of information on Meso- realms. diagenesis in modern and fossil reefs
zoic-Cenozoic carbonates. Machel, H., 1985, Cathodoluminescence in are treated in 21 papers.
Folk, R.L., 1965, Some aspects of recrystall- calcite and dolomite and its chemical
ization in ancient limestones, in Pray, interpretation: Geoscience Canada,
L.C. and Murray, R.C., eds., Dolomitiza- v. 12, p. 139-147.
( tion and Limestone Diagenesis, a sym- An excellent overview of the chemical
posium: Society of Economic Paleon- considerations that should be taken into
l tologists and Mineralogists, Special account when using cathodolumines-
Publication, No. 13, p. 14-48. cence.
6 A good introduction to a complex topic. Meyers, W.J., 1974, Carbonate cement Originally published in
Folk, R.L., 1973, Carbonate petrography in stratigraphy of the Lake Valley Forma- Geoscience Canada v. 10 Number 4
the post-sorbyan age, in Ginsburg, R.N., tion (Mississippian) Sacramento Moun- (December 1983)
ed., Evolving Concepts in Sedimen- tains, New Mexico: Journal of Sedimen- Revised 1988
tology, Johns Hopkins Press, Baltimore, tary Petrology, v. 44, p. 837-861.
MD, p. 118-159. A landmark paper introducing the con-
A thoughtful and readable essay on the cept of cement stratigraphy and illustrat-
petrography of carbonate diagenesis. ing the use of cathodoluminescence in
Friedman, G.M. and Sanders, J.E., 1978, carbonates.
Principles of Sedimentology: John Wiley,
New York, 792 p.
A short section on diagenesis.
c
12 Diagenesis Geoscience Canada Reprint Series 4 c
(
c
c
c
c
c
(
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
e
(

Cements fabrics in ooid peloidal grainstone, Stubbs Cay, Turks and Caicos Islands, British c
Bahamas . Sample is from a Pleistocene exposed surface immediately below a Holocene,
eolian, ooid sand dune. Early meniscus cement between grains is blocky, anhedral low
magnesium calcite. Later cement, filling cavity, is randomly oriented rhomb ic . needle and
bladed low magnesium calcite. Enlargement illustrates the complex arrangement of rhomb
c
units within the later cement fabric. Thesub-structure of the bladed crystals is similar to that of c
"Iublinite ' ~ Subaerial-vadose environment. Photograph courtesy of A. Oldershaw (University
of Calgary) . c
c
c
~;;-'2tA.-:.;:.;" ~.
c LJ-'VZO £:(/./ {n <./
1'1 ~ b~aA'1~
LlF" -,.{

( Limestones - The Sea-Floor Diagenetic Environment _ J0J


jVVt l->.. J'l - ~ II:s ) fc:) d r cr« /Q":;' ( 13
_ (.AI,",~o-- _ C~{o~o. k\ c.~ Itr.'J..J' 'VI). ~~
(
s:- e.g. (r l/VIJ M t Q. ). • J

c knowledge would be a powerful tool


fJ flu ~::... n () k{!-t>"w et~
10 cm/1000 years) from the fallout of
o when attempt ing to predict trends of
reservoir lithologies in subsurface
calcareous plankton in the ocean
worldwide. Sediments on the slopes of
o carbonates .
Carbonates lying on the sea floor are
shelves and platforms are mixtures of
shallow-waterand pelagic components.
( affected by a variety of chemical and Whereas shallow-water deposits accu-
o biological processes. Precip itation of mulate quickly and form impressively

o CaC0 3 predominates in shallow tropi-


cal marine environments, whereas dis-
solution is im ortant at nig latitudes
thick carbonate bodies, comparatively
thin pelagic carbonates , because of
their enormous extent covering more
Limestones - The and in deeB..'lolat~. The most important than a quarter of the Earth's surface,
( bIOlogical process is infestation of car- account for over two-thirds of the car-
Sea-Floor Diagenetic
o Environment
bonate hosts by a s~%ctr~ of large ang
small boring organisms Because geolo-
bonate currently being extracted from
seawater (Scholle et al., 1983). Current
o gists are so preoccupied with lithifica-
tion, any pore-lining or pore-filling car-
estimates indicate that between 75 and
95 percent of pelagic carbonate is sub-
c Noel P. James bonate precipitate is commonly called sequently dissolved (Broecker, 1974) at

o Department of Geological Sciences


Queen's University
"cement", whether it acts as a binding
agent or fills a pore inside a grain. Since
the sediment-water interface in the deep
sea (Adelseck and Berger, 1975).
o Kingston, Ontario K7L 3N6 both carbonate genesis and diagenesis
occur within the environment of depo-
In the perspective of geologictime it is
important to recall that carbonate sedi-
c Philip W. Choquette sition, often under identical conditions, ments made up of pelagic organisms

o Department of Geological Sciences


University of Colorado
the line between the two is often blurred.
In this essay we arbitrarily consider all
are largely a Mesozoic and Cenozoic
phenomenon and are insignificant in
Boulder, Colorado 80309-250 processes outside direct biomineraliza- Paleozoic and Precambrian strata.
tion as being diagenetic, even though Vertical Zonation. The general pat-
INTRODUCTION some processes involve actual particle terns of carbonate accumulation have
Diagenesis commonly begins as soon formation. been known for over a century (Murray
as carbonate sediments are formed: Sedimentary particles and cements and Renard, 1891; Murray and Hjort ,
o tests of foraminifers settling onto the are either calcite or aragonite. The cal- 1912). The primary controls on carbon-

o deep sea floor gradually dissolve; living


bivalves are infested w ith boring
cite may be enriched in magnesium up
to about 18 mole% . Calcites are com-
ate precipitation and dissolut ion are
Pea?and wa~r~m peratu re and pres- ~ lJi:
o sponges; cement precipitates in coral
pores just below the living surface.
monly referred to as calcite or low-
magnesium calcite or LMC_(less.tba0.2
sure. Although water pressure in-
~ses in a linear fashion with depth,
o These early changes are in many cases mole% MgC0 3 ) and Mg-calcite or high- water temperature does not. Seawater

o the most critical in the history of a lime-


stone because they both modify depo-
magnesium calcite or HMC (12-18
mole% MgC03 ) . While this has proven
at low latitudes is temperature stratified
and comprises three layers (Figure 1):
o sitional facies and direct the pathways
of future diagenesis. For example - if
a useful separation in the past because
most shallow water components are
a warm, homogeneous, near-surface
mixed layer;!!J.e thermocline, a zone at
crusts of lithified sediment sporadically one or the other, discovery of precipi- rapid temperature decreasEU:l/ith deptb
develop on the surface of a carbonate tates in deeper waters with interme- to around 5°C; and a deep-water zone
sand shoal through precipitation of diate amounts of magnesium (2-12 where temperature is more or less con-
intergranular cement, a new hard sub- mole% MgC03 ) has made the differen- stant to abyssal depths.
strate suitable for colonization by skele- tiation somewhat artificial. Precise determination of the solubility
tal invertebrates is created where none In the following pages, we first sum- of calcite and aragonite in seawater
existed before. This new community of marize our current understanding of has proved to be one of the more elusive
organisms may in turn build reefs - the diagenesis of carbonate sediments quests of low-temperaturegeochemists,
and so, in a very short time , a sand on the modern sea floor, and then and as Morse and Berner (1979, p. 531)
( shoal facies has been replaced by a assess the applicability of these obser- point out, "after 100 years of study
reef facies with no change in the vations to the rock record. the major problem of determination of
environment except partial lithification the saturation state of the deep ocean
of the sediment. The effect of this local ZONES OF SEA-FLOOR remains largely unresolved ". At pre-
cementation will continue as these car- DIAGENESIS sent our understanding rests on the
bonate sands pass through subse- There are two realms of carbonate often conflicting results of laboratory
quent diagenetic environments - the deposition in the modern ocean :' exper imentation, mapping of bottom
unlithified and porous parts will be the, ( 1 ) shallow water, characterized ....Qy sediments, and field observations of
first flushed by new diagenetic fluids;~\l ra idl accumulatin sediments ca. particles hung in open containers at
the cemented, non-porous parts will be t 100 cm/1000 years) ~.hich form mainly various depths in the ocean. These
,. affected more slowly. Thus, if the rela in warm tro u.o.a a d ~J,! bt ro ical envi- data have most recently been synthe-
tive intensity of sea-floor diagenesis ronments; and (2 dee -w !!~ sized by Broecker and Takahashi (1978)
could be tied to depositional facies, this by slowly accumulating sedir:R9Ats-(ca. and Morse and Berner (1979). For a
r
c
14 Diagenesis Geoscience Canada Reprint Series 4 c
c
summary of carbonate dissolution and lysocline", that zone determined byfield lysocline and compensation depth are
c
precipitation kinetics the reader is experiments in the water column, and poorly known. A good practical mea- c
referred to the excellent review by
Morse (1983).
the "sedimentary lysocline", marking
an increase in the amount of dissolution
sure for aragonite saturation is the dis-
solution behaviour of pteropods, small c
In general, near-surface tropical and
subtro pical seawater appears to be
on the sea floor (Berger, 1975). In fertile
regions, near the continental margins in
pelagic gastropods with an aragonite
shell (Berger, 1978). In marginal seas
c
supersaturated with re~m.e.Q.L1P-b.Q!b. particular, the sedimentary lysocline with anti-estuarine circulation, such as c
aragonite and calcite to depths of about
500 metres in the Pacific and 2,000
may rise toward the surface and
become diffuse.
the Mediterranean Sea, Red Sea and
Persian Gulf, pteropods are common in c
metres in the Atlantic (Takahashi, 1975).
Below this supersaturated water, sedi-
But what of sediments on the sea floor
in the several thousand metres between
sediments at all depths, indicating arag-
onite saturation of these waters. At low
c
ments on the sea floor are exposed to the shallow saturated waters and the latitudes in the open ocean pteropods c
more and more undersaturated water
with increasing depth because of
lysocline? Why, if water pressure is
the main control , is there not a gradual
disappear below about 1,500 m with
depth valuesshoaling toward the higher c
increasing pressure and, to a lesser
~temperature. Thus,
but steady increase in dissolution latitudes. On average, the aragonite
com ensfltion..depthTACDTIl:igUl:eJ n~
c
sediments are subjeCtetl to Ilrster and
with depth, and why do the particles
that lie on the sea floor show only shallower by3 kilometres than the CCO, c
faster dissolution rates until finall y a
depth is reached where the rate of . -
scant evidence of corrosion? The
answer appears to be a complex inter-
llYt this maY~rY. As with the CCO, tile
ACD is deeper in the Atlantic than ii1tlie
c
so u Ion IS equal to the rate of sediment play between rates of carbonate accu- Pacif ic because Atlantic waters are c
supglv from above. !3elow this depth,
c alled the carbonate cO,JJJP.ensation-
mulation, kinds and sizes of sedimentry
particles and, perhaps most important,
closer to being saturated for calcite and
aragon ite due to different overall pat- c
oop th or ~(Figure 1), !ill-QaLcite..is-
dissolved. In regions where carbonate
the kinetics of dissolution (Morse and
Berner, 1979; Morse, 1983). In addition,
tern S-.oLdeep_water_c~. In the
northeast Pacific and eastern tropical
c
productivity and resulting sedimenta- orthophosphate, present as strongly Pacific aragonite dissolution begins c
tion rates are high, such as those near
the equator, the CCD is depressed.
adsorbed coatings on grain surfaces, is
an inhibitor of calcite and Mg-calcite (but
right below the mixed layer (500 m)
within an oxygen minimum layer. c
Oceanic Q.CD.for.calcite is now at about not aragonite) dissolution (Berner and Zonation with Latitude. There is a c
~n the Pacific ~~d 5,500 m in
the Atlantic. _and is sfiallowesCiii1he
ri9.Ltb..ea~ifjc.ancld~.e.p-estJRi~ii
"*
Morse, 1974).
T~D is the deRth at whiJ:<ILG.alcite
much poorer understanding of latitude
variations in shallow-water carbonate c
~nt1c. Variations of the CCD in the
dissolution balances deposition; the
other two common seaimenta~ry-car­
solubility. Obvious changes in carbon-
ate sediments are complicated or c
world oceans are discussed in detail by
Kennett (1982). Hills that rise from
bonate minerals, Mg-calcite and arag-
onite, likewise have compensation
masked by the effects of surface cur-
rents, terrigenous sedimentation and
c
abyssal depths up through the CCD can depths. Because there are no signifi· climate, as well as by the fact that out- c
be pictured as "the snow-capped moun-
tains of the deep sea" (Berger, 1975),
cant Mg-calcite plankton the Mg-calcite side the tropics many of the carbonates
c
their lower slopes below the CCD cov- TEMPERATURE °c "10 CARBONATE c
ered by red clays and siliceous ooze,
and their tops above the CCD mantled 0
OF SEAWATER
,0 20 30 0
IN SEDIMENT
50 100 c
with white carbonate sediment.
0 0
c
7
I ZONE OF
Evidence for dissolution can be seen PRECIPITATION
at depths considerably shallower than ",0
-t....'i..'if.
c\,\~'i..
c
the CCD. This gives rise to the concept
of tb!!JYAo.cUoe (Berger, 1968), or depth ZONE OF
c
where evide[lC_e~of.conside.r.able.(selec­
tive) dissolution is first .e n c9M.r.tt~ d .
:l:
~2
:n: DISSOLUTION
AND
c
The lysocline is in general 1,000 m shal- x
.....
PRECIPITATION
c
lower than the CCD and most dissolu-
tion takes place within this 1,000 m
Q.
ILl
Cl 3
DEEP
WATER 3 c
interval. Broecker and Takahashi (1978)
have demonstrated that to within
ll:
ILl m:
ZONE OF
ACTIVE
e
± 200 m the depth of the calcite lyso-
cline can be explained in terms of car-
.....
c(
~ 4 4
DISSOLUTION
c
ZONE OF (
bonate ion concentration in deep :nL NO
waters: the lysocline lies at greatest
5 5
CARBONATE
c
depth where waters with high carbon-
ate ion concentrations extend to the c
bottom.
It should be noted that there is often a
Figure 1 Generalized diagrams illustrating the relative positions of calcite and aragonite
solubilityprofiles in the modern tropical ocean and the variation in temperature with depth. The
c
difference between the "hydrographic major zones of diagenesis are plotted to the right. c
c
c
(

C' Limestones - The Sea-Floor Diagenetic Environment 15


(

C. are relict (Emery, 1968; Ginsburg and skeletons from latitudes above 40° . near the surface in polar seas, are dis-
o James, 1975).
In general, rapid fixation of biogenic
Although the actual removal of carbon-
ate is thought to be mostly by physical
tinguished by wholly biogenic calcite
accumulation showing abundant evi-
o and inorganic carbonate in shallow abrasion aided by maceration, dissolu- dence of corrosion.

o water appears to be limited tothetropics


and subtropics and rarely extends north
tion "opens up" the grains and aids in
these processes. There is no clear evi-
IV. Zone of No Carbonate. Wholly
deep-sea settings, below the CCD
o or south of 30° latitude .Although acorn-
plete spectrum of carbonate skeletons
dence of dissolution on a large scale.
Thus, in shallow-water environments
where no carbonate is accumulating.
It should be stressed that this is a
o is produced in these environments,they
are distinguished by abundant produc-
north andsouth of the tropics conditions
seem to be similar to those below the
generalized zonation and appl ies
chiefly to the open ocean and to associ-
tion of corals and green algae, both of zone of saturation and above the ated shelf-slope and platform-slope
o which are aragonite . Lees and Buller lysocline in the deep tropical ocean. systems. The major part of the following

o (1972)have, as a result, designated this


the Chlorozoan assemblage to differen-
On balance we can roughly differenti-
ate four zones in the modern ocean in
discussion on sea-floor diagenesis is
focussed on Zones 1 and II.
o tiate it from the Foramol assemblage of
temperate and polar seas.The principal
which the conditions for carbonate dia-
genesis are the same (Figures 1 and 2). ZONE I: WARM SHALLOW WATER
o contributors to the cooler water carbon- I. Zone of Precipitation. These are PLATFORM CARBONATES

o ate assemblages are molluscs, foramin-


ifers and bryozoans with echinoids, bar-
shallow tropical to subtropical settings
in which a complete spectrum of skele-
Mineralogy of Precipitates.
Sedimentary particles on \he modern
o nacles and coralline algae often
present. The bulk of these higher latl -
tal and non-skeletal particles of arag-
onite, Mg-ealcite andlor calcite occur,
shallow sea floor in tropical regionscon-
sist of aragonite or calcite or magne-
o tude carbonates are Mg-ealcite or cal- as well as aragonite and Mg-calcite sium-enriched calcite (Mg-calcite).

o
*
cite with rare aragonite, and in mixed- cements. The lower limit of this zone Although some organisms precipitate
layer mineralogies there are lower where seawater becomes undersatu- skeletons of calcite , only Mg-calciteand
amounts of aragonite in colder climates rated with respect to aragonite is about aragonite appear to precipitate directly
(Milliman, 1974). Non-skeletal grains 1,000 m (varying between 500 m and
o (ooids, peloids and lumps) and marine
cements do not generally occur in these
2,000 m depending on the ocean) in the
tropics and shoals to the surface around
from seawater here.
It is still not clear what control
the mineralogy and crystal habit of
cooler waters and are restricted to the 30 0N and 30 0S latitude . these minerals or why both Mg-calcite
tropical zone, although Alexandersson II. Zone of Dissolution/Precipita- and aragonite are so common (see
(1974) has found aragonite and Mg- tion. Shallowtemperatewatershelfset- Bathurst, 1980,for summary). The com-
o calcite cements inside coralline algae tings north and south of about 30° lati- plexities involved as well as the dif-

o nodules in the North Sea where waters


are undersaturated, suggesting strong
tude to the polar regions, which are
characterized by wholly biogenic car-
ferences between experimental results
and natural observations are discussed
o biological influence.
Even though rates of carbonate pro-
bonate accumulat ion (mainly Mg-
calcite and calcite), no intergranular
and debated by Given and Wilkinson
(1985a,b) and Morse (1985). From a
() duction are much lower in cooler latl- cementation, and minor dissolution. thermodynamic standpoint, calcite with
o tudes than in the tropics, carbonates
may locally constitute up to 50% of the
Deep-water tropical slope and basin
settings from the base of Zone I to the
from 2 to 7 mole% MgC03 is the pre-
ferred stable phase in seawater(Berner,
o sediment. Observing the high produc- calcite lysocline are likewise cnarac- 1975). It has been suggested that the

o tivity and lack of terrigenous mater ial in


such areas, however, the amount of car-
terized by local dissolution of alloch-
thonous aragonite and ?Mg-calcite
presence of strongly hydrated Mg2+
ions absorbed onto the crystal surface
o bonate is somewhat lower than might be
predicted - suggesting removal of
components, neomorphism and preci-
pitation of calcite (LMC) cements.
(the Mg/Ca ratio in seawater is ca. 511)
inhibits the growth of calcite, and that
o some portion (Milliman, 1974; p. 105). It III. Zone of Active Dissolution. Deep- the Gibbs free energy needed to dehy-

o is common to observe the effects of


dissolut ion in both calcite and aragonite
sea settings between the calc ite
lysocline and the CCD which may rise to
drate the ions and form aragonite is
lower (Bathurst, 1968). On the other
o ~
hand, it is also known that calcite crys-
tals may precipitate and absorb large
o . : \...

~'\'\~ 70 60
NORTH

50 40 30 20
LATITUDE

10 0 10 20 30
SOUTH

40 50 60 70 quantities of Mg2+ as they grow


(Berner, 1966). The Mg-calcites so
6
\~ :\'~ mnTTfm~W~w'm7TI77J
[7'
formed are in non-exchange kinetic
C lCJ-
equilibrium with seawater.
The main conclusion of much experi-
mental work and observat ion of natural
:x:
l- systems appears to be, as summarized
n. 4 -
w
o by Mackenzie et al. (1983) and echoed
5 - by Given and Wilkinson (1985a,b), that
ZONE n
6 - ' - - - - - - -- - - - - - - - - - - - - -- - - ' the MgC0 3 contents of magnesium cal-
cite precipitated from seawater, includ-
Figure 2 Variations in the different zones of sea-floor diagenesis in the modern ocean. ing organism skeletons and cements,
c
16 Diagenesis Geoscience Canada Reprint Series 4 c
c
are related to temperature and CO~' Petrography of Precipitates. entirely filled. Thus, the addition of Mg-
c
concentration of the water. The amount Magnesium calcite (Figure 3). calcite micrite cement may, in the pro- c
of MgC0 3 in the calcites increases with:
(1) increasing temperature (Burton and
Magnesium-enriched calcite precipi-
tates generally contain a range of
cess of lithification, change the texture
of a grainy sediment from a grainstone c
Walter, 1987), (2) increasing carbonate between 12 and 19 mole% MgC03. The to packstone . (
ion concentration (Given and Wilkin- crystals (trigonal CaC0 3) precipitate Of interest here is the ubiquitous
son, 1985) and (3) increasing Mg/Ca
ratio of the fluid (Mucci and Morse,
either as tiny rhombs less than 4 micro-
metres across (micrite-size) or as fibres
association of micro-peloids, ranging in
sizefrom 20 to 100 mlcrornetres on aver-
c
(
1983). It is also clear that the rates of a few tens of micrometres long. Al- age, with micrite cement. This is the
fluid flow are important. Mg/Ca ratios do
not seem to be sufficently variable in the
though iron can be accomodated in the
calcite crystal lattice, microprobe analy-
structure grumuleuse of Cayeux (1935),
a fabric of numerous clots or vague
c
modern ocean to account for observed sis of these cements reveals no detect- small peloids (aggregates of Mg-calcite c
trends in mineralogy. Since tempera-
ture and carbonate ion concentration
able Fe2 + . Probably th is is because
there is very little iron in seawater and
rhombs), surrounded by micr ite and
microspar. While these may well be
c
are covarient in the ocean it is difficult to
determine which is the most critical
most precipitation takes place under
oxidizing conditions where any iron pre-
sedimentary particles of uncertain ori-
gin, the persistent association has led
c
factor. The importance of temperature sent is the Fe3 + state, and the partition Macintyre (1983) and Marshall (1985) to c
has been stressed by Burton and Walter
(1987) who confirm that the growth rates
coefficient is close to one (Richter and
Fuchtbauer, 1978). Because strontium
suggest that the peloids are the resutrof
sp-ontaneous nucleation and preciRita-
c
of aragonite versus calcite increase with its relatively large ionic radius fits ·tion-ofMg-calcite in the water column C
with increasing temperature. Aragonite
has about the same solubility as Mg-
uneasily into the calcite lattice, Mg-
calcite rarely contains contains more
Which- men settle out of suspension.
Ttiis precipitation may be eIther i:lirector r
calcite with ca . 12 mole% MgC03 (WaI-
ter and Morse, 1984; Walter, 1985).
than a thousand ppm Sr2 + (Kinsman,
1969).
organically induced. Chafetz (1986) has
found that the finely crystalline nucleus
C
Seawater has been described as Micrite-size crystals. This is the most contains rods of bacteria , suggesting C
"a dilute electrolytic organ ic soup" so common type of Mg-calcite cement that the crystallites originated as a pre-
that prediction of any reactions that occurring in awide variety of sediments . cipitatewithin and around active clumps C
lead to precipitation must also take into
account the large amount of organic
It ranges from thin rinds only tens of
micrometres thick around particles and
of bacteria and that the vital activity of
the bacteria influenced precipitation of
C
material. That organics affect precipita- algal filaments to complete fillings of the calcite . C
tion is clear, but their role is ambiguous pore spaces. Although micrite is easily Fibrous crystals. This cement (Figure
(Mitterer and Cunningham, 1983). Inthe seen as cement when encircling parti- 3) is generally found as isopachous C
first place, all particles are coated with
layers of organic molecules which
cles or lining ooids, it is difficult to dif-
ferentiate from lime mud if the pores are
encrustations up to several hundred
micrometres thick.The elongatecrystals
C
inhibit nucleation, allowing seawater to C
maintain supersaturation (Suess, 1970, SHALLOW MARINE CEMENTS
1973). At the same time, organic matter
C
extracted from ooids is similar in com- C
position to that found in skeletons (Mit- MAGNESIUM CALCITE ARAGONITE
terer, 1971). These proteins and humic C
substances contain carboxyl groups
with similar geometry and charge as the
C
carbonate anion. Thus, there may be C
substitution by the anion for the organic
group, and so crystals may be nucle-
MICRITE
C
ated and grow by epitaxy. The presence
of more 13C in marine cements than
expected if they were completely
Ye.,{o·, ~ ~
Ctl l-WV"·
11 \~ (<t(ll ~
OOp/)
IlIl MESH OF
NEEDLES
C
C
inorganic precipitates (Milliman and
Muller, 1977) also points to some sort of 000" c
involvement by organics.
~ Although in general Mg-calcite
e
r'\
appears to be the most widespread
marine cement (James and Ginsburg,
c
1979), aragonite is common in waters of
slightly elevated temperature and salin-
ity. Finally, in ooids it appears that the FIBROUS TO BLADED
BOTRYOIDAL c
degree of seawater agitation mayfavour RINDS 10 -.r~( erA (D ""8 ~
the precipitation of one mineral over .£'7 1-(e.' <. C--l/ '~ r:-r~.(A Ci..- 1_n
another (Davies et sl., 1978). Figure 3
/)/c<-, /-
Different types of modern sea-troor carbonate cements. I 1t:lV\.L
L
t.( V'
1'oW)
/'<-.0 II, ~ II-./'
C
J
rd.r
o
J~)
U,-"tn.f
/h-CJUl tJ,"""
,
I
C
'7 f' ·o /11,R .I ~/

c
l
( Limestones - The Sea-Floor Diagenetic Environment 17

c are either nucleated picket-fence style increasin g organics favouring nanno-


flO C
tures" in the form of 0180/160 and
( on the substrate or located at intervals, J1,rains. The cements are reviewed and ~otoPic ratios as well as minor
cation (e.g., Sr2+, Mg2+, Na +) con-
o and grow as small spherulites which
quickly interfere with one another as
illustrated in a recent article by Sand-
berg (1983). Strontium isthe majortrace!J centrations (Viezer, 1983). Many ana-
o they develop. The spherulites are often
arranged in tiers in the cement rind.
element in a'ragonite whose orthorhom-
bic structure accomodates it easily and
lyses have been done on carbonate
sediments and on many of their more
c Blocky or equant crystals. These cement crystals usually carry about common constituents, such as ooids,

o small crystals, ranging in size from 20 to


50 micrometres, are not common as
shallow marine precipitates, but do
8,000 to 9,000 ppm, as do most arag-
onite skeletons (Kinsman, 1969; Bath-
urst, 1975). The major exceptions are
calcareous green and red algae, corals,
brachiopods, molluscs, lime mud, etc.
(Figure 4). Milliman (1974), Bathurst
occur locally in both reefs and hard- aragonite molluscs which contain (1975) and Morrison and Brand (1986)
o grounds. between 4,000 and 1,000 ppm Sr2+ , have summarized many of these iso-

o Epitaxial crystals. Although particles


of echinoderm skeletons, composed
The needles occur in a variety of dif-
ferent habits (Figure 3): (1) Isopachous
topic data on Recent marine carbonate
sediments including the pioneering
o generally of a single crystal of Mg-
calcite, are common elements in many
rinds, particularly common in ooid and
skeletal sands and as epitaxial growths
work of Gross (1964).
Though much of the spectrum of
o modern carbonate sediments, the on aragonite substrates such as corals, marine cements and cementation pro-

o development of marine epitaxial Mg-


calcite cement on these grains has not
green algae and gastropods. (2) An
intergranularmesh of crystals nucleated
cesses is poorly understood, enough
isotopic data has been gathered to sug-
o yet been reported. The closest occur-
rence is the presence of epitaxial crys-
randomly on grain surfaces and grow-
ing in a variety of directions into a void
gest some general relationships. ~
know most about cements being pre-
o tallites developed on cores of echino- until the void is completely filled by an cipitated in modern sediments and reefs

o derms in ooid cortices (Marshall and


Davies, 1975).
irregular growth of crystals or crystal-
lites. (3) Botryoids, which range in diam-
at low latitudes, in warm shallow-shelf
and platform setti nqs. These cements
o Aragonite (Figure 3). Aragonite eter from tens of micrometres to cen- have relatively heavy, 180-enriched

c (orthorhombic CaCOa ) precipitates are


either microcr ystalline or needles a few
timetres, sometimes developed in
coarse carbonate sands but most spec-
oxygen-isotopic compositions of 0 to
+ 3%0 (Gross, 1964; Shinn, 1969; Milli-
o micrometres or tens of~icrometres
long. Loreau (1982) separates these
tacular in reef cavities.
Isotopic Composition of Precipitates.
man, 1974; James and Ginsburg, 1979),
and their 13CS are heavier (ca. + 2 to
nannocrystals, from largest to smallest, When CaCOa is precipitated from sea- + 5%0) than would be expected had they
into needles (generally cements), water - whether in calcareous skel- been precipitated in isotopic equilib-
baguettes (generally in the ooid cortex) etons, as non-skeletal grains such as rium with seawater ( + 2.0 to + 2.5%0 at
o and nannograins, with increasing tur-
bulence favouring needle formation and
ooids, or as marine cements - it ac-
quires characteristic chemical "signa-
25°C; Lloyd, 1971). Specifically (Fig-
ure 5), relative to calcite equilibrium
o compositions, aragonite cements are

o enriched by 1.0to 1.4%0 013C and 1.5to


2,0%0 018 0 while magnesium calcites
o +6
,------,---,----,---,-----, ..
o ARAGONITE

o +4

o o
-e
o
o
o ~ +2
z
Seds.

oCD
0' a:
cl
u OI--------------i----------i~.-:.:--1-~~-_t
MAGNESIUM
...---!
SEDIMENTS 8
// /
CALCITE
r:
SKELETONS, Recent,
Shallow Warm Water
II '
\ / .,
8 \
,' ....... _,,'"
-2 ,,///
/

-2 -, ., '2 +3
OXYGEN i "0 ('M)

Figure 5 Isotopic composition of aragonite


Figure 4 Cross-plot of carbon versus oxygen isotopic compositions for recent sediments and and Mg-calcite cements in modern reefs from
component particles, and for buried chalks. PDB-1is the isotopic standard in this diagram. Data Bermuda, Enewetak, Bikini and Belize.(Modi-
are from Gross (1964), Anderson and Schneidermann (1973), Milliman and Muller (1977), ~ fi d from Gonzalez and Lohmann, 1985).
Schlager and James (1978) and Rao and Green (1982). V fa..e n /L, (. 'df~ C O\.~·
--
X/pV:"'J
( ~ fit. ( I~
(<(
~.~ Ill"~5yfl--f ..
C) It~ ~'/i Q M' .... ~6.J::O;......,.-.-r-rN~"""r,--.-
I of, eQ

('PIJ-,~0 {h( y":;r'l 1 ,$'1 LI ~ t I


t..~tI.,!VV!J.:
c
18 Diagenesis Geoscience Canada Reprint Series 4 c
c
(average 16 mole% MgC0 3) are en- Loreau, 1982), although Mg-calcite cipitates lining chambers and other
c
riched by 0 .3 to 0.4%0 <5 13C and 1.8 to ooids (Marshall and Davies, 1975) and pores inside skeletal elements (Alex· c
1.9%0 <5 180 (Gonzalez and Lohmann,
1985). Because of the consistent frac-
even bimineralic ooids (Land et al.,
1979) do form locally.
andersson, 1978; James et al., 1976)
and as precipitates in micro- and macro- c
tionation relative to predicted composi-
tions it is clear that the cements do not
Although there is compelling evi-
dence that the lime mud found in many
borings. Thus, it is not unusual in the
fossil record to find grains exhibiting
c
represent equilibrium precipitates. shallow marine settings IS mostly bio- good evidence of internal ssa -noor c
Since the aragonitic thalli of calcareous
green algae and the Mg-calcite of mic-
genic in origin (Stockman et aI., 1967;
Weumann and Land, 1975), some may
CaC03 precipitation, yet showing little
or no indication that they were actually c
rite rims produced by endolithic algae
also have heavy <5 13Cs, dominantly of
be due to direct precip itati on. The cemented together in the sea-floor c
+ 2 to + 6%0, several workers have pro-
clouds of aragonite crystallites or "whit-
ings" seen in many shallow tropical
environment.
Between Particles. This type of c
posed that these groups of algae are
" involved" if not directly responsible for
EWvironments are commonly thou ght to
be mud derived from benthic sources
precipitation is the least common in the
sea-floor environment but the most
c
the origin of marine CaC0 3 cements stirred up by feeding fiSh - yet in some important geologically because it is c
(Lloyd, 1971; Schroeder, 1972; Moore,
1973; Milliman and Muller, 1974). Bio-
cases they may be products of sponta-
neous precipitation. In the Persian Gulf,
"rock-making" cement.Thuslimestones
may be formed soon (tens to thousands c
logically mediated precipitation should
result in isotopically depleted carbon-
for example, there are few aragonitic
~Igae~ yet numerous whitin gs and mu ~
ofyears)after deposition ifconditionsare
right in the environmentof accumulation
c
ates due to incorporation of metabolic mud , and many fish . While Loreau (Figure 6). The habitats of these inter- c
CO2(Viser, 1983), yet cements depleted
in 13C and 180 are not known from shal-
(1982) suggests, on the basis of Sr2+
and Mg2+ contents, that both Persian
granular cements are varied.
(1) Platforms. The most desirable c
low marine environments.
I/t...- In any event, marine cements in mod-
Gulf and Bahamian aragonite needle"
muds are likely inorganic precipitates ,
conditions for interparticle cementation
appear to be water turbulence and sta·
c
~ern warm/shallow environments can be Ellis and Milliman (1985) found thattlTe- bilized sediment. Both conditions are c-
clearly differentiated isotopically from
Late Cenozoic meteoric vadose to
suspended sediments in the Persian
Gulf and..Bed-Sea...ar:.ELbl..ogenic and
met on the insides of reefs, especially at
or near the platform margin (Ginsburg c
shallow-phreatic cements, and the evi- detrital. and Schroeder, 1973; James et al., 1976; c
dence is accumulating that these dif-
ferences survive, though often much
While most readers will agree that we
are stretching the concept of sea-floor
Macintyre , 1977 ; Aissaoui et al., 1986)
or on the windward sides of platform c
reduced, in the face of complex diage-
netic histories spanning tens to hun-
diagenesis by including these sedi-
ments, we have done so to place the
reefs (Marshall, 1986). Likewise, sand
shoals near the platform edge are
c
dreds of millions of years. whole topic in context. likely locales, but here most lithification c
Precipitated Particles.
Perhaps the most important precipi-
Style of Cementation.
Inside grains and skeletons. This
takes place when the sediments are
at rest inside the sand shoals or bound c
tates in terms of the amount of CaC0 3
removed from shallow seawater are
type of precipitate, found inside parti-
cles and/or skeletons, is the most wide-
by micro-organisms in sheets (Dravis,
1979) or stromatolites (Dill et al., 1986).
c
ooids. They may have a cortex of tan- spread CaC0 3 "cement", occurring In contrast, muddy lagoonal sediments c
gentially or radially oriented crystallites.
In the modern ocean the overwhelming
even in grains still rolling around on the
sea floor. The cements occur between
are rarely Iithified, probably because of
sluggish water movement, continuous c
majority are aragonite (Simone, 1980; silt-size particles inside peloids, as pre- bioturbation and general reducing
c
c
ZONE I • : : • • • • ~ . .. . '0 .'1. ';,.
..... . ..:,.....
~ ,,', -.-.. '. c
100'S
to ' :_ .0. ; : : :. ;: .;:.•..: v-
c
1000'S
of meters
DEEP BASIN SHALLDW IPLATFORM or LAGOON I c
MARGIN
c
ZONE ]I
.' ~. , 0, . ," , ', : . , :', ' : •• • ••
L-::.'-='-'-' sANDSHQAls
extenSive
hardoroundS
or
hardQrounds

REEFS
SAND SHEETS - sporadic lithification or
extensive hardgrounds
REEFS- sporadIC lithIfIcatIon
SANDYBEACH
beachrock e
Carbonate ....... ..;.' pi '" of sand extenS ive MUDDYTIDAL
Sediment '" : "" " and limestone cemen tat ion MUDDY LAGOON - no cementation FLAT
Lysocl ine- blocks
hardgrounds In upper
ZONE ill port crusts, dolomIte
- - CCD
ZONE IS[
-- no
DEEP SEA Carbonate ~
;-' REEF MOUNDS
eJlU!ns iwe c
I~~~~:::='ii=-~)~ c
cementation
neomorphism

Figure 6 The locations of sea-floorprecipitation and neomorphism on a shallow carbonate platform and in adjacentdeep-water settings. In a/l .
of these habitats, most sediments are unlithified. l
('.
Limestones - The Sea-Floor Diagenet ic Environment 19

c. conditions . Strandline sands also are


( commonly cemented but this may notbe
entirely due to reaction with seawater.
G Even though the majority of sediments
o on shallow carbonate platforms are not

o cemented, when viewed in total there


appears to be a facies preference for
precipitation.
(
While this generalization may hold
c true for muddy shelves and platforms,

c cemented crusts or hardgrounds (Fig-


ure 7) are common in extensive sand
sheets on parts of the Bahama Banks
(Taft et a/., 1968), wide gently dipping
shelves such as off the Trucial Coast in

c the Persian Gulf (Shinn, 1969),and par-


tially enclosed embayments such as
Shark Bay, Australia (Read, 1974). Lithi-
fication is most intense at the surface
and decreases in intensity downward,
generally ceasing within tens of cen-
timetres below the sediment-water
interface. As Wilkinson et al. (1982)
point out in a discussion of fossil hard-
grounds , the processes of lithification
may be quite different between plat-
form-margin reefs which have large
Figure 7 An irregular submarine hardground (between 129 and 128 em on the tape) cavities and are subject to strong cur-
developed in Lower Cambrian ooid limestones of the Forteau Fromation, western Newfound- rents or waves moving large volumes of
land . The photomicrograph illustrates the truncated ooids and cements at the hardground
normal seawater, and non-reefal sands
surface (arrow indicates location; scale bar 0.5 mm).
where current velocities are reduced,
pore volumes small and communication
with surrounding waters limited.
(2) Shallow enclosed basin. In rela-
tively shallow basins such as the east-
ern Mediterranean and the Red Sea,
where there is anti-estuarine circulation
and warm waters extend to the seafloor,
basin-floor sediments are locally
cemented by Mg-calcite and occa-
sionally aragonite to form crusts
(Gevirtz and Friedman, 1969; Milliman
and Muller, 1977).
(3) Slope and deep basin. The ocean-
facing slopes of shelves and platforms
r:
illustrate a range of Iithified sediments.
The top of the slope, which generally
comprises deep portions of the mar-
ginal reef and forereef, locally exhibits
extensive cementation (James and
~ G i n s b u rg , 1979;Land and Moore, 1980).
gementation seems to die opt with
increasing water depth so that below,
300 m OI-SO ha.J:dgrQullds-give way
first to nodules alliLt b~ILto unlithified
~e dime ot (James and Schlager, pers.
Figure 8 A debr is flow from the Ordovician part of the Cow Head Group , a carbonate slope
deposit in western Newfoundland, illustrating the effects of multi-generation sea-floor cemen-
observ. , 1979; Mullins et al., 1980).
tation. The tabular clasts are fragmented thin-bedded lime mudstones that were lithitied.on the These partly to completely lithified
slope before being eroded and incorporated into the flow. The boulders of tabular clast breccia slope sediments are commonly subject
to the left of the hammer and at upper right were debris flow deposits lithified on the sea floor to failure and become clasts in gravity
before being incorporated into yet another flow. Photograph, M. Coniglio. flow deposits (Figure 8).
(
20 Diagenesis Geoscience Canada Reprint Series 4 (
(

Hardgrounds are common off the have been redeposited as sediment equant, bladed and radiaxial fibrous cal-
C
western Bahama Banks where the sea gravity flows. Cementation in shallow- cite, both clear and inclusion rich. In Cre- r
floor is swept by the Gulf Stream. In water temperate carbonates appears to taceous limestones the cements are
depths of 600 00 or so, Iithified mounds be limited to prec ipitation within lntrapar- medium to coarsely crystalline (100-300 C
(lithoherms) formed by numerous
superimposed crusts and populated by
ticle pores (Rao, 1981) and there are to
date no reports of sea-floor neomor-
micrometres) equant spar.
These calcites contain low to inter-
C
deep-sea ahermatypic corals and cri- phism.ln contrast, in deep-water tropical mediate amounts of magnesium , in C
noids rise 50 m or more above the bot- settings where the sea floor lies within accordance with the experimental re- (
tom (Neuman net al., 1977). The cement the thermocline or just below it, waters sults of Fuchtbauer and Hard ie (1976)
in these structures is Mg-calcite.
Below these depths (Figure 6) is the
are close to or below aragon ite satu ration
but supersaturated with respect to cal-
and BurtonandWalter(1986)which indi-
~e that calcites precipitated from
C
transition zone where water tempera- cite. Thus, a situation is created similar waters of decreasing tem r on- C
tures decrease rapidly in the thermo- to that in meteoric environments (see tarnpro essrve y less magnesium. The
cline and waters at the sea floor pass James and Choquette, this volume) in l inely crys talffiie calcite cements in C
from Zone I (precipitation) to Zone II
(dissolution and precipitation).
which the metastable carbonates have a
high "diagenetic potential" to alter to
Bahamian peri platform ooze contain
3-5 mole% MgC03 while the radiaxia
C
Neomorphism. calcite through dissolution and precl- calcite cements from Enewetak contain C
On the shallow tropical sea floor, when pitation . There are relatively few docu- 5.0-11.6 mole% MgC03.
aragonite and Mg-calcite are precipi- mented cases of this diagenesis, be- Neomorphism. C
tated they appear to remain I r.ge.ly cause of the great difficulty in studying While some aragonite pteropods are I C
unchange untl a fected by waters of a such sediments in waters 100s to 1000s dissolved, others are partially miCj
radicallyaTferen character. Neverthe- of metres deep. ritized. There is also selective alteration C
less, there are some reports of re- (1) Holocene fore-reef limestones off of Mg-calcite allochems, e.g., some for-
crystallization: Mg-calcite foraminifers Jamaica appear to be undergoing local aminifera illustrate crystal enlarge-
C
and coralline algae altering to aragonite neomorphism (Land and Moore, 1980). ment. C
(Murray, 1966; Kendall and Skipwith. (2) Pleistocene periplatform ooze in Isotopic Compositions.
1969; Purdy, 1968); aragonite cements the Bahamas is lithified by dissolution While the 0'3C values for lithified Baha- C
partially replacing aragonitic mollusc
shells (Shinn, 1969); parts of aragonitic
and reprecipitation when exposed for
long periods as vertical erosional valley
mian peri-platform ooze in the Tongue of
the Ocean are roughly similar to the
C
cements and skeletons changing to Mg- walls in isolated troughs (Schlager and values from shallow water precipitates, C
calcite (Alexandersson, 1972; Scherer, James, 1978) or buried in the shallow the heavier oleo values clearly ind icate
1974). These occurrences seem to be subsurface (less than 30 00) on ocean precipitation from cold ocean waters C
rare but do point out again the subtletie-S.
governing prec iRit at ion of different
facing slopes (Mullins et et., 1985) .
Metastable components in carbonate
(Figure 4). The isotopic record of the
radiaxial and equant calcites is, how-
C
cac 0 3 phases and tell us that the pos- turbidites are also altered in a similar ever, unclear. These are clearly marine C
Sibi lities fo r ne-o.mar.pfiiSii'CCti5-ex.lSf; fashion (Gomberg and Bonatti, 1970). precipitates but their isotopic composi-
although they ma~ not be co m!J.lQD.J.o. (3) Relict sediments on seamounts tions do not confirm precipitation from C
today's sbaIlQW.S.e.as._ are altered when exposed and win-
nowed for IQngperiods (Milliman, 1966).
cold waters. i
The importance of this deeper water
C
ZONE II: TEMPERATE WATER (4) Cretaceous to Miocene shallow neomorphism in the modern ocean is C
SHELVES, TROPICAL CARBONATE water limestones which have subsided difficult to ~~ at present. It is
SLOPES into deep water by vertical platform localized to areas hich receive meta- C
Perhaps the single most intriguing accretion suffer dlssolutlon and calcite stable sediments from platforms. In C
advance in our understanding of sea-
floor diagenesis since this article was
first written (James and Choquette.
1983) has been the confirmation that
fabric-selective dissolution, calcite
precipitation (Saller, 1985; Freeman-
Lynts et aJ. , 1986).
Di~owtron.
Aragonite appears to be the only mi -
j
eral undergoing dlssolutton, resulting i
most of the deep ocean, where sedi-
ments are composed of calcite plank-
tonic organisms, there is little "diage-
netic potential". In the Paleozoic when
there were virtually no planktonics and
C
C
(
cement precipitation and calcitization of
metastable carbonates do take place in
partial to complete fossil molds.
Precipitation.
all deep-water carbonate sediments
including lime mud came episodically c
some cool Qcean water 89tliR§s. Cool-
water environments occur in two
All of the precipitates are calcite. In deep
water Bahamian muds the crystals are
from nearby platforms or shelves, the
times between sedimentation events
e
locales; (1) in shallow temperate en- blocky calcite, 2-4 micrometres in size, as equid have been periods of recrystalliz-
vironments where carbonate sediments cement QvergrQwing coccoliths, as druse ation and cementation by calcite on the
are dominated by the foramol assem- in foraminifera chambers, calcispheres, sea floor. "-
blage (Mg-calcite and calcite); (2) and the molds of pteropod shells. Calcite (
in deepwater, along the margins ottropi- also precipitates as epitaxial overgrowths ZONES III AND IV: DEEP BASINAL
cal carbonate platforms and on the on echinoid particles. In MiQcenereef car- ENVIRONMENTS
tloors of intervening basins where shal-
low water sediments of the chlorozoan
bonates intergranular pores, sponqe bor-
ings and aragQnitefossil molds are IQcally
For deep-water environments, numer-
ous studies confirm that very little dis- c
assemblage (araqonite and Mg-calcite) lined with crusts, 0.05 to 2.0 moo thick, of solution occurs as particles settle c
(
c
c
(
Limestones - The Sea-Floor Diagenetic Environment 21

o
C' through the water column; most carbon- death, filling of their holes by fine sedi- (Zankl and Schroeder, 1972;James and
o ate is dissolved at the sediment-water ment and/or cement. Ginsburg, 1979; Land and Moore, 1980).

o interface.
If the sea floor is overlain by well-
Particle Alteration.
On a microscale this process involves
The end result, however, is the same: a
skeletal-rich rock is transformed by sev-

o oxygenated water, as is the case in most boring by endolithic algae or fungi into
sand-sized particles. Algae, mostly
eral generations of alteration into a
muddy limestone and much of the ori9.!:..

--
modern oceans, then burrowing allows
( mixing of interstitial and overlying blue-green and green, appear to be JiaL texture is lost.
waters, and thus dissolution may take most effective in the upper part of the
( place some centimetres below the sedi- photic zone to depths of about 70 m STRANDLINE DIAGENESIS
c ment surface.
::::J.t- If euxini c ~nditions prevail and the
(Budd and Perkins, 1980). Fungi extend
to depths of 500 m and more, whereas
Diagenetic processes that characterize
the sbaU~GfiiiOllQor iiIso pre-
( ' \ ~verlying waters are CO2 rich, corrosion heterotrophic algae and bacteria occur dominate in the intertidal and supratidal
may take place on the sediment surface. to abyssal depths (Friedman et a/., zones.gHere the environment IS more
Dissolution ceases once the carbonate is 1971). Infestation appears to be most complex: (1) instead of a simple rock-
buried just below the surface, because active (Kobluk and Risk, 1977) when water system the setting is three-phase,
an increase in alkalinity within the sedi- grains are at rest in lagoonal or other on- rock-water-air; (2) freshwater flow from
ment is brought about by bacterial sul- shelf settings. land extends seaward out underneath

c phate reduction (Berner, 1971). Carbon-


ates may not suffer dissolution in euxinic
In shallow tropical environments
where precipitation is dominant (Zone I)
the shore, with the water table at or just
below the strandline sediment surface;
basins or on slopes where the oxygen- the vacated holes of endoliths are filled and (3) the waters themselves are com-
minimum zone impinges on the sea floor. by Mg-calcite and/or aragonite cement monly mixtures of marine and meteorip
Although corrosion surfaces have been (Margolis and Rex, 1971; Alexanders- fluids. __ £r() /),/.1- , W/VJ t::j"w47
reported in limestones of basins inter- son, 1978).If the numerous generations Beaches. ~ 10. (er.R.cll1~{
preted as rather restricted (e.g., Lind- of boring endoliths are restricted to the The most com ffl6~ifestation of
strom, 1979), signs of dissolution grain margin, a rind of microcrystalline strandline precipitation is beachrock-
beneath such surfaces appear to be Mg-calcite or aragonite called a "micrite layers of cemented beach calcarenite
extremely rare. In fact, under the right envelope" (Bathurst, 1966) develops. (Figure 9) that dip seaward at the same
conditions carbonate precipitation will The formation of these envelopes is attitude as beach sediments and are
occur, the chemistry of which is dis- often critical to grain preservation in composed of the same grains as the
cussed by Hesse (this volume). later diagenetic environments. beach sand, which can be anything from
Summary. If infestation is intense and prolonged carbonate to quartz to volcanic litho-
In summary, there is a clear zonation in the entire grain may be transformed to clasts; good reviews are to be found in
,. diagenesis along the margins of tropical microcrystalline Mg-calcite or arag- Stoddart and Cann (1965)and Milliman
carbonate platforms facing deep water onite, with little trace left of the original (1974). Some tropical. intertidal zones
(Figure 6); parts of shallow water reefs structure (Kendall and Skipwith, 1969). are all beachrock, others have only scat-
and sand shoals are commonly lithified This pervasive micritization is par- tered layers, and many are without it.
early by aragonite and Mg-calcite, as ticularly common in grapestone lumps Strata generally are localized to the
are the adjacent fore-reef sediments (Bathurst, 1975) and in stromatolites intertidal zone extending up into the
(Zone I); .lithification decreases down (Logan, 1974). These "diagenetic pel- zone of wave splash and disappearing
.§lQp.e, as the waters become cooler, oids" are in some instances difficult if seaward, landward, and with depth into
grading from pavements to nodules to not impossible to distinguish from fecal unconsolidated sediment. The beach-
little cementation; in cold wate..!§., which pellets or Mg-calcite cement aggre- rock may be present as scattered nod-
,..
are undersaturated with resRectto arag- gates. As a result, it should be stressed ules, isolated slab-like layers, or whole
onite, dissolution of the metastable that the term "peloid" applies to grains thicknesses of beach sediment, gener-
sediments and precipitation of calcite, that may have had very different origins ally developing a few centimetres below
resulting in cementation, may occur but look the same. the sediment surface.
(Zone II); in very cold deep waters most Outside the tropics and in deeper water The surface of the beachrock is com-
(Zone III) or all (Zone IV)ofthe carbonate (Zone II)infestation is often just as intense monly pitted and bored and exhibits dis-
is dissolved. but the holes are not filled because of the solution basins or potholes. In cross-
lack of precipitation and so the grains are section beachrock is well laminated and

or: BIOLOGICAL ALTERATION


Even though neomorphism sensu
gradually broken down into smaller parti-
cles (Alexandersson, 1979).
the base of each layer is sharp. The rock
is characteristically jointed into blocks
strictu is not a common process in shal- Limestone Alteration. and textured by cracks and channels.
low-water carbonates, sedimentary Voring also occurs on a macroscale with Erosion of rock slabs and reworking dur-
particles and rocks do undergo drastic ~ 'sponges, bivalves and polychaete ing intense storms leads to conglomer-
alteration to micrite or mudstone worms being the excavating organisms. ates or ramparts of beachrock clasts.
through a combination of biological and Particularly common in reefs and on The grain-size of the sediment ranges
chemical processes. The mechanism hardground surfaces, the cavities cre- from sand to boulders.
involves infestation of the carbonate ated by these larger excavating inverte- Induration varies from loosely ce-
host by one of a variety of boring or Qrates may be filled with fine sand- to mented sand that can be disaggre-
endolithic organisms and, after their
-silt-sized sedirrumt,and/or .ceme.riC:. gated by rubbing to well-lithified rock
c
22 Diagenesis Geoscience Canada Reprint Series 4 c
c
that can be broken only with a hammer. beaches predominate, but the rate and cite. In the more seaward channel belt,
c
Commonly the surface is hard and the intensity of peritidal diagenesis appear crusts are peloidal sediment without c
inside soft. Cements are aragonite or
Mg-calcite with the same spectrum of
to be functions of climate . On humid
tidal flats, as typified by the Bahamas,
filaments cemented by Mg-calcite mic-
rite (and often containing dolomite) in c
fabrics as on the sea floor, but micro-
crystalline aragonite cement is par-
cemented crusts are relatively rare.
Only a few centimetres thick (Figure
which cracks and fenestrae are filled
with acicular to bladed aragonite
c
ticularly common (see numerous arti-
cles in Bricker, 1971). In some localities
10), they are found just above the
normal high-tide mark. In the inland
(Hardie, 1977).
On arid tidal flats, such as those
c
these cements have a pendulous or marshes crusts are composed of algal along the Trucial Coast of the Persian
mini-stalactite orientation, signifying
vadose precipitation in an air-filled
filament molds encrusted with Mg-cal- Gulf (Taylorand lIIing, 1969)and around c
void. c
Beachrock forms at surprisingly
rapid rates on the order of years to c
tens of years, so that today coins, bot- c
tles, skeletons and other artifacts are
commonly found in beachrock. Most c
workers now seem to agree that pre-
cipitation of beachrock cement is from
c
seawater by evaporation and CO 2 (
degassing in the intertidal zone during
low tide (Bricker, 1971; Meyers, 1986), c
although the composition of the water
may be modified greatly by meteoric
c
mixing (Moore, 1983). Other alterna- c:
tives are by degassing of CO 2-rich
carbonate-saturated groundwaters c
which have migrated into shore areas
(Hanor, 1978), or by biologically in-
c
duced precipitation. c
Beachrock is particularly susceptible
to alteration by biological alteration c
(James and Choquette, 1984).
Figure 9 A group of geologists walking on the black, algal-infested surface of beachrock
composed of ooid and grapestone particles cemented by aragonite on the shore of Cock- c
Aragonite crusts. Aragonite crusts
up to 20 mm thick and called "conia-
roach Cay, Berry Islands, Bahamas. The white sand near the trees (right) and the sediments
beneath the water (left) are unlithified. c
tites" (Purser and Loreau, 1973) often
coat beachrock, carbonate grains and c
exposed bedrock in the splash zone. c
These coatings, which look like grey to
cream-coloured enamel paint, range c
from smooth encrustations to porous
surfaces that resemble tufa or traver-
c
tine. Beneath overhangs or in beach- c
rock they have dripstone morpho-
logies. These crusts appear to develop c
only when the substrate is imperme-
able. In the fossil record such crusts
c
could easily be mistaken for ~ea-f1oor
precipitates. ~ \Vv 1J'I'N~ V"'oj \ ~
c
Tidal Flats. \ c
Diagenesis of carbonate sediments on -
wide, muddy tidal flats is discussed in
e
part in other articles in Geoscience (
Canada (James, 1984; Kendall, 1984;
Morrow, this volume). The diagenetic c
processes are complex and involve not c
only CaC0 3 precipitation but also the
formation of dolomite and evaporite c
minerals.
In terms of limestone formation in
Figure 10 Brecciated crusts composed of peloids and algal tubules, cemented by Mg-
calcite and containing minor dolomite in the supratidal zone of the muddy tidal flats along the
c
particular, the same processes seen on western side of Andros Island, Bahamas (handle of the dive knife is 10 em long). c
c
c
Limestones - The Sea-Floor Diagenetic Environment 23

Shark Bay, (Logan, 1974), cementation from the Phanerozoic, with little informa- once they undergo neomorphism to cal-
is more extensive and crusts extend tion on Precambrian limestones. cite in another diagenetic environment,

c over the whole tidal range . Crypto-


crystalline aragonite is the most com-
Biological Alteration.
Microborings. Endol ithic algae are
and (2) were aragonite and Mg-calcite
always the normal precipitates on shal-
mon cement, quickly lithifying intertidal known in carbonates as old as Precam- low carbonate platforms in the past?

o stromatolites and algal-bound sed i-


ment.ln Shark Bay,this grades seaward
brian (Campbell, 1982) and micritized
grains are an integral part of most shal-
In our experience , marine cementa-
tion is not a common or widespread
r into acicular aragonite cementing hard-
grounds offshore. In some instances,
low-water limestone suites.
Macroborings. Macroboring ichno-
feature in ancient limestones. It is usu-
ally documented from fossil reefs (Fig-
Q the aragonite cement forms pendant fossils are known in limestones as old as ure 11), especially from reef-mounds
growths from the ceilings of farge voids Lower Cambrian (James et a/., 1977) (James, 1983, 1984) and reef blocks in
( and fenestrae. but only one, Trypanites (a probable fore-reef deposits (Figure 12), where
( Perhaps most useful as signatures of siphonculid worm trace), is found until marine cement may make up 50% or
shoreline precipitation are the large- the Middle Ordovician when reefs con - more of the rock volume . It is commonly
( scale structures produced. Rapid inter- taining large skeletons developed and inferred to be present from field evi-
granular precipitation at or near the there was a rapid diversification of endo- dence of hardgrounds yet rarely is dem-
sediment surface produces expansion liothictaxa(Kobluketal., 1978). Thebor- onstrated there on the petrographic
fractures and arcuate to polygonal ings of various small bivalves, sponges level, possibly because micrite-size
ridges and tepees. These broken crusts and echinoids are found in reefs , reef- cements are the norm and cannot be
may in turn be reworked by storms to mounds and hardgrounds of later resolved microscopically. Fibrous ce-

o produce pavements of tabular clasts.


Micritization of skeletal and oo id
Paleozoic and particularly Mesozoic
and Cenozoic age (Warme, 1975).
ments are rarely seen in marine-shelf
gra instones but have been described
o grains in many of these crusts is so
intensive that peloidal sediment is in
Cementation.
Confident recognition of sea-floor
from fossil beachrocks (Purser, 1969;
Choquette and Steinen, 1980).
part depositional and in part diagenetic. cementation and its spectrum of pro- Recognition of Sea-floor Lithification.
ducts is a critical part of any study in Prior to any analysis of sea-floor cement
THE FOSSIL RECORD carbonate petrogenesis, yet two pro- fabrics the following criteria are useful
C The products of sea-floor diagenesis can blems bedevil this seemingly simple in establishing early lithification on the
be recognized in carbonates of all ages. task: (1) what precisely are the fabr ics of sea floor (Figure 13):
O Almost all information, however, comes the aragonite and Mg-calcite cements (1) If in bedded sediments, are the litho-
o I).
1,J!./
qt. o "~J-
I\
logic contacts knife-sharp, and if grains
or cements are present are they trun-
O~ ~D c " cated (e.g., Figure 7)?
,...", ..' (2 Is the surface sta ined by iron or man-
ganese salts or phosphate minerals?
(3) Are there cobbles or pebbles of lime-
stone or sand-grade lithoclasts similar in
composition to the matrix, and if so are
they encrusted with organisms?
(4) Is the surface encrusted by orga-
nisms that require a solid substrate?
(5) Is the rock surface bored and, in thin
section , if cements are present, are they
bored as well?
(6) If in reefs, is the first-stage cement
localized to the reefs?
r (7) If in reefs or hardgrounds, is the first-
stage cement interlayered with marine
sediment in cavities (Figure 14)?
(8) If in reefs, are there n ep.tu ~n ("J-IJ
dykes? s:r...-rAIJI~ r.~('" 'tfI'(.pt 'I r
~ . H'.~ r.e.all)~
(9) In reef talus, are there clasts with
first-stage cement or clasts of the
cement (Figure 12)?
(10) If in bedded sed iments, are expan-
sion ridges and polygons present?
While these features point to early lith-
Figure 11 Photomicrograph of reef mound limestone composed of the ? phyllo id alga ification, many alone may be the result
Palaeoaplysina (P)surroundedby several generations offibrous calcite submarine cement (C) of a short-lived period of subaerial
(interpreted to have been Mg-calcite originally) and internal sediment (5); Lower Permian exposure.
Nansen Formation, Ellesmere Island, NWT. (scale 0.5 em). Photograph, G. Davies.
c
24 Diagenesis Geoscience Canada Reprint Series 4 c
c
(

c
c
c
c
Figure 12 Fore-reef debris from an Upper
Devonian reef, Canning Basin, WesternAus-
c
tralia. Theclast at centre is composed of reef c
limestone (R) (mostly the alga Renalcis and
small stromatoporoids) and fibrous calcite c
(C). Thiscement is abundant in contempora -
neous reef deposits. Such clasts are often c
good evidence that the reef itself was subject
to sea-floor cementation. c
c
c
c
c
c
(;
c
Sediment
overlying
cement
c
Clasts of
cemented l imestone c
Figure 13 Criteria for the recognition of
Encrusting
fossils c
see-tloor cementation.
Fe/Mn/P c
impregnated
surface c
dork colour
increase in c
c
amount of
sea floor cement
r
c
c
c
c
c
Figure 14 Photomicrograph of i nter-
layered marine sediment and radiaxial c
fibrous calc ite cement in laminar cavities
from a Middle Ordovician reef mound at c
Meiklejohn Peak, Nevada. (scale 1 mm).
e
(

c
c

c
(
(
(

Limestones - The Sea-Floor Diagenetic Environment 25


r
r

..
il!.,_""""_~ ,,.r m lc robOnngs
roun ded groins
f ibrous or
rnrcrocr ystcltine
cement

Figure 15 Criteria for the recogn ition of


fossil beachrock,
pilled and
( corroded
surfaces

Figure 16 Photomicrograph of a bioclas-


tic grainstone from the Ste. Genevieve For-
mation (Mississippian) Bridgeport Field ,
Illinois Basin , in which the first cement is a
fringe of fibrous calc ite that is thickest on the
undersides of grains (arrows) resembling
c small stalactites. Thisearly cementprobably
developed while the sediment was beach-
rock . (scale 2 mm).

r:

--
8 '
~
I _ _ FASCICULAR
) OPTIC
C) I I' CALCITE

curved
FIBROUS
0
.- CALCITE
cleo~Dges

~
RAOIAXIAL
FIBROUS
CALCITE
'--' Figure 17 Fabrics and morphologies of
coarse marine cements . Fibrous calcite is
generally interpreted as derived from calcite
,- or Mg-calcite and spherulitic calcite from
" reloC~
botryoidal aragonite.
PARAMORPHIC
raYs~
'- REPLACEMENT
SPHERULITI C
square
CALCITE
-~
SPAR-FILLED
'- MOLDS

spherulitic cetcue
cement
c
26 Diagenesis Geoscience Canada Reprint Series 4 c
c
In the fossil record, beachrock can be is almost unknown from modern set- 1985). On balance, the wide variety of c
differentiated from sea-floor hard- tings, and so has long been an enigma- fabrics shown by these cements in the
fossil record (James and Klappa, 1983),
c
grounds only with difficulty, butthis may
be facilitated by the observation of fea-
tic cement fabric. These two types are
not mutually exclusive and may grade even when dolomitized (Tucker, 1983), c
tures such as (1) associated edgewise
conglomerates, (2) intertidal erosion
laterally into one another along the
same cementfringe.lt seems clear that
and the wide range of magnesium con-
tents in Miocene radiaxial fibrous cal-
c
features, (3) jointing, (4) keystonevugs, these cements were originally precipi- cites, suggest that these fibrous ce- c
(5) meniscus or pendulous cements,
and (6) associated facies (Read and
tated as calcite (Sandberg, 1985). The
problem is whether this calcite was
ments may have had a rangeof magnes-
ium contents originally, depending c
Grover, 1977; Donaldson and Ricketts,
1979; Figures 15 and 16).
low-magnesium calcite, and sois moreor
less original, or whether it was high-
upon the chemisty of the precipitating
waters. Thus, those that were LMC have
c
Cement Petrography. magnesium calcite which subsequently remained unaltered while those that c
A helpful guide is the petrographic
nature of the cements themselves.
altered to its present form . This is com-
plicated because diagenesis appears
were HMC have neomorphosed.
These fibrous calcites are generally c
Accumulated evidence from the fossil
record suggests that most "fibrous"
to favour selective alteration of com-
positionally uniform Mg-calcite (re-
preferentially enriched in Mg2+ and
have c5 13 C values consistent with pre-
c
cements as well as many "spherulitic" flecting differences in the original crys- cipitation from seawater (e.g., Davies, c
or mammillary cements were marine
originally, although they are also pre-
tal structure) leading to calcite with
highly variable magnesium contents
1977; Walls et al., 1979; Given and
Lohmann, 1985; Kerans et al., 1986). c
sent in speleothems. Although micro-
crystalline calcite, or Mg-calcite and
(Videtich, 1985). On the one hand, cal-
cite skeletons, known to have been
Stromatactis. An important struc-
ture in fossil carbonates, especially mud
c
possibly aragonite, were precipitated HMC originally, now contain tiny mounds, is stromatactis, loosely de- c
from seawater in the past as they are
today,the small size of the crystals, their
rhombs of dolomite, 1-10 micrometres in
size (Macqueen and Ghent, 1970).
fined as irregular masses of fibrous cal-
cite spar often displaying a flat base.
c
similarity to carbonate mud and their Since many, but not all, fibrous calcites These features originally were thought c
susceptibility to rapid recrystallization
all make their identification difficult
also contain these dolomite inclusions
they are likewise interpreted to have
to be the recrystallized remains of a
mound-forming organism, but since the c
(Mountjoy and Riding, 1981).
Fibrous calcites. These cements
been HMC originally (Lohmann and
Meyers, 1977). On the other hand, on
work of Bathurst (1959) are now known
to be sediment-floored cavities filled
c
(Figure 17) fall into two general groups: the basis of petrography and geochem- with fibrous , radiaxial calcite cement. c
(1) fascicular-optic (Figure 18) cones of
fibrous calcite with divergent optic
istryof Paleozoic and very young Ceno-
zoic radiaxial fibrous calcites it seems
Furthermore, Bathurst (1982) thinks
that the whole structure is marine in c
axes (Kendall, 1977), and (2) radiaxial-
fibrous crystals (Figure 19) with conser-
that these cements precipitated as LMC
and HMC (Kendall, 1985 ; Saller, 1986).
origin and forms by a complex history of
multigeneration sea-floor cementation
c
tal boundaries and convergent optic The peculiar fabric of radiaxial fibrous and cavity formation . c
axes (Bathurst, 1959; Kendall and
Tucker. 1973). While common in fossil
calcite is thought to form by a process of
asymmetric growth within calcite crys-
Epitaxial cement. In contrast to the
modern sea floor, there seems to be c
reefs and reef mounds. radiaxial calcite tals undergoing split-growth (Kendall. abundant evidencefromthe fossil record c
c
~
c
c
c
c
c
e
c
c
c
Figure 18 Photomicrograph in partially polarized light of fascicular
optic calcite cement from Lower Cambrian reef mounds in the Forteau
Figure 19 Photomicrograph in partiaffy polarized light of radiaxial
fibrous calcite cements in the Middle Ordovician reef mound at c
Formation, southern Labrador. The numerous nested cones have the
same irregular crystal boundaries as radiaxial fibrous calcite but lack
Meikeljohn Peak, Nevada. The crystals characteristicaffy have con-
certal boundaries, curved twins, convergent optic axes and contain c
the curved twins and have divergent optic axes. (scale 0.5 mm). diverging subcrystals. (scale 0.5 mm).
c
c
c
C'
C Limestones - The Sea-Floor Diagenetic Environment 27

C
C that syntaxial overgrowths of Mg-cal- and Riding, 1983). Lasemi and Sand- than near-surface meteoric or burial-
o cite cement on echinoderm particles
were common phenomena in the shal-
berg (1982) have discovered that those
micrites and microspars with appar-
diagenetic cements. Compared with
co-existing skeletal debris believed to
(
low marine environment (Meyers, 1974; ently aragonite-dominated lime mud have been low-Mg calcite originally and
r Lohmann and Meyers, 1977) . In some
localit ies, marine epitaxial cements are
precursors have neomorphic calcite
crystals which show pitted surfaces
thus relatively stable (e.g., brachio-
pods, bryozoans, trilob ites), marine ce-
( also common on brachiopods, corals, and/or relic aragonite inclusions in pol- ments have roughly the same e5 13 C but
stromatoporoids, calcispheres and ished and etched sections . In contrast, e5 18 0 which may be lighter or heavier. It
C ooids (Kerans et al., 1986). micrite with apparent calcite-dominated now seems clear that these cements,
o Scalenohedral cement. Clear col-
umnar crystals which contain few inclu-
precursors are characterized by finely
crystalline < 4 micrometre textures,
along with all other CaC0 3 components
of limestones, undergo varying degrees
( sions and display unit extinction are lack any inclus ions and have unpitted of geochemical alteration from slight to
c locally common and interpreted as
marine cements (Kerans et a/., 1986).
crystal surfaces .
Isotopic Signature of Fossil Marine
extensive (Brand and Veizer, 1980, 1981;
Given and Lohmann , 1985) depending
o Spherulitic calcite. There are
numerous instances of spherulitic cal-
Cements.
From a number of careful studies involv-
in part upon whether the majority of
their diagenesis took place in closed,
cite (Figure 20) which mimic the geome- ing selectively sampled cements and partly closed or open systems with
o try of Holocene aragonite sea-floor
cements, especially in reefs. Like for-
other components of limestones (e.g.,
Choquette, 1968; Hudson, 1977; Dick-
respect to pore wate r. Given and
Lohmann (1985) have argued , using
o mer aragonite skeletons, the fabric in son and Coleman , 1980; Brand and both cathodoluminescence petrogra-

o these botryoids is preserved either as a


mosaic of tiny crystals or as a para-
Veizer, 1981; Given and Lohmann, 1985;
Lohmann, in press), it is clear that
phy and a large body of isotopic ana-
lyses, that closed-system diagenesis
o morphic replacement (Assereto and
Folk, 1980; Mazzullo, 1980) or even as
marine and other CaC0 3 cements in the
fossil record have by and large pre-
operates on a microscale to preserve
the isotopic signatures of many marine
chert (Grotzinger and Read, 1983). For a served enough of their original signa- cements.

o detailed discussion on styles of altera-


tion see Sandberg (1985) and the follow-
ture to be distinguishable from one
another (Figure 21). In general , the
There is growing evidence that iso-
topic compositions of botryoidal (former
o ing chapter on meteoric diagenesis.
Actual aragonite cement crystallites
marine cements (isopachous, radiaxial
fibrous, micritic and botryo idal) contain
aragonite) and fibrous calcite cements
show systematic yariations through the
preserved in calcite have been dis- isotopically heavier carbon and oxygen Phanerozoic which seem to transcend

o covered in rocks as old as Pennsylva-


nian (Sandberg and Popp, 1981). These
replaced aragon ite spherulites are +6

o sometimes still enriched in Sr and again


have a e5 13 C consistent with marine
o precipitation .
+4

..
Microcrystalline calcite. Finely
o crystalline calcite is extremely difficult
~

o to interpret as a fossil cement (Mountjoy


o
~ +2
z
o

o lD
II:
e:t
ol-------------_.,....",...,.,=-.:-----t--------I
o o

o
o -2

(
- ~1L,.2-....L..-+-.l.---,1,----l--!---l--+-.l.----!1,----l-~-....L..-+--.l----'·
l -6 -4 -2
OXYGEN, 8 180 ("10.)
+4

C.
( Figure 21 Cross-plot of carbon versus oxygen isotopic compositions of Holocene and
ancient fibrous and spherulitic (botryo idal) carbonate cements. The values shown are the
" heaviest" compos itions from covar iate populations of data, believed to approximate most
Figure 20 Photomicrograph of coa- closely the original marine-isotopic compositions of the cements (method of Given and
lesced, strontium-rich calcite botryoids Lohmann, 1985). The data are from James and Ginsburg (1979), Moldavanyi and Lohmann
(interpreted to have been aragonite origi- (1982), Marshall and Ashton (1980), Given and Lohmann (1983), Davies and Krause (1975),
/" nally) from a reef mound in the Nansen For- Lohmann (1983) , MeyersandLohmann(1983), Walls etal.(1979), MattesandMountjoy(1980),
mation (Lower Permian) Ellesmere Island, Cercone and Lohmann (1983), Sears and Lucia (1980), Ross et al. (1975), and James and
NWT. (scale 2 mm). Photograph, G. Davies. Klappa (1983), listed in order of increasing age of the stratigraphic units involved.
; . ? '" • !.'''-''''''v- ';;~ L~C'r-v--
J 11C) -. I (in\' )lQ!J..;a.--
c
28 Diagenesis Geoscience Canada Reprint Series 4 c
c
regional differences in diagenetic his- An original model of linear change patterns in the lithosphere. Sea level c
tory (Figures 21 and 22). These varia- from calcite seas in the early and middle is high and shallow seas vast because (
tions are consistent overall with the vari- Paleozoic to later aragonite seas has of extension in the length and width of
ability of isotopic compositions through now been replaced by a non-linear the mid-ocean ridge system; the "sub- c
Phanerozoic time for whole-rock lime-
stones (e.g., Veizer and Hoefs, 1976)
model tied to changes in atmospheric
PC0 2 (Mackenzie and Pigott, 1981;
mergent mode" of Wilkinson et al.
(1985). c
and for brachiopods (Pigott, 1981). Iso- Pigott, 1981; Sandberg and Popp, 1981; Aragonite Seas. Theatmosphereisin c
topic variations ofthis magnitude can be
explained in a number of ways, includ-
Sandberg, 1983). This most recent
model has more universal appeal as it is
the "icehouse" mode with lower Pco,
because of the reduced volcanism due c
ing differences in degree of diagenetic
alteration and re-equilibration (e.g.,
also related to world-wide sea-level fluc-
tuations (e.g., Vail et ei., 1977) and
to sluggish plate movement and aggre-
gated continents. Sea level is low and
c
Dickson and Coleman, 1980). There is a global tectonics. Fischer (1981) usesthe shallow seas reduced to narrow strips c
grOWing basis for believing that the oxy-
gen isotopic composition of seawater
term "greenhouse mode" to label times
when the atmosphere contained more
along continental margins because the
mid-ocean ridge system has dropped;
c
itself has varied since Precambrian
time (Brand and Veizer, 1981; Popp et al.,
CO 2 than it does today and so the sur-
face of the earth was warmer, and the
the "emergent mode" of Wilkinson et al. c
1981; Lohmann, 1988). Differences of
up to 5.5%0 in 0180 between present-day
term "icehouse" to characterize times
(1985).
The systematic variations in isotopic c
and past seawater have been postu-
like the present, with lower CO 2 , cooler
temperatures and continental glacia-
composition of brachiopods (Veizer et
et., 1986; Poppetal., 1986), fossil marine
c
lated by Brand and Veizer (1981), and
differences in 013C may have been
tion. Integrating these concepts, it is
postulated that in the past shallow-
cements (Figures 20 and 21) and car-
bonates in general (Veizer and Hoefs,
c
nearly as great (Figure 22). water carbonate deposition took place (
1976) tend to support this hypothesis

THE PRESENT IS NOT ALWAYS THE


under one of the following conditions
(Figure 22):
since "aragonite seas" and "calcite
seas" should be characterized by heav-
c
KEY TO THE PAST Calcite Seas. The atmosphere is in ier and lighter 013C, respectively. Since c
One of the guiding tenets of carbonate
petrology is uniformitarianism . espe-
the "greenhouse" mode with high PC0 2
because of increased volcanism result-
marine carbonates show a linear rela-
e
tionship between 013 and 0180 (Milli- c
cially the concept that, as in present
times, aragonite and Mg-calcite were the
ing from rapid and complex convective man and Muller, 1974), we would expect c
most common carbonates forming on EUSTATIC c
shallow sea floors ofthe past. This axiom
has recently been challenged, and it now
MARINE
bleo s
CEMENTS
~p C.
RISING - SEA LEVEL--FALLING c
c
0/00
seems quite likely that an alternative is 8 0 +8 W
o o
possible, i.e., thatthere were times when
calcite was the normal sea-floor precipi- W T c
tate (see Sandberg, 1983 and an excel-
lent review by Wilkinson, 1982).
(f)
:::l
0 c
I
K
Twenty-five years ago, Lowenstam
(1963) pointed out that the composition
Z
W
w
100
c
of marine skeletons apparently had
0:
(9
II II
J C
200
changed during the Phanerozoic:
Paleozoic seas were dominated by cal-
w
(f)
ARAGONITE
SEAS
R E
~
:::l
cite-secreting invertebrates, Cenozoic 0
I C
and modern seas were characterized by W

organisms which secreted aragonite ~ C 300 C


and Mg-calcite skeletons, and Meso-
zoic seas contained roughly equal num-
w
(f)
:::l 0 C
bers of each. In the last few years, on the
0
I
S
400 C
c
Z
basis of new data from fossil skeletons W
W
(Wilkinson, 1979; Pigott, 1981), ooids 0:
0
(Sandberg, 1975; Pigott and Mack-
enzie, 1979; Wilkinson et al., 1984),
(9
500 e
c.
i
cements (Folk, 1974; Wilkinson, 1982; £
Sandberg, 1983), and carbonate muds
(Folk, 1974; Sandberg, 1975), it appears pe; 600 c
that much carbonate in the fossil record
was deposited or precipitated as cal-
c
cite. Milliken and Pigott (1977) coined Figure 22 (Right) The possible distribution of "calcite" and "aragonite" seas in geologic
(
the term "calcite seas" to differentiate
these periods from times similar to the
history. Modified from Fischer (1981) and Wilkinson (1982).
(Left) Variations in oxygen and carbon isotopic compositions of marine cements through
c
"aragonite seas" of today. Phanerozoic time. The data are from the sources acknowledged in Figure 21 (caption).
(
c' Limestones - The Sea-Floor Diagenetic Environment 29

c:
c that radiaxial fibrous , botryoidal and of these features . There is a clear zona- read by R.G.C. Bathurst, N. Chow, M.
(, other marine CaC0 3 cements also tion present on reef-rimmed platforms Coniglio, P. Sandberg and R.K. Ste-
should have had original isotopic signa- with cementat ion decreasing into the vens, to all of whom we owe special
o tures which were heavier during times of
"aragonite seas" and lighter during
lagoon, onto the platform and down-
slope into deep water. If the lower parts
thanks. N.P. James acknowledges the
Natural Sciences and Engineering
C times of "calcite seas", This is exactly of the slope are in waters undersatu- Research Council of Canada for on-
o the relationship we appear to be seeing
in Figure 22, where, from groups of ana-
rated with respect to aragonite, then
lithification may take place in deep cold
going financial support

( lyses the heaviest (most nearly original) waters by dissolution and reprecipita- REFERENCES
o isotopic values have been plotted
versus geologic time, The departure of
tion. Such azonation is less apparent on
open platforms and ramps, where ex- General References and Reviews
( the curves for 0'80 and 0'3C in late tensive lithification of sand sheets to
Bathurst , R.G.C., 1975, Carbonate Sedi-
Carboniferous through Triassic time form hardgrounds is common. ments and Their Diagenesis: Elsevier,
( implies a diagenetic and/or original sea- The major prerequisites for early sea- North Holland, 658 p.
o water temperature effect But the gen-
eral relationship suggests some con-
floor cementation appear to be an oxi-
dizing environment, a stable substrate
Chapter 9 and the updated appendix are
a good introduction to this topic.
( sistent non-linear trends in seawater and good water exchange. Recognition Bathurst, R.G.C., 1980, Lithification of car-

o composition through the Phanerozoic


which show a close tie with first-order
of submarine cements in the fossil rec-
ord depends upon a combination of
bonate sediments: Science Progress
Oxford , v. 66, p. 451-471.

o sea-level excursions and temperature


variations ,
field, petrographic and geochemical
techniques , and even then their pre-
An excellent update to the material cov-
ered in the 1975 text.

o The question of whether seawater sence is easily inferred but proven with
Bathurst , R.G.C., 1986, Carbonate diagen-
esis and reservo ir development: conser-
o isotopic composition has, indeed, var-
ied significantly and systematically
difficulty.
The present is but a general guide to
. vation, destruction and creation of
pores , in Carbonate Depos it ional
through time is critically important in sea-floor dia enesis in the ast. Th~ Environments; Part5: Diagenesis 1, Col-
any attempts to interpret the origins of world ocean appears to have oscillated orado School of Mines Quarterly, v. 81,
o carbonate cements and carbonate between periods when calcite was th p.1-24.

o rocks using geochemical compositions,


If this is the case then the discussion of
main precipitate and periods when, Iik
today, aragonite and Mg-calcite we
An essay focussed on porosity highlight-
ing the importance of early diagenesis.

o carbonate precipitation on the modern


sea floor outlined in this essay applies
dominant Geochemical interpretations
of fossil precipitates are further compli-
Br icker, O .P., 1971, ed . , Carbonate
Cements: The Johns Hopkins University

o mainly to specific times in the past :


(1) late Precambrian and Cambrian,
cated by the fact that the isotopic com-
position of seawater seems to have var-
Press, Baltimore, MD, p. 201-236.
Theearly work on sea-floor diagenesis is
G (2) Pennsylvanian to Triassic, possibly ied with time.
well documented in 7 important papers.
Hudson, J.D., 1977, Stable isotopes and
o Jurassic and (3) Cenozoic - the " emer-
gent" modes. During the early and
The implications of sea-floor cemen-
tation are profound in the creation of
limestone lithification: Journal of the

o middle Paleozoic and much of the new environments, maintenance of


Geological Society, v. 133, p. 637-660.
An excellent overview of stable isotopes,

o Mesozoic abiotic carbonate precipita-


tion in shallow seas would have been
large carbonate structures and the pre-
servation of depositional textures and
carbonates and seawater.
James, N.P.and Ginsburg, R.N., 1979, The

o mostly calcite.
Another impliction is that clear, rhom-
fabrics. ~xtensive intergranular pre-
cipitation, however, reduces dramat-
seaward margin of Belize barrier and
atoll reefs: International Association of
( bic calcite cement, generally thought to ica y the depositiona porosl yan per-
Sedimentologists, Special Publication
3,199 p.
o be characteristic of precipitation from
fresh water (see the next article in this
meabilit of s ecific aCles ren erm
them unsuitable as reservoirs for hydro-
A detailed, well-illustrated documenta-

o series) is not diagnostic alone as evi- carbons a e metals.


tion of early diagenesis along a modern
platform margin setting.

o dence of exposure to meteoric fluids


(Given and Wilkinson , 1985), and may
be a sea-floor precipitate (Wilkinson et
ACKNOWLEDGEMENTS
This series of articles is an outgrowth of
Milliman, J.D. and Muller, J., 1977, Charac-
teristics and genesis of shallow-water
and deep-water limestone , in Anderson,
al., 1982). a graduate-level course in carbonate N.R. and Malahoff, A., eds., The Fate of
petrogenesis given at Memorial Univer- Fossil Fuel CO2 in the Oceans: Plenum
Press, New York, p. 655-673.
SUMMARY sity and a carbonate training seminar
A summary of the attributes of marine
Taken as a whole, marine sea-floor presented to Marathon Oil Company.
c diagenesis is not common in either mod-
ern or ancient carbonate sediments.
We thank all those willing and unwilling
participants who helped shape our
cements.
Schneidermann, N. and Harris, P.M., 1985,
eds., Carbonate Cements: Society of
Cementation, however, is of major ideas . K.C. Lohmann generously Econom ic Mineralogists and Paleon-
importance in certain facies, namely allowed us to use some of his unpub- tologists, Special Publication No. 36,
along platform and reef margins, on lished data on the isotopic composition 379 p.
sand shoals and in the strandline. Early, of fossil cements, thus enabling us to A collection of papers on modern and
shallow water lithification of platform present a much more coherent picture ancient carbonate cements, a good
and reef margins is probably one of the than would otherwise have been possi- source of current information on the
topic.
main reasons for the structural integrity ble. This article was originally critically
c
30 Diagenesis Geoscience Canada Reprint Series 4 c
c
Schroeder, J.H. and Purser, B.H ., 1986, Morse , J.W and Berner, R.A., 1979, Chem- Given, R.K. and Wilkinson, B.H ., 1985a,
c
eds., Reef Diagenesis: Springer-Verlag, istry of calcium carbonate in the deep Kinetic control of morphology, composi- c
New York, 455 p.
A series of articles devoted entirely to the
oceans, in Jenne, E.A., ed., Chemical
Modelling in Aqueous Systems: Amer i-
tion and mineralogy of abiotic sedi-
mentary carbonates: Journal of Sedi· c
diagenesis of reefs , modern and ancient,
including a review of current thinking on
can Chemical Society, Washington ,
p.499-535 .
mentary Petrology, v. 55, p. 109-119.
Given, R.K. and Wilkinson, S.H ., 1985b, c
the topic. Morse, J.W., 1983, The kinetics of calcium
carbonate dissolution and precipitation,
Reply - Kinetic control of morphology,
composition and mineralogy of abiotic c
Zones of Sea-floor Diagenesis in Reeder, R.J., ed., Carbonates, their
mineralogy and chemistry: Reviews in
sedimentary carbonates : Journal of Sedi-
mentary Petrology, v. 55, p. 921-926.
(
Adelseck, C.G. and Berger, WH., 1975, On
the dissolution of planktonic foramini-
Mineralogy, v. 11, p. 227-264.
Richter, D.K. and Fuchtbauer, H., 1978, Fer-
Loreau, J.P., 1982, Sediments aragoniti-
quesetleurgenese: Memoirdu Museum
c
fera and associated microfossils during roan calcite replacement indicates for- National D'Histoire Naturelle, New (
settling and on the sea floor, in Sliter,
W.V., Be, AW.H. and Berger, WH ., eds. ,
mer magnesian calcite skeletons: Sedi-
mentology, v. 25, p. 843-860.
Series Tome XLVII, 483 p.
Kinsman, D.J.J ., 1969, Interpretation of c
Dissolution of Deep Sea Carbonates:
Cushman Foundation Foraminifera
Scholle, P.A.,Arthur, M.A. and Ekdale, A.A.,
1983, Pelagic environment, in Scholle,
Sr +2concentrations in carbonate miner-
als and rocks: Journal of Sedimentary c
Resources, Special Publication 13,
p.70-81.
P.A., Bebout, D.G. and Moore, C.H o,
eds ., Carbonate Depositional Environ-
Petrology, v. 39, p. 489-508.
Morse, J.W., 1985, Discussion - Kinetic con- c
Berger, WH., 1975, Deep-sea sedimen-
tation, in Burk, C.A. and Drake , C.L.,
ments: American Association of Petro-
leum Geologists, Memoir 33, p. 619-
trol of morphology, composition and
mineralogy of abiotic sedimentary car-
c
eds., The Geology of Continental Mar- 692. bonates: Journal of Sedimentary Petrol- c
gins : Springer-Verlag, New York,
p.213-243.
Sliter, W.V., Be, AW.H . and Berger, WH .,
1975, eds., Dissolution of Deep Sea Car-
ogy, v. 55, p. 919-921.
Mackenzie, F.T., Bischoff, W.D., Bishop, c
Berger, WH ., 1978, Deep-sea carbonate:
pteropod distribution and the aragonite
bonates: Cushman Foundation Fora-
minifera Research, Special Publication
F.C., Loijens, M., Schoonmaker, J. and
Wollast, A., 1983, Magnesian calcites : c
compensation depth: Deep Sea
Research, v. 25, p. 447-452.
13, 159 p.
Takahashi, T., 1975,Carbonate chemistry of
low temperature occurrence, solUbility
and solid solution behaviour, in Reeder,
t;
Berner, A.A., 1966, Diagenesis of carbon-
ate sediments: interaction of magne-
seawater and the calcite compensation
depths in the oceans, in Sliter, W.v., Be,
A.J ., ed., Carbonates, their mineralogy
and chemistry: Mineralogical Society of
c
sium in sea water with mineral grains:
Science, v. 153, p. 188-191.
A.W.H. and Berger, W.H., eds ., Dissolu-
tion of Deep Sea Carbonates: Cushman
America, Reviews in Mineralogy, v. 11,
p.97-144.
c
Berner, A.A. and Morse, J.W, 1974,Dissolu- Foundation Foraminifera Resources, Mitterer, R.M., 1971, Influence of natural (
tion kinetics of calcium carbonate in sea
water IV, theory of calcite dissolution :
Special Publication 13, p. 11-26. organic matter on CaC03 precipitation,
in Bricker, O.P., ed. , Carbonate Ce- c
American Journal of Science, v.274,
p.l08-134.
Modern Carbonate Sediments ments: The Johns Hopkins University
Press, Baltimore, MD, p. 252-258. c
Broecker, WS. and Takahashi , T., 1978, The
relationship between lysocline depth
Zone I: Warm Water, Shallow Tropical
Environments
Mitterer, R.M . and Cunningham, R., Jr.,
1985, The interactions of natural organic
c
and in situ carbonate ion concentration: matter with grain surfaces: implications c
Deep Sea Research, v. 25, p. 65-95.
Fuchtbauer, H. and Hardie, L.A., 1976,
Experimentally determined homo-
Mineralogy of Precipitates

Bathurst, A.G .C., 1968, Precipitation of


for calcium carbonate precipitation, in
Schneidermann , N. and Harris, P.M.,
eds ., Carbonate Cements: Society of
c
geneous distribution coefficients for ooids and other aragonite fabrics in Economic Mineralogists and Paleon- (
precipitated magnesium calcites:
application to marine carbonate
warm seas, in Muller, G. and Friedman,
G.M., eds., Recent Developments in
tologists, Special Publication No . 36,
p.17-32. c
cements: Geological Society of Amer-
ica, Abstracts with Program, p. 877.
Carbonate Sedimentology in Central
Europe: Springer, Berlin, p. 1-10.
Mucci, A. and Morse , J.W., 1983, The incor-
poration of Mg2+ and Sr 2+ into calcite
c
Ginsburg, R.N . and James, N.P., 1975, Berner, R.A., 1975, The role of magnesium overgrowths: influences of growth rate c
Holocene carbonate sediments of conti-
nental shelves, in Burk, C.A. and Drake,
in the crystal growth of calcite and arag-
onite from seawater: Geochimica et
and solution composition: Geochimica
et Cosmochimica Acta, v. 47,p. 217-233. c
C.L., eds., The Geology of Continental
Margins: Springer-Verlag, New York,
Cosmochimica Acta, v. 39, p. 489-504.
Berner, R.A., 1980, Early Diagenesis: a the-
Suess, E., 1970, Interaction of organic com-
pounds with calcium carbonate -I : asso- c
p. 137-157.
Hsu, K.J. and Jenkyns, H.C., 1974, eds. ,
oretical approach: Princeton University
Press, 241 p.
ciated phenomena and geochemical
implications: Geochimica et Cosmo- c
Pelagicsedimentson land and under the
sea: International Association of Sedi-
Burton, E.A. and Walter, L.M., 1987, Rela-
tive precipitation rates of aragonite and
chimica Acta, v. 34, p. 157-168.
Suess, E., 1973,Interaction of organic com-
e
mentologists, Special Publication 1, Mg calcite from seawater: Temperature pounds with calcium carbonate - II: (
778 p.
Kennett, J .P., 1982, Marine Geology :
or carbonate ion control: Geology, v. 15,
p. 111-114.
organocarbonate association in recent
sediments : Geochimica et Cosmo- c
Prentice-Hall, Englewood Cliffs, 813 p.
Lees, A. and Buller, A.T., 1972, Modern
temperate-water and warm-water shelf
Davies, P.J., Bubela, B. and Ferguson, J.,
1978, The formation of ooids: Sedimen-
tology, v. 25, p. 703-731.
chi mica Acta, v. 37, p. 2435-2447.
Walter, L.M., 1985,Relative reactivity of skel-
etal carbonates during dissolution:
c
carbonates contrasted: Marine Geol- Folk, R.L., 1974, Natural history of crystal- implications for diagenes is, in Schneider-
(
ogy, v. 13, p. 67-73. line calcium carbonate: effect of magne-
Milliman, J.D., 1974, Marine Carbonates: sium content and salinity: Journal of
mann, N. and Harris, P.M., eds ., Carbon-
ate Cements: Society of Economic Miner-
C
Springer-Verlag, New York, 375 p. Sedimentary Petrology, v. 44, p. 40-53 . alogists and Paleontologists, Special
Publication No. 36, p. 3-16.
l
C
(
(

( Limestones - The Sea-Floor Diagenetic Environment 31

c
C' Walter, L.M. and Morse, J.w., 1984, Magne· Viezer, J., 1983, Trace elements and iso- Land, L.S. and Moore , C.H., 1980, lithifica-
sium calcite stabilities : are-evaluation : topes in sedimentary carbonates , in tion, micritization and syndepositional
Geochimica et Cosmochim ica Acta , Reeder, R.J., ed., Carbonates, the ir min- diagenes is of biolithites on the Jama i-
o v. 48, p. 1059·1069. eralogy and chemistry: Mineralogical can Island slope : Journal of Sedimen-

o Petrography of Precipitates
Society of America, Reviews in Miner-
alogy, v. 11, p. 265-300 .
tary Petrology, v. 40, p. 357-371.
Marshall , R.J., 1986, Regional distribution

o Chafetz, H.S. , 1986, Marine peloids: a pro-


duct of bacterially induced prec ipitation
Precipitated Partlc/es
of submarine cements with in an epicon -
tinental reef system : Central Great Bar-
rier Reef , Australia, in Schroeder , J.H.
( of ca lc ite: Journal of Sed imentary Ellis, J.P. and Milliman , J.D., 1985, Calcium and Purser, B.H., eds ., Reef Diagenes is:
( Petrology, v. 56, p. 812-817. carbonate suspended in Arabian Gulf Springer-Verlag, New York, p. 8-26.
Macintyre, I.G. , 1985, Submarine cements- and Red Sea waters: biogenic and de- Macintyre , I.G., 1977, Distribution of sub-
( the peloidal question , in Schneider· trital , not " chemogenic" : Journal of Sedi- mar ine cements in a modern Caribbean
mann, N. and Harris , P.M., eds ., Carbon- mentary Petrology, v. 55, p. 805-808. fringing reef , Galeta Point , Panama :
( ate Cements : Society of Econom ic Land, L.S ., Behrens. E.W. and Frishman , Journal of Sedimentary Pstrolcqy, v. 47,

o Mineralogists and Paleontologists, Spe-


cial Publication No. 36, p, 109·116.
SA, 1979 , The ooids of Baffin Bay
Texas: Journal of Sedimentary Petrol-
p.503-516.
Pierson, B.J. and Shinn, E.A., 1985 ,

o Marshall , J.F., 1983, Submarine cementa-


tion in a high-energy platform reef: One
ogy, v. 49 , p. 1269-1278.
Marshall , J.F. and Davies , P.J., 1975, High-
Cement distribution and carbonate min-
erai stabilization in Pleistocene lime-
o Tree Reef, southern Great Barrier Reef :
Journal of Sedimentary Petrology, v. 53,
magnesium calcite ooids from the Great
Barrier reef : Journal of Sedimentary
stones of Hogsty reef, Bahamas , in
Schne idermann , N. and Harris , P.M ..
p. 1133-1149. Petrology, v. 45, p. 285-291. eds., Carbonate Cements : Society of
Sandberg, P., 1985, Aragonite cements and Neumann , A.C. and Land, L.S., 1975, Lime Economic Mineralogists and Paleon-
a their occurrence in ancient limestone , mud deposition and calcareous algae in tologists , Special Publicat ion No. 36,

o in Schneidermann, N. and Harris, P.M.,


eds. , Carbonate Cements : Society of
Economic Mineralog ists and Paleon -
the Bight of Abaco, Bahamas: a budge t:
Journal of Sedimentary Petrology, v. 45,
p.763-786.
p. 153-169 .
Read, J.F., 1974, Carbonate bank and wave-
built platform sedimentation, Edel Prov-
tologists , Special Publ ication No. 36 , Simone , L., 1980, Ooids: a review: Earth ince, Shark Bay. Western Australia, in
p.33-58. Sciences Reviews, v. 16, p.319-355 . Logan, B.W., et al., eds., Evolution and
Stockman, K.W., Ginsburg, R.N. and Shinn , diagenesis of Quaternary carbonate se-
o Isotopic Geochemistry of Precipitates E.A ., 1967, The production of lime
mud by algae in south Flor ida: Journal
quences. Shark Bay, Western Australia :
American Assoc iat ion of Petroleum
Gonzalez, L.A. and Lohmann, K.C., 1985, of Sedimentary Petrology, v.37, Geolog ists . Memoir 22, p. 1-61.

o Carbon and oxygen isotopic compost-


t ion of Holocene reefal carbonates :
p.633-648. Shinn , E.A., 1969, Submarine lithification of
Holocene carbonate sediments in the

o Geology, v. 13, p. 811-814.


Gross, M.G., 1964, Variations in the 18 0 / 160
Cementation of Sand Shoal,
Reef and Fore-reef Sediments
Persian Gulf: Sedimentology, v. 12,
p. 109-144.
r and 13C/'2C ratios of diagenetically Taft, W.H., Arr ington , F., Hainov itz, A., Mac-
altered limestones in the Bermuda Aissaoui, D.M, Bu igues, D. and Purser, donald , C. and Woolheater, C., 1968,
o Islands: Journal of Geology. v.72 ,
p. 170-194.
B.H., 1986, Model of reef diagenesis:
Mururoa Atoll, French Polynesia , in
Lith ification of modern carbonate sedi-
ments at Yellow Bank, Bahamas : Bul-
o Keith, M.L. and Weber, J.N., 1965, Carbon
and oxygen isotopic compositon of
Schroeder, J.H . and Purser, B.H., eds.,
Reef Diagenesis: Springer-Verlag. New
letin of Marine Science, v. 18, p. 762-
828.
o selected limestones and foss ils: Geo-
chimica et Cosmochimica Acta, v. 40,
York, p. 27-52.
Dill, R.F., Shinn , E.A., Jones, A.T., Kelly, K. Cementation on Carbonate Slopes and in
p. 1095-1108 . and Ste inen, A.P.• 1986. Giant subtidal Shallow Basins

o Lloyd , A.M., 1971, Some observations on


recent sediment alteration ("micriti-
stromatolites forming in normal salinity
waters : Nature, v. 324, p. 55-58. Gevirtz, J.L. and Friedman, G.M., 1966,
o zation") and the possible role of algae in
submarine cementation, in Br icker. D.P.,
Dravis, J., 1979, Rapid and widespread gen-
eration of recent oolitic hardgrounds on
Deep sea carbonate sediments of the
Red Sea and their implication on marine
ed. , Carbonate Cements: The Johns the high energy Bahamian Platform, Ele- lithification : Journal of Sedimentary
Hopk ins University Press. Baltimore, uthera Bank, Bahamas: Journal of Sedi- Petrology, v. 36, p. 143-151.
MD, p. 72-79. mentary Petrology, v. 49, p. 195-209. Mullins, H.T.A., Neumann, C., Wilber, R.J.
Moore, C.H., 1973, Intertidal carbonate Ginsburg, R.N. and Schroeder, J., 1973, and Boardmann, M.R., 1980, Nodular
cementation , Grand Cayman , West Growth and submarine fossilization of carbonate sediment on Bahamian
Indies: Journal of Sedimentary Petrol- algal cup reefs, Bermuda: Sedimen- slopes: possible precursors to nodular
ogy, v. 43, p. 591-602. tology, v. 20 , p. 575-614. limestones: Journal of Sedimentary
Morrison, J. and Brand, U., 1986, Geochem- James , N.P., Ginsburg, R.N., Marszalek, Petrology, v. 50, p. 117-133.
istry of Recent marine invertebrates: D.S. and Choquette, P.w., 1976, Facies Neumann, A.C., Kofoed , J.w. and Keller,
Geoscience Canada, v. 13, p. 237·254. and fabric spec ificity of early subsea G.H., 1977, Lithoherms in the straits of
Schroeder, J.H ., 1972, Calcified filaments cements in shallow Belize (British Hon- Florida: Geology, v. 5, p. 4-10.
" of an endolithic algae in recent Bermuda duras) reefs: Journal of Sedimentary
reefs : Neues Jahrbuch fUr Geologie, Petrology, v. 46, p. 523-544. Neomorphism
Palaeontology Montash v. 1, p. 16-33. Land, L.S. and Goreau, T.F., 1970, Sub-
marine lith ification of Jamaican reefs: Kendall, C.G.C. and Skipwith, P.A., 1969,
Journal of Sedimentary Petrology, v. 40, Holocene shallow-water carbonate and
p.457-461. evaporite sediments of Khor alBazam,
Trucial Coast, Southwest Persian Gulf :
c
32 Diagenesis Geoscience Canada Reprint Series 4 c
c
American Association of Petroleum Schlager, W. and James, N.P., 1978, Low Jones, B. and Goodbody, Q.H., 1984, Bio-
c
Geologists, Bulletin, v. 53, p. 841-869 . magnesium calcite limestones forming logical alteration of beachrock on Grand c
Murray, J.w., 1966, The foraminifera of the
Persian Gulf. 4: Khor al Bazam: Pal-
at the deep sea floor, Tongue of the
Ocean, Bahamas: Sedimentology, v. 15,
Cayman Island, British West Indies: Bul-
letin of Canadian Petroleum Geology, c
aeogeography, Palaeoclimatology, Pal-
aeoecology, v. 2, p. 153-169.
p.675-702. v. 32, p. 201-215.
Logan, B.W., 1974, Inventory of diagenesis c
Purdy, E.G., 1968, Carbonate diagenesis :
an environment survey : Geologica
Biological Alteration in Holocene - Recent carbonate sedi-
ments, Shark Bay, Western Australia, in c
Romana, v. 7, p. 183-228.
Scherer, M., 1974, Submarine recrystalli-
Alexandersson, T., 1978, Micr itization of
carbonate particles: processes of pre-
Logan, BW., et al. , Evolution and Dia-
genesis of Quaternary Carbonate Se-
c
zation of a coral skeleton in a Holocene
Bahamian reef: Geology, v. 3, p. 499-
cipitation and dissolution in modern
shallow-water sediments : Bulletin of
quences, Shark Bay, Western Australia :
American Association of Petroleum
c
500. Geologists Institution , University Geolog ists, Memoir 22, p. 195·250. (
Zone II: Temperate water, shallow shelves
Uppsala , New Series 3, p. 201-236.
Bathurst, R.G.C., 1966, Boring algae, mic-
Meyers, J.H., 1987, Marine vadose beach-
rock cementat ion by cryptocrystalline c
and deep water tropical slopes and basins rite envelopes and lithification of mol-
luscan biosparites: Geological Journal,
magnesian calcite- Maui, Hawaii:Journal
of Sedimentary Petrology, v. 57, p. 558- c
Alexandersson, T., 1974, Carbonate cemen-
tation in coralline algal nodules in the
v. 5, p. 15-32.
Bromley, R.G. , 1978, Bioerosion of Ber-
570.
Purser, B.R. and Loreau, J.P., 1973, Arag-
c
Skagerrak, North Sea: biochemical pre- muda reefs: Palaeogeography, Palaeo- onitic, suprat idal encrustations on the c
cipitation in undersaturated waters:
Journal of Sedimentary Petrology, v. 44,
climatology, Palaeoecology, v. 23 ,
p. 169-197.
Trucial Coast, Persian Gulf, in Purser,
B.H., ed., The Persian Gulf: Springer- c
p.7-26.
Alexandersson, T., 1978, Destructive dia-
Budd, D.A. and Perkins, R.D., 1980, Bathy-
metric zonation and paleoecological
Verlag, p. 343-377.
Stoddart, D.R. and Cann , J.R., 1965, The c
genesis of carbonate sediments in the
Eastern Skagerrak, North Sea: Geology,
significance of microboring in Puerto -
Rican shelf and slope sediments : Jour-
nature and origin of beachrock: Journal
of Sedimentary Petrology, v.35, c
v. 6, p. 324-327. nal of Sedimentary Petrology, v. 50, p.243-247.
Alexandersson, T., 1979, Marine macera- p.881-905. Taylor, J.D .M . and IIling, L.V., 1969,
tion of skeletal carbonates in the Skager- Friedman, G .M., Gebelein, C.D. and Holocene intertidal calcium carbonate c
rak North Sea: Sedimentology, v. 26,
p.845-852.
Sanders,J .E., 1971, Micrite envelopes of
carbonate grains are not exclusively of
cementation , Qatar, Persian Gulf: Sedi-
mentology, v. 12, p. 69-109. c
Freeman-Lynde, R.P., Whitley, K.F. and
Lohmann , K.C., 1986, Deep-marine ori-
photosynthetic algal origin : Sedi-
mentology, v. 16, p. 89-96. The Fossil Record c
gin of equant spar cements in Bahamian
escarpment limestones: Journal of Sedi-
Kobluk, D.R. and Risk, M.J., 1977, Rate and
nature of infestation of a carbonate sub-
Biological Alteration c
mentary Petrology, v. 56, p. 799-811.
Gomberg, D.N. and Bonatti, E., 1970,High-
stratum by a boring alga: Journal of
Experimental Marine Biology and Ecol-
Bromley, R.G., 1975, Trace fossils at omis- c
magnesium calcite : leach ing of magne- ogy, v. 27, p. 107-115.
sion surfaces , in Frey, R.W., ed., Study
of Trace Fossils: Springer-Verlag, New c
sium in the deep sea: Science, v. 168,
p. 1451-1453.
Margolis, S. and Rex, R.W., 1971, Endolithic
algae and micrite envelope formation in
York, p. 399-229.
Campbell, S.E., 1982, Precambr ian endo- c
Milliman, J.D., 1966, Submarine lithifica-
tion of carbonate sediments: Science,
Bahamian oolites are revealed by scan-
ning electron microscopy: Geological
liths discovered: Nature, v.229,
p.429-431.
c
v. 153, p. 994-997.
Mullins, H.T., Wise, S.W., Jr. , Gardulski,
Society of America, BUlletin, v.82,
p.843-852.
James, N.P., Kobluk, D.R. and Pemberton, c
A.F., Hinchey, E.J., Masters, P.M. and
Siegel, D.I., 1985, Shallow subsurface
Neumann , A.C., 1965, Processes of recent
carbonate sedimentation in Harrington
S.G., 1977, The oldest macroborers :
Lower Cambrian of Labrador : Science, c
diagenesis of Pleistocene periplatform
ooze: northern Bahamas: Sedimen-
Sound, Bermuda: Bulletin of Marine Sci-
ence, v. 15, p. 987-1035.
v. 197, p. 980·983 .
Kobluk, D.R., James, N.P. and Pemberton, c
tology, v. 32, p. 473-494 . Zankl, H. and Schroeder, J.H., 1972, Inter-
S.G., 1978, Initial diversification of
macroboring ichnofossils and exploi- c
Nelson, C.S. and Lawrence, M.F., 1984,
M~thane-derived high·Mg calcite sub-
action of genetic processes in Holocene
reefs off North Eleuthera Island,
tation of the macroboring niche in the
lower Paleozoic : Paleobiology, v. 4,
c
marine cement in Holocene nodules from
the Frazer Delta, British Columbia, Can-
Bahamas : Geologische Rundschau,
v. 61, p. 520-541.
p. 163-170. c
ada: Sedimentology, v. 31, p. 645-655.
Rao, C.P., 1981, Cementation in cold-water Strandline Diagenesis
Warme, J.E., 1975, Borings as trace fossils
and the processes of bioeros ion, in Frey, c
bryozoan sand, Tasmania, Australia:
Marine Geology, v. 40, p. m23-m33. Hanor, J.S ., 1978, Precipitation of beach-
R.W., ed., Study of Trace Fossils:
Springer-Verlag , New York, p. 181-229. e
Rao, C.P. and Green, D.C., 1983, Oxygen rock cements: mixing of marine and Petrography of Sea-floor and c
and carbon-isotope composition of cold
shallow-water carbonates of Tasmania,
meteoric waters vs . CO 2 degassing :
Journal of Sedimentary Petrolgy, v. 48,
Shallow Marine Burial Cements
c
Australia: Marine Geology, v.53 ,
p. 117-129.
Saller, A.H., 1986, Radiaxial calcite in Lower
p.489-501 .
Hardie, L.A ., 1977, Algal structures in
Bathurst, R.G.C ., 1959, The cavernous
structure of some Mississippian stroma- c
cemented crusts and their environmen- tactis reefs in Lancashire, England: (
Miocene strata , subsurface Enewetak tal significance, in Hard ie, L.A. , ed., Journal of Geology, v. 67, p. 506-521.
Atoll: Journal of Sedimentary Petrology, Sedimentation on the Modern Carbon- Bathurst, R .G .C., 1982, Genes is of (
v. 56, p. 743-762. ate Tidal Flats of Northwest Andros stromatactis cavities between sub-
Island, Bahamas: Johns Hopkins Press,
Baltimore , MD, p. 159-178.
marine crusts in Paleozoic carbonate
mud buildups : Journal of the Geological
C
Society, v. 139, p. 165-181. (
C
Limestones - The Sea-Floor Diagenetic Environment 33

r
Bromley, R.G., 1978, Hardground diagene - Mountjoy, EW. and Riding , R., 1981, Fore- Choquette, P.w. and Steinen, R.P., 1980,
sis, in Fairbridge , R.W. and Bourgeo is, slope stromatoporoid-renalcid bioherm Mississippian non-supratidal dolomite,
J., eds ., The Encyclopedia of Sedimen- w ith evidence of early cementation , Ste . Genev ieve Li mestone, Ill inois
o tology: Dowden, Hutch inson and Ross, Devonian Ancient Wall reef complex, Basin : evidence for mixed-water dolo-

c Stroudsburg, PA, p. 397-400 .


Davies , G.R. and Krause , H.R., 1975, Car-
bon and oxygen isotopic composition of
Rocky Mounta ins: Sedimentology, v. 28,
p. 299-321.
Richter, D.K. and FGchtbauer, H., 1978, Fer-
mitization, in Zenger, D.H., Dunham ,
J.B. and Ethington , R.L., eds., Concepts
and Models of Dolomit ization: Society of
Late Paleozoic carbonates - Canadian roan calcite replacement indicates for- Econom ic Paleontologists and Mineral-
() Arctic Archipelago - prelim inary results
and interpretations: Geological Survey
mer magne sian calcite skeletons: Sedi-
mentology, v. 25, p. 843-861.
ogists, Special Publication No. 28,
p. 163-196.
r
of Canada, Pape r 75-18 , p.215-220 . Sandberg, P., 1985, Aragon ite cements and Donaldson, J.A . and Ricketts, B.D., 1979,

c Davies , G.R., 1977, Former magnesian cal-


cite and aragon ite submarine cements
in Upper Paleozoic reefs of the Cana-
their occurrence in ancient limestone , in
Schneidermann , N. and Harris , P.M. ,
eds ., Carbonate Cements: Society of
Beachrock in Proterozo ic dolostone of
the Belcher Islands, Northwest Terri-
tories , Canada: Journal of Sedimentary
dian Arct ic: a summary: Geology, v. 5, Economic Mineralogists and Paleon - Petrology, v. 49, p. 1287-1294.

o p. 11-15.
Grotzinger, J.P. and Read , J .F., 1983,
tologists, Special Publication No. 36,
p.33-58.
Purser, B .H ., 1969 , Syn-sed imentary
marine lithification of Middle-Jurassic
Evidence for primary aragonite preci- Sandberg, P.A. and Popp, B.N., 1981, Penn- limestones in the Paris Basin : Sedimen-
pitat ion , lower Proterozo ic (1.9 Ga) sylvanian aragonite from southeastern tology, v. 12, p. 205-230.
o Rocknest Dolomite, Wopmay Orogen ,
northwest Canada : Geology, v. 11,
Kansas - environmental and diage-
netic implications (abstract): American
Read, J.F. and Grover, G.A., 1977, Scal-
loped and planar erosion surfaces, Mid-
o p.710-713.
James , N.P. and Klappa, C.F., 1983, Petro-
Association of Petroleum Geolog ists ,
Bulletin, v. 65 , p. 985 .
dle Ordovician limestones, Virginia :
analogues of Holocene exposed karst or
o genesis of Early Cambrian reef li me- Stoakes, FA, 1980, Nature and control of tidal rock platforms: Journal of Sedi-

o stones, Labrador, Canada : Journal of


Sed imentary Petrology, v. 53, p. 1051·
shale basin fill and its effect on reef
growth and termination : Upper Devo-
mentary Petrology, v. 47, p. 956-972.

o 1096.
Kendall , A.C., 1977, Fasc icu lar-opt ic cal-
nian Duvernay and Ireton Format ions of
Alberta, Canada: Bulletin of Canadian
Isotopic Geochemistry of Precipitates

o cite : a replacement of bundled acicular


carbonate cements: Journal of Sedi-
Petroleum Geology, v. 28, p. 345-411.
Tucker, M.E., 1983, Diagenesis, geochem-
Brand, U. and Veizer, J., 1981, Chemical
diagenesis of a multi-component car-
o mentary Petrology, v. 47, p. 1056-1062. istry, and or igin of a Precambrian dolo - bonate system - 2: stable isotpes: Jour-

o
r
Kendall , A.C., 1985, Radiaxial fibrous cal-
cite: a reappra isal, in Schneidermann,
N. and Harris, P.M., eds., Carbonate
mite: the Beck Spring Dolomite of east-
ern California: Journal of Sedimentary
Petrology, v. 53, p. 1097-1119.
nal of Sed imentary Petrology, v.51,
p.987-999.
Choquette, P.w., 1968, Marine diagenesis
Cements: Society of Economic Miner- Videtich, P.E., 1985, Electron microprobe of shallow marine lime-mud sediments :
rl alogists and Paleontologists , Spec ial study of Mg distribu tion in recent Mg insights from 0'80 and O'3C data : Sci-
V Publication No. 36, p. 59-78. calcites and recrystallized equivalents ence, v. 161, p. 1130-1132.
o Kendall , A.C. and Tucker, M.E., 1973, Radi-
axial fibrous calcite: a replacement after
from the Pleistocene and Tertiary: Jour-
nal of Sed imentary Petrology, v. 55,
Dickson, J.A.D. and Coleman , M.L., 1980,
Changes in carbon and oxygen isotope
o ac icular ca rbonate: Sedimentology,
v. 20 , p. 365-389.
p.421-429.
Walls, R.A., Mountjoy, E.W. and Fritz, P.,
composition during limestone diagene -
sis: Sedimentology, v. 27, p. 107·118.
o Lindstrom, M., 1979, Diagenesis of Lower 1979, Isotopic composition and diage- Davies, G.R. and Krouse, H.R., 1975, Car-

o r:
Ordovician hardgrounds in Sweden :
Geologica et Palaeontologica, v. 13,
p.9-30.
netic history of carbonate cements in
Devonian Golden Spike reef, Alberta,
Canada: Geological Society of America,
bon and oxygen isotopic composition of
Late Paleozoic calc ite cements , Cana-
dian Arct ic archipelago - preliminary
Lasem i, Z. and Sandberg, P.A., 1984, Trans- Bulletin, v. 90 , p. 963-982 . results and interpretation: Geological

o formation of aragon ite-dom inated lime


muds to microcrystalline limestones:
Wilkinson, B.H., Janecke, S.V. and Brett,
C .E ., 1982, Low-magnesian calcite
Society of Canada , Pape r 75 -1 B,
p.215-220.
Geology, v. 12, p. 420-423 . marine cement in Middle Ordovician Given, R.K. and Lohmann , K.C., 1985, Deri-
Lohmann, K.C. and Meyers, w.J., 1977, hardgrounds from Kirkfield, Ontario: vation of the original isotopic composi-
o Microdolomite inclusions in cloudy pris- Journal of Sedimentary Petrology, v. 52, tion of Permian marine cements : Jour-

o mat ic calcites - a proposed cr iter ion for


former high magnesium calc ites: Jour-
nal of Sedimentary Petrology, v.47,
p.47-59.

Strandline Diagenesis
nal of Sed imentary Petrology, v. 55,
p.430-439 .
Kerans, C., Hurley, N.F. and Playford, P.E.,
p. 1078-1088. 1986, Marine diagenesis in Devonian
Mazzullo, S.J., 1980, Calc ite pseudospar Asseretto , R. and Kendall , G.C., 1977, reef complexes of the Canning Basin ,
replac ive of mar ine acicular aragon ite Nature, or igin, and class ification of peri- western Australia, in Schroeder, J.H.
and implications for aragonite cement tidal teepee structures and related brec- and Purser, B.H., eds ., Reef Diagenesis:
d iagenesis : Journal of Sedimentary cias: Sedimentology, v. 24, p. 153-210. Springer-Verlag, New York, p. 357-380.
Petrology, v. 50, p. 409-423. Asseretto, R. and Folk, R.L. , 1980, Dia- Lohmann, K.C., 1983, Diagenetic history of
Macqueen, R.W. and Ghent , E.D., 1970, genet ic fabrics of aragon ite calcite and carbonate reservo irs - integra tion of
Electron microprobe study of magne- dolomite in an ancient peritidal-spelean petrogrpahic and geochemical tech -
sium distribution in some Mississippian environment: Triassic Calcare Rosso , niques , in New Ideas and Methods for
ech inodern limestones from Western Lombard ia , Italy: Journal of Sedi- Exploration for Carbonate Reservoirs,
Canada: Canad ian Journal of Earth Sci- mentary Petrology, v. 50, p. 371·395. Amer ican Assoc iat ion of Petroleum
ences, v. 7, p. 1308-1317. Geolog ists , Short Course Notes , Dallas,
TX, Apr il 16-17, 1983.
c
34 Diagenesis Geoscience Canada Reprint Series 4 c
c
Lohmann, K.C., in press, Covariant carbon Lohmann, K.C., 1988, Geochemical pat- Wilkinson, B.H., Owen, R.M. and Carroll,
c
and oxygen isotopic trends in calcitized terns of meteoric diagenetic systems A.R., 1985, Submarine geothermal c
marine cements - estimation of marine
isotopic signatures:Journal of Sedimen-
and their application to studies of paleo-
karst, in James, N.P. and Choquette,
weathering , global eustacy and carbon-
ate polymorphism i n Phanerozoic c
tary Petrology, in press.
Marshall , J.D. and Ashton , M., 1980, Iso-
P.W., eds., Paleokarst: Springer-Verlag,
New York, p. 58-80 .
marine oolites: Journal of Sedimentary
Petrology, v. 55, p. 171-183. c
topic and trace element evidence for
submarine lithification of hardgrounds
Mackenzie, ET. and Pigott, J .D., 1981, Tec-
tonic controls of phanerozoic sedimen- Other References Cited In Text
c
in the Jurass ic of Eastern England : Sedi- tary rock cycling : Journal of the Geologi- (
mentology, v. 27, p. 271-289. cal Society of London, v. 138,p. 183-196. Alexanderson , T.F. and Schneidermann,
Mattes, B.W.and Mountjoy, E.W., 1980,Bur- Milliken, K.L. and Pigott, J.D ., 1977, Varia- N., 1973,Stable isotope relationships in c
ial dolomitization ofthe Upper Devonian
Miette buildup, Jasper National Park,
tion of oceanic Mg/Ca ratio through time
- implications for the calcite sea: Geo-
pelagic limestones from the central
Caribbean : Leg 15 Deep Sea Drilling c
Alberta, in Zenger, D.H., Dunham, J.B.
and Ethington, R.L., eds., Concepts and
logical Society of America, South-Cen-
tral Meeting , Abstracts, p. 64-65.
Project , in Edgar, N.T., Saunders, J.B., et
el. , eds., Initial Reports of the Deep Sea c
Models of Dolomitization: Society of
Economic Paleontologists and Mineral-
Pigott, J.D., 1981, Global tectonic control of
secular variations in Phanerozoic sedi-
Drill ing Project, Vol. XV, p. 795-803.
Berner, R.A., 1971, Principles of Chemical c
ogists , Special Publication No. 28 ,
p.259-297.
mentary rock/ocean/atmospheric
chemistry (abstract) : American Associ-
Sedimentology: McGraw-Hili, New York,
240 p.
c
Popp, B.N., Sandberg , P.A. and Anderson, ation of Petroleum Geologists, Bulletin , Broecker, W.S., 1974, Chemical Ocean- c
T.E, 1981, Coord inated textural isotopic
and elemental analysis of constituents in
v. 65, p. 963.
Pigott, J.D. and Mackenzie, F.r., 1979, A
ography : Harcourt, Brace and Jovano-
vitch, New York, 214 p. c
some Middle Devonian limestones
(abstract): Geological Society of Amer-
signature of paleo-ocean and atmo-
spheric chemistry: Geological Society
Cayeux, L., 1935, Les Roches Sedimen-
taires de France: Roches carbonatses : c
ica, Abstracts with Programs, p. 531.
Ross, R.J., Jr., Jaanusson, V. and Fried-
of America, Abstracts with Program ,
p.495-496.
Masson, Paris, 436 p.
James, N.P., 1983, Reef environment, in c
man, I., 1975, Lithology and origin of
Middle Ordovician calcareous mud-
Popp, B.N., Anderson, T.F. and Sandberg,
P.A., 1986, Brachiopods as indicators of
Scholle, P.A., Bebout, D.G. and Moore,
C.H ., eds ., Carbonate Depositional
c:
mound of Meiklejohn Peak, Southern original isotopic conpos itions in some Environments: American Association of
Petroleum Geologists , Memoir 33 ,
c
Nevada: United States Geological Sur-
vey, Professional Paper 871, 48 p.
Paleozoic limestones : Geological
Society of America, Bulletin, v.97, p.345·440. c
Sears, S.D. and Lucia, EJ., 1980, Dolomiti-
zation of northern Michigan Niagara
p. 1262-1268.
Sandberg , P.A., 1975, New interpretations
James, N.P., 1984, Shallowing-upward
sequences in carbonates , in Walker, c
reefs by brine refluxion and freshwater/
seawater mixing , in Zenger, D.H., Dun-
of Great Salt Lake ooids and nonskeletal
carbonate mineralogy: Sedimentology,
°R.G., ed., Facies Models, Second Edi-
tion : Geological Association of Canada, c
ham, J.B. and Eth ington, R.L., eds .,
Concepts and Models of Dolomitization:
v. 22, p. 497-537.
Sandberg, P.A., 1983,An oscillating trend in
Geoscience Canada Reprint Series 1,
p.213-228 .
c
Society of Economic Paleontologists Phanerozoic non-skeletal carbonate James, N.P., 1984, Reefs, in Walker, R.G., c
and Mineralogists, Special Publication
No. 28, p. 215·237.
mineralogy: Nature, v. 305, p. 19-22.
Vail, P.R., Mitchum, J.R. and Thompson, S.,
ed., Facies Models, Second Edition :
Geological Association of Canada, Geo- c
Veizer, J. and Hoefs, J., 1976, The nature of
180 /180 and 13C/12C secular trends in
11I,1977, Seismic stratigraphy and global
changes in sea-level, part 4, in Peyton,
science Canada Reprint Ser ies 1,
p.229-244. c
sedimentary rocks : Geochimica et Cos-
mochimica Acta, v. 40, p. 1387-1395.
C.E., ed., Seismic Stratigraphy: Ameri-
can Assoc iation of Petroleum Geolo-
Kendall , A.C., 1978, Evaporites, in Walker,
R.G., ed., Facies Models, Second Edi- c
Walls, R.A., Mountjoy, E.W. and Fritz, P. ,
1979, Isotopic composition and diage-
gists , Memoir 26, p. 83-97.
Veizer,J., Fritz, p. and Jones, B., 1986,Geo-
tion : Geological Associat ion of Canada,
Geoscience Canada Reprint Series 1,
c
netic history of carbonate cements in chemistry of brachiopods: oxygen and p.259-296.
Devonian Golden Spike reef, Alberta,
Canada: Geological Society of America,
carbon isotopic records of Paleozoic
oceans : Geochimica et Cosmochimica
Murray, J.L. and Renard, A.F., 1891, Report
on deep sea deposits based on the c
Bulletin, v. 90, p. 963-982. Acta, v. 50, p. 1679-1696.
Wilkinson, B.H., 1979, Biomineralization,
specimens collected during the voy-
age of H.M.S. Challenger in the years c
Temporal Variations In the Mineralogy
and Isotopic Composition of Sea-floor
paleoceanography and the evolution of
calcareous marine organ isms: Geology,
1872-1876, 525 p. [Reprinted by
Johnson Reprint, London, 1965. J c
Precipitates v. 7, p. 524-527.
Wilkinson, B.H., 1982, Cyclic cratonic car-
Murray, J. and Hjort, J., 1912, The Depths of
the Oceans: Macmillan , London. 831 p.
c
Fischer, A.G., 1981, Climatic oscillations in
the biosphere, in Nitecki, M.H ., ed.,
bonates and phanerozo ic calcite seas:
Journal of Geological Education , v. 30,
e
Biotic Crises in Ecological and Evolu- p.189-203. (
tionary Time: Academic Press , New
York, p. 103-133.
Wilkinson, B.H., Bucynski, C. and Owen,
R.M., 1984, Implications from Upper c
Lowenstam, H., 1963, Biologic problems
relating to the composition and diagene-
Pennsylvan ian calcite-aragonite ooids
of southeastern Kansas: Journal of
Originally published in
Geoscience Canada v. 10 Number 4 c
sis of sediments, in Donnelly, T.W., ed.,
The Earth Sciences: University of Chi-
Sed imentary Petrology, v.53,
p.932-947.
(December 1983)
Revised 1988
c
cago Press, Chicago, p. 137-195.
vV
c
\\1 (

sy --- \/)/ (
C
Limestones - The Meteoric Diagenetic Environment 35

r: ~The meteoric diagenetic env iron- large skeletons of the same mineralogy
/~ent is one with many apparent contra- change more slowly. Individual grains

o dictions. For example, the main process


is carbonate dissolution , yet here is
will also alter at diffe rent rates, depend-
ing upon the crystal size and relative
c where soft sediment is transformed into
hard limestone, the same waters that
amount of organic material. Finally,
porosity and permeability of the sedi-
precipitate CaC0 3 when mixed may dis- ment, which govern the rate at which

c solve CaC0 3 ; while spectacular caves


are being excavated, delicate fossils are
fluids flow through and the length of
time they are in contact with the sedi-
being preserved. ment or rock, affect the speed at which
Limestones - The The environment has been studied changes take place.
more intensively than any other diage- Perhaps the most "cruclal extrinsic
Meteoric Diagenetic netic realm, yet we are really only rea- factor is climate; in areas of extensive
Environment sonably confident about processes and rainfall and warm temperatures diagen-
o products that occur above the water
table.
esis proceeds quickly and with great
vigour, whereas in warm arid regions,
Noel P. James The wide variety of limestones that because of little water, sediments are
r Department of Geological Sciences
Queen's University
result from meteoric diagenesis -
often beginning with the same sedi-
often unchanged for long periods, or
are virtually unaffected by subaerial
Kingston, Ontario K7L 3N6 ment - are the end result of several exposure. As the dissolving power of
reactions, governed by intrinsic and fresh water is largely controlled by bio-
( Philip W. Choquette extrinsic factors (Figure 2) that may logically produced CO2 , the amount of
Department of Geological Sciences proceed at different rates for varying large vegetation is also important.
University of Colorado lengths of time. The most important Finally time is critical: the longer a sedi-
Boulder, Colorado 80309-250 intrinsic factor is original mineralogy: ment is exposed in the meteoric
sediments composed of several CaC0 3 environment, the more intensive the
minerals , dominated by aragonite and changes will be.
INTRODUCTION magnesium-rich calcite (Mg-calcite),
Carbonate sediments, born in the sea, which are metastable with respect to THE METEORIC SETTING
remain largely unaltered while bathed in fresh water, alter most; those sedi- As outlined in the introduction to this
c their embryonic fluids of high ionic
strength. With time, however, the com-
ments composed only of various calcite
minerals alter least. Grain size control
series on limestone diagenesis, the me-
teoric environment can be subdivided in
position ofthe pore waters will inevitably the rate at which these components most general terms into vadose and
change , and if exposed to circulating change; fine-grained sediments and phreatic settiogs.(Figure 3).
ground water, the sediments may finely crystalline particles, because of ~he water table marks the top of the
undergo profound and geologically their large ratio of surface area to parti- phreatic zone and represents the level
rapid diagenesis (Figure 1). cle size, change most rapidly, whereas at which hydrostatic pressure is equal
to atmospheric pressure. The most
common aquifers are unconfined, or
open to the atmosphere, and the hydro-
r static level is within the water-bearing
unit. There are two types of gravity.
induced flow in this situat ion (White,
1969). Under conditions of diffuse flow

METEORIC DIAGENESIS

CONTROLS SETTINGS -. C
INTRINSIC ;l"" fi ll
~ ~ : ~ : a / .' .
MINERALOGY
.~ • .,'-"<>.

ll";~I
GRAIN SIZE
POROSITY" PERMEABlUTY
ZONE

EXTRINSIC
.. ~ .

CUIoIATE WATER TABLE


. ~

VEGETATION
PHREATIC
TIME ZONE
I ~
'r ..XING ZONE

Figure 1 Theshore of Bimini, The Bahamas. The rock on the right is carbonate sediment that Figure 2 The principal controls on, and
has been cemented by exposure to meteoric waters over the last several thousand years. settings of, meteoric diagenesis.
c
36 Diagenesis Geoscience Canada Reprint Series 4 c
c
there is a well-defined water table and Unconfined aquifers characterized limestone via a network of tiny fractures
c
water movement obeys or nearly obeys
Darcy's law. The sediment or rock has
by diffuse flow are most usefully divided
into the vadose zone, above the water
or small pores. In contrast, vadose flow
(Thrailkill, 1968) is the relatively rapid
c
relatively homogeneous porosity and table; the active, shallow, freshwater movement of water downward via joints, c
permeability characteristics, karst phreatic zone or lenticularphreatic zone large fissures and sinkholes, ofte ~ 1.,":/ (
landforms are rare and subdued on a
generally low-relief surface , small cav-
(Jakucs, 1977), below the water table;
and the sublenticular mixing zone, also
directly to the water table. ~""~
The Wafer Table. Dl<;S1:>W . ~ ,,,IT'
e c
ities are somewhat randomly arranged referred to as the transition, mixing, As will be discussed later;-CUie water
and flow is relatively deep. In contrast, diffusion or dispersion zone. The gen- table is'a surface of great inportance in C
under free flow conditions water moves
through integrated conduits which func -
eral relationships of these settings are
shown in Figure 3.
carbonate diagenesis. In older, pre-
Pleistocene limestones its former pre-
c
tion like a series of three-dimensional The Vadose Zone. sence and position can often only be C
subterranean rivers. The water table is Rainwater, meltwater or runoff enters a recognized approximately if at all
discontinuous or difficult to recognize at carbonate sequence either directly on because of long and complex diage- C
all, but there is nevertheless a continu-
ous potentiometric surface. Diffuse
bare rock or through a calcrete or soil.
The zone of infiltration (Figure 3) is a
netic histories . Some criteria that can be
helpful in delineating paleowater tables
C
flow aquifers with a well-defined water realm of complex carbonate-water in- are presented later in this article. On C
table are typ ically developed in newly teraction. Although water may pass relatively small , present-day limestone
exposed young carbonate sediments, directly into the rock, in most situations islands the water table is usually very C
but with time and diagenesis aquifers
evolve into the free flow type charac-
there is a soil or protosoil on top of
bedrock. Biological activity in the soil
gently bowed upward toward the island
interior, as a rule rising less than a metre
C
terized by conduit flow and a discon- not only alters the composition of the per kilometre (Figures 3 and 4). Beneath C
tinuous water table. In this paper the fresh water but, in many cases, induces widespread carbonate platforms and
focus is on diffuse flow aquifers. carbonate precipitation. This zone is mainland carbonate plains underlain by
C
The other entirely different type of subject also to evaporation or evapo- flat-lying strata the water table appears C
flow is confined. The aquifers are transpiration, especially in the tropics, to have almost imperceptible relief (Fig-
bounded by aquitards (impermeable so that some of the downward percolat- ure 3). For example, two of the better C
layers), and are not connected vertically
to the atmosphere. Waterflow is by pres-
ing waters are drawn back up to the
surface, again leading to carbonate
known karst terrains of North America
- the northern Yucatan and the south-
C
sure and will rise above the level of the precipitation. ern peninsula of Florida (Back and C
aquifer inwells (artesian flow). Confined The underlying and more extensive Hanshaw, 1970; Back et et., 1976)
aquifers are particularly important as zone of gravity percolation is charac- regions of about 50,000 km2 - have C
conduits by which fresh water can flow terized by pores variably filled with watertable elevations which reach max-
deep into sedimentary basins and con- water andlor air or organically produced ima of only a few metres and mostly less
C
siderable distances out beneath the gas. Under conditions of vadose than 20 metres, respectively. C
continental shelf. seepage water trickles through the
C
C
THE METEORIC C
ENVIRONMENT ~
C
C
C
C
SHALLOW PHREATIC LENTICULAR ZONE
(FRESH WATER) .> -: >:MA~INE' ::
-: :"::::\::'2 :. '.'
c
~
~
~
r :
: . : ...'.: . .::- ·.: · · PHREATIC ~ e
MIXING ZONE (BRACKISH WATER)
? .. . . .
. ~ .. ..... :-:: ::.:.::::.-:: ::::.-:::.:..: .:.:.:-: . .. ZONE
.
<.".::'
-
c
::: ::::::::::::::::::::::::.:::::: ::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::::: ::::.:.: ::::::::::.::::::.::::::::.:.::: ::::. :: :.:: (.S~~ ~.~~~ c
-:.:.:-:.:-:-:-:..:.::-:-:-:-:.:.: -:-:-:".::-:-:..::":-: DEEP PHREATIC ZONE .:-:-:.:":.:-:..:.::..:.::..::..:.:.::...: : : : : : . : : :." ...":-. :-:- :-:-:"....:
:::::::::::::::::::::::::::::::::: :::::::::::::::::::::::::: .(~~l:~~. ~~:r.~~). ::::::::::::::::.::::::: ::::::::::::::::::::': :::::" .::':::::::::::'.::::.: '::::::::.:: C
.... ... .. . .. .. . . . . . . . .. \.
. . . . . . . . . . ... .. .. .. . . ... . .. ... .. . . . . . . . . . . . . ... . .. . . . . . . . .. . .. . ... . . .. . . . .. . .. ..... . ... . .-. . . . . .. - . ,

C
Figure 3 A sketch outlining the main zones of the meteoric diagenetic environment.
C
C
C
~
( ~y~-'~~~'\tJt!'~ Q~J fhJ~ kJ«I-!?Vv~ ;nC-rr~ ..
~ :::;6171) L,.-. l r- ~ 0 - l .;;) ;:'V'v""'.- J. I'Yr.f t.. /Al 0 /~
C p.
(J" ,f'. -
~9' O l!.imestones "f The Meteoric Diagenetic Environment ... l,I C/V'-
-
....... ~ I

37

C tJ' ~~ fv'~t..fo"~-l~ (ODD~ clJ'~ CO~1l <;:kx-l<J..t, ri


C' (oJ"' > w~ en s: 6a ~~ ;.-v-- F"f7.s:k
f-
The r Jnticular Zane. less, the important point is that only relationship. In strongly dynamic sys-
(' This zone has as its lower boundary minorelevation above sea level can lead tems, "tongues" of fresh water may
either an aquiclude or a water mass of to deep penetration of meteoric water extend many tens of kilometres sea-
G- different composition (Figure 4). A and attendant diagenesis. ward beneath the continental shelf in
r common situation today is one in which
the freshwater lens "floats", iceberg
Inthiszonewater, which fills the avail-
able pore spaces, is actively moving.
confined aquifers (Manheim, 1967;
Johnson, 1983).
C style, balancing on a column of denser Except in regions of relatively high ele- The Transition or Mixing Zone.
marine water beneath it. Early ob- vation, water movement in the lenticular The brackish water zone at the base of
C servers (DuCommun, 1828; Ghyben, zone is largely horizontal or subhorizon- the freshwater lens is of great geologic
1888-89; Herzberg, 1901, cited by Fet- tal (Figures 3 and 4) and directed toward as well as practical interest. It has been
C ter, 1980) noted in unconfined coastal the local baselevel of erosion which may suspected since the early 1970s that
C aquifers that the depth to which the
lenticular zone extends below sea level
be a spring, river or other inland water
body, or the ocean.
this zone may be a site where earlY
dolomitization take.s.place (see Morrow,
(
is about forty times the height of the If the aquifer is very permeable and this volume). Processes that occur in
o water table above sea level. This rela-
tionship is commonly called the Ghyben-
there is dynamic water movement in the
lenticular zone, the interface may be
the transition zone are still poorly un-
derstood, but its hydrologic and chemi-
C- Herzberg principle (e.g., Todd, 1980). deeper and displaced seaward toward cal characteristics are becoming better
The precise configuration of the lens is the coast compared to what would be known through studies such as those
O dependent also upon, amongst other predicted by the Ghyben-Herzberg rela- on which this brief discussion is largely
o things, the permeability of the rock and
rate of ground-water recharge (Bud-
tionship, because the marine water
beneath the lens is actively moving
based: Bear and Todd(1960); Back and
Hanshaw (1970); Back et al. (1976);
o demeir and Oberdorfer, 1986). Regard- rather than static, as assumed for the Vacher (1974); Plummer et al. (1976);

o SMALL SAND CAY OR OCEANIC ATOLL


Wigley and Plummer (1976); and Back
et al. (1979, 1984, 1986).
o In general, the transition zone is a

o product of physical and diffusive mix-


ing. It is thickest in more permeable
o strata where these mixing processes

~ mm;:-~2 ~~@»
are more effective, and also it isthickest
toward the coast because of both the

c '~; ~ .......
... :: :;:..;: :.:: : : : : : : : : :: : :: : " . _. . __ ._-- - - _.. -- ... - .. . ...... .
higher velocities of ground-water flow
near coastal discharge points and the
o .. .. ..
'

,
, • • I • ,
influx of seawater drawn shoreward and
upward in the shallow subsurface to
a LARGE CARBONATE PLATFORM replace the discharge.

o Salinity profiles in the transition zone


- as well as profiles of water velocity,
o concentrations of single and multiple
ion species and such water-dependent
o mass properties as electrical conduc-

o tivity - have the form of an s-shaped


curve (Figure 5). Because flow velocity
o and salinity are inversely related, pro-
files of the two essentially mirror one
o another; therefore, flow will be faster

o and waters more dilute in the upper part


of the transition zone. The importance
o TECTONICALLY UPLIFTED TERRANE of these relationships here is that both
conditions should have a bearing on
c whether carbonate will dissolve or
~~~ t precipitate.
It is important to be aware that,
c ~ although the transition zone is often
portrayed as being quite thin compared
to the freshwater zone above it, the
zone can be quite thick in permeable
carbonates of oceanic islands. Figure 5
illustrates the variations in transition
zone thickness that Vacher(1974) found
in the main freshwater lens on Ber-
Figure 4 A sketch showing different scales and configurations of freshwater lenses . muda, where the transition zone is
......
,'" ,
c
38 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
c
c
E c
W
c
~
WATER
-l
CD Page l Fm
et
I-
0:
\ (low permeab il i ty) c
Figure 5 A hydrological case study : map
of the water table and profiles of the transi-
UJ
I-
-c
~
\
\
c
tion (mixed-water brackish) zone in the main ~ 15
\
-,
!.-- <,'00% _ _
/ 1 ......
./ C
(Devonshire) lens on the main island of Ber- o -,

muda . (Mod ified from Vacher, 1974).


-l
UJ
CD 20L-
./ / 1 Belmont Fm .
---l.--....::........: --=-_--'
'(h igh permeab il ity)
C
:x:
l-
m
HYDROGEOLOGIC CROSS SECT ION C
ll. WITH RELATIVE SALINITY CONTOURS THRU
UJ
o TRANSITION ZONE C
TRANSITION ZONE
PROFILES IN 5 WELLS
C......
o 50 100
C
REL. SALINITY, %

C
C
IK m
C
V1lJ Pagel Fm C
March 1974 ' . , C
AVG . ELEVATION OF WATER TABLE C
C
C
C
C
C
C
® C~~~:'~N <. \~'t~~\
SIMPLE
,~,\~~~\~\
~,~~\\ ~ \;\~ \\:~\ \\\
;---7" PRECIPITATION
e-;
C
(j) CORROSION ~ ;X ~~ \ \ \~ \ \\
(C02 LOSS)
C
C
WATER TABLE ~~ ~ L..----'~
~ ~ DEGASSING
C
C
FRESH WATER
.s> E
.> MARINE
l_
WATER C
C
MIXED WATER C
Figure 6 A sketch illustrating the areas of dissolu tion (corrosion) and prec ipitat ion of carbonate dur ing the exposure of calc ite limestone to
C
percolating meteoric waters ; surface features are sketched in Figures 12 and 14, detail of square in Figure 21. (.

<---
(
t:
( Limestones - The Meteoric Diagenetic Environment 39

c
c often as thick as or thicker than the processes which are happening at rosion is the dissolution brought about
r freshwater lens itself (as defined by the
1% relative salinity contour) . To a close
once is much like learning to juggle:
having finally mastered the art of keep-
by rainfall on bare rock surfaces
(Figure 6).
o approximation the Ghyben-Herzberg ing three objects in the air, you are Biogenic corrosion. Air in the soil

c relationship, which assumes no mixing


of waters, would apply in effect to the
handed several more and told to put on a
good show!
zone has a significantly higher Pco 2
than the atmosphere because of plant
o part of the lens bounded by the 50% The reaction between carbonate
minerals and meteoric waters in general
respiration and decay of organic matter.

o relative salinity surface and the water


table (Vacher, 1978). is most simply expressed by the
As rainwater percolates through the
soil, addition of biogenic CO2 increases
o Deep Phreatic.
Water in the deeper phreat ic zone may
equation
CaC03 + H20 + CO2 = Ca2 + + 2HCO; .
the CO2 content , typ ically to an equiv-
alent PC0 2 of about 10 - 1.0 atm. Values
C~ be slowly moving or almost stagnant
The exact mechanisms of the CaC0 3 of 1-2% are common, but in some poorly
ground water, or in the case of young
ventilated tropical soils may be as high
\ exposed carbonate platforms or
- CO2 - H20 chemical system are com-
plex, involving a series of reversible and as 20-25% (PC0 2 = 1O- 0 .7 atm). Conse-
o islands, it may be seawater.
An important result of the dominance
mutually interdependent reactions, all quently, waters emerging from below
o of vertical, gravity-controlled seepage
proceeding at different rates and each
regulated by different equilibrium con-
the soil are very "aggressive " chemi-
cally and can rapidly dissolve orders of
o and flow in the vadose zone, compared
with horizontal water movement in the
straints. Recent reviews can be found in
Bathurst (1975), Plummer et al. (1979),
magnitude more.carbonate than could

o phreatic zone, is that large solution cav-


ities formed in the two zones have dif-
Bogli (1980), and Drever (1982).
ordinary rainwater.
Mixing corrosion. Runnels (1969)
o ferent elongation , commonly vertical in
Under natural conditions this equilib-
rium reaction is represented by (1) dis-
has emphasized that mixing of two solu-
tions which are both saturated with
c the vadose zone, but mostly horizontal
along and for a short distance below the
solution of carbonate, (2) oversatu- respect to a given mineral may lead to a

o water table. Caves that clearly have


formed in brackish-water transition
rat ion and (3) precipitation of new
carbonate. Diagenetic processes would
mixture which is either supersaturated
or undersaturated depending upon the
o zones have been documented along
be relatively simple if this reaction were
all that was involved, but dissolution and
character of the original solutions and
on the minerals in question . These non-
o the eastern Yucatan coast (Back et el.,
1979), a setting where one would expect
precipitation rates are often slowed linear relations can result in extensive

o them to be elongate parallel to the main


flow direction, as suggested in Figure 3.
down or halted altogether by kinetic fac-
tors. Kinetics are particularly important
subsurface limestone alteration .
Mixing of waters in the subsurface
o Where dissolution in the phreatic zone
in slowing down precipitation and thus
maintaining supersaturation.
can be expected to bea common pheno-
menon in all carbonate terranes. In the
o is strongly influenced by flow rates,
transition-zone caves may tend to be
Dissolution (Corrosion). simplest cases this may involve (1) mix-
o larger and more numerous toward the
coast where flow rates are particularly
Dissolution and precipitation of CaC0 3
are controlled in most natural situations
ing of different meteoric waters, (2) mix-
ing of meteoric and deeper subsurface
o high.
by the flux of CO2 in and out ofthe water.
Addition of CO2 by any means will drive
br ines, and (3) mix ing of meteoric

o Changes in base level due to tectonic


disturbances or world-wide sea level
the reaction to the right, resulting in
waters and seawater.
When carbonate ground waters are

o changes must inevitably shift the posi-


dissolution. The simplest way is to
increase pressure or decrease temper-
mixed, the resulting saturation state
depends upon (1) the PC0 2, (2) the tem-
o tions and spatial relationships between
the major hydrologic zones of the mete-
ature. Kinetic effects do not seem to be
significant. In the meteoric environ-
perature, (3) the ionic strength (salin-
o oric environment.
ment, dissolution (corrosion) is brought
ity), (4) the degree of calcite saturation,
and (5) the pH of the end member solu-
o DISSOLUTION AND PRECIPITATION
It is well kn that limestone d' -
about in several ways (Figure 6), some
of which are quite unexpected. The
tions prior to mixing.
Chemically, the simplest type of mix-
reader is referred to excellent treat-
...§pl\l en ex osed to fres ing occurs when two bodies of meteoric
ments of th is topic by Thrailkill (1968)
( Although the processes are easily water, isolated from contact with the
and Bogli (1980).
observed and the general theory is well atmosphere and each at equilibrium but
Simple corrosion. The amount of
G understood, some of the principles gov-
CO2 dissolved in water open to the air
with different CO 2 contents , come
erning the dissolution and precipitation together (Figure 6). The resulting mix-
depends upon the part ial pressure of
of carbonate are still poorly known. This ture will lie somewhere along the
c is because we must deal with a multi-
component system simultaneously
CO2 (PC0 2 ) in the air at the air/water
interface. Calcite is soluble to the extent
straight dashed line joining A and B in
Figure 7, depending upon the propor-
c involving all three natural phases -
gas, liquid and solid. An additional com-
of about 12 to 15 ppm in pure water
(depending upon the temperature).
tions of each.The composition will move
up and to the left until the saturation
plicating factor is that in perhaps the Rainwater, however, is in equilibrium line is reached, with dissolution occur-
with atmospheric CO2 , which averages
" more important case, the transforma-
tion of sediment into limestone, we must about 0.03% by volume (PC0 2 about
ring in the process. This has been called
"mixing corrosion " by many authors,
also deal with a suite of several different 10- 3 .5 atm) and so is in reality an but Wigley and Plummer (1976) prefer

I
minerals. Trying to understand all the extremely weak acid. Thus simple cor- to call it the PC0 2 effect, because

,-.
c
40 Diagenesis Geoscience Canada Reprint Series 4 c
c
there are other types of mixing corro- ventilated caves this is more than bal- tions . As might be expected, mixing of c
sion as outlined below. This process is
most effective when each of the waters
anced by precipitation from waters
supersaturated with respect to calcite.
waters with varying pH may also lead to
corrosionwith the degreeof undersatura-
c
mixed is saturated with respect to the When otherwise similarly saturated tion increasing with decreasing pH. c
calcite. If one of the waters is supersatu-
rated, then the effect is diminished or
solutions with differing ionic strengths
are mixed, appreciable undersaturation
Undersaturationcan also resultfrom a
decrease in Ca2 + concentration in sur-
c
negligible, as can be seen in Figure 7 by
joining waters of compositions A and C.
may result. In natural systems, because
waters of differing salinity generally
face streams during times of high flow,
which then descend to the water table by
c
In natural systems this mixing can be have unlike PC0 2 and pH values and are vadose flow and mix with ground water. c
envisaged as the mixing of high Pco 2 at different saturation states when Hydrostatic corrosion. As the (
vadose water with low Pco 2 phreatic mixed, the results may bequite variable; hydrostatic head increases in the phre-
water. The effect is much reduced, how- a spectrum of expected situations has atic zone, so pressure increases, and c
ever, if the vadose water is in equilib-
rium with a low PC0 2 (e.g., vadose
been synthesized by Plummer (1975).
Although the precise curves for any
thus fluids are able to dissolve more
carbonate . This process was thought by c
flow), the phreatic water is in equilib- given pair of variables are different, the many European karst workers to be at
least as important as mixing corrosion in
c
rium with a high PC0 2 (because of slow results follow the same general trend
(Figure 8), showing that as seawater the subsurface (Jakucs, 1977). c
degassing), or if the vadose seepage or
ground water is supersaturated with
mixes with carbonate-bearing ground
water the mixtures initially become
Oversaturation and Precipitation.
Under this topic we must consider two c
respect to calcite.
A similar corrosion effect may be
increasingly undersaturated with reactions: (1) a first-order reaction in
which precipitation occurs because of
c
achieved by mixing waters of different
temperature. This can occur when
respect to calcite. With continuing addi-
tion of seawater undersaturation Pco 2 variations in the meteoric water, c
vadose seepage is cooled at the water
decreases, so that mixtures containing
large amou nts of seawater are oversatu-
here called water-controlled precipita-
tion, andlor (2) a second-order reaction
c
table. If the system is closed to PC0 2,
then the effect is minimal; but if it is open
rated. Once in the field of oversatura- in which precipitation is brought about c
to Pco 2 , changes as small as 1°C can be
tlon, precipitation should result but is
generally inhibited kinetically by high
by differences in CaC0 3 mineral solu-
bility, here called mineral-controlled c
significant. In reality, however, in well- Mg2+, PO~- and SO~- concentra- precipitation. .
J'/ Q'v'" <v- c
)J 1 {I\","
.;,\\ J,/.fr[. v[v.
c
OVERSATURATION
I
/'VI I' /1''1 t-v(.I
w· c
20 c
>< 1.0 c
III
Q
z
0.8 Undiluted
Seawater~ c
z 0.6 OVERSATURATION c
oj: 0.4 c
e(
~ 0.2 /
Calcite-Saturated
Fresh Groundwater c
~
l-
e(
c
tn
w -0.2
c
I-
(j -0.4 · .
c
..J
-e
~.-.""'--'--'

-0.6 ::· :: :: :: ::: : :: :: :: :: : UNDERSATURATION ::.


c
(J
.· . . . . . . . . . . . . . . . . . . . . . . . . . .. c
-0.8
o 20 40 60 80 100 e
5 10 15 20 25 30 % SEA WATER IN MIXTURE L
4
EQUILBRIUM ~02(atm)X 1 0 C
Figure 7 A diagram illustrating the non-linear relationship
Figure 8 A generalized diagram based on families of curves from C
Yucatan, Bermuda and Florida illustrating the effect on calcite sat-
between equilibrium PC0 2 and dissolved CaC03- The mixing uration in groundwater by mixing waters of different ionic strength, in C
this case seawater and meteoric groundwater. The curve is a spec-
of waters such as A andB in any proportion will result in undersatura-
tion. The mixing of waters such as A and C will lead mostly to trum ofblends representing the mixing of seawater with a groundwa- C
oversaturation. (After Thrailkill, 1968). ter that is exactly saturated with respect to calcite.
C
C
C
(
( Limestones - The Meteoric Diagenetic Environment 41

c.
c Water-controlled precipitation.
Precipitation of calcite (low magnesium
dynamic drive is reached that is suffi-
cient to overcome the kinetic problem.
in relative terms, magnesium-calcite
components with more than 12 mole%
(
calc ite, i.e., calci te with less .~ As rates are commonly the main pro- MgC0 3 should be the most soluble and
o mole% MgC03 ) can occur only under blem given sufficient time precipitation so alter the most rapidly, followed by

c conditions of oversaturation. From the


earlier equatl ori it can be seen that one
will occur.
At our present level of understanding ,
aragonite and magnesium calcites with
about 12 mole% MgCOa and then mag-
( way in which this may be achieved is by it seems that the phreatic lens and tran- nesium calcites with less magnesium,
removing some CO2 from the system, sition zones in calcite-only systems are the least soluble phase of all being cal-
o most simply by heating the water,
decreasing the pressure, or evapora-
zones of dissolution, and if, cementa-
tion does take place there, the process
cite with virtually no magnesium . In
( addition, many of these components,
tion. Nearthe top ofthevadose zonethis by which it does so is poorly understood. because they are either biogenic or are
c. occurs by either evaporation or loss of
CO2, Assimilating plants also can take
An exception might occur near the
shoreline where CO2 evasion, induced
precipitated from seawater and have
variable microstructures, relatively high
( their CO2 from the water, causing pre- by tidal pumping, is important (Hanor, trace cation contents as well as organic

o cipitation. Vadose waters that are at


equilibrium with a high PC0 2 degas and
1978).
Mineral-controlled precipitation.
and fluid inclusions, are slightly more
soluble than pure minerals. In certain
o precipitate carbonate when emerging Aragonite, magnesium-calcite (HMC) situations grain-microstructural com-

o into a cave or the atmosphere with a


lower PC0 2'
and calcite (LMC) are the CaC0 3 miner-
als that make up most shallow-water
plex ity can override thermodynamic
restraints (Walter and Morse, 1985). In
o If the CO 2 content of the water carbonate sediments. The processes of
dissolution described above are equally
the Pleistocene Miami Oolite for, exam-
ple, aragonite ooids have dissolved but
o remains constant as in the phreatic
zone, for example, where it is isolated
from contact with the atmosphere, then
applicable to these minerals, but pre-
cipitation is another matter. Because we
magnesium-calcite foraminifera are
unchanged (Evansand Ginsburg, 1987).
theoretically the subsurface waters are now dealing with a group of minerals All of the CaC0 3 mineral transforma-
should be saturated with respect to cal- with differing solubilities, the main pro- tions take place by dissolution of one
cess is not one of calcite dissolution, but
o cite. But they should not be oversatu-
rated, because there are calcite nuclei instead (1) dissolution of the more sol-
uble phases (aragonite and magne-
mineral and precipitation of calcite.
What is important in this process is
that, unlike the simple calc ite-water
O· everywhere in the surrounding lime-
stone available for precipitation. In addi- sium-calcite), (2) resultant oversatura- interactions described previously, large
o tion, from the previous discussion of
dissolution it is clear that if two waters
tion with respect to calcite, and
(3) precipitation of new calcite.
amounts of water are not necessary.
Consider, for example, the aragonite-
saturated with respect to calcite are calcite reaction, which can be en-
o mixed, dissolution and not precipitat ion
will occur, and the same situation seems CaCO a ~
calcite
Ca 2 + + CO~-
visaged as occurring in a beaker of
fresh water (Figure 9-1) in which two
o to be true for seawater-freshwater aragonite carbonate minerals, a piece of arag-

o mixing .
Under natural conditions, however,
Mg-calcite onite and a piece of calcite, are immer-
sed. Immediately after immersion (Fig-
o ground waters are commonly super-
saturated. Once the waters are satu-
The important point here is that,
in this process, calcite is never dis-
ure 9-2) both the calcite and the
aragonite begin to dissolve until the
o rated, calcite will precipitate if it can, but solved because oversaturation is water is saturated. As noted in the ear-

o is often prevented from doing so by


various inhibiting factors. This aspect is
achieved and maintained by dissolution
of aragonite, and to a lesser degree by
lier section , this reaction is almost in-
stantaneous. However, since calcite
o poorly understood and several things,
such as kinetics of crystal growth, flux of
magnesium-calcite. In addition, this
process leads to a wholesale change in
is less soluble than aragonite, the water
becomes saturated with respect to cal-
o CO2 and inhibition by other ions, serve mineralogy, from metastable carbon- cite first, but is still undersaturated with
c to illustrate the problems . It is well
known, for example, that more energy is
ates to calcite.
Aragonite and magnesium-calcite
respect to aragonite, so the aragonite
continues to dissolve. But now (Figure
r. needed to grow a crystal than to dissolve are stable when bathed in warm sea- 9-3) the water is oversaturated with

c it, and so the rate of crystal growth is


slow relative to dissolution . Also, the
rate at which CO2 gas dissolves in water
waterbecause it was from this seawater,
with its high ionic strength , that they
respect to calcite, and as there is a
calcite crystal present, CaC0 3 will pre-
cipitate as calcite crystal cement. With
were precipitated. All three minerals,
is very fast, but the rate at which a solu- however, are soluble in fresh water, but this precipitation the solution is now
tion evolves CO2 to the atmosphere is to differing degrees. Specifically, the undersaturated with respect to arag-
very slow, and the rate of calcite growth solubility of magnesium-calcite pro- onite again, and so more aragonite dis-
is slower still. Finally, ions such as gress ively increases with increasing solves. Thus the process continues,
Mg2+, SO~ - and PO~ - are known to magnesium content, as the calcite lat- with aragonite continuing to dissolve
inhibit both dissolution and/or precipita- tice becomes more and more distorted . but never contributing enough CaC03
tion . If precipitation is prevented, then Aragonite is also more soluble than cal- to reach saturation because of continu-
the saturation state will continue to rise, cite and has the same solubility as mag- ing calcite precipitation. Eventually
with the solution becoming progres- nesium-calcite with about 12 mole% (Figure 9-4) all the aragonite is gone
sively oversaturated, until a thermo- MgC03(Walterand Morse, 1984).Thus, and the process stops, the final product
c
42 Diagenesis Geoscience Canada Reprint Series 4 c
(

being an original calcite crystal or grain throughoutthesystem isgone, and now, within grains, orcan be precipitated on a c
surrounded by newly precipitated cal- in a monomineralic all-calcite system, microscale inside a particle, replacing c
cite. This process, in which dissolution
is followed by precipitation of a second-
precipitation is localized and largely
water-controlled.
the original aragonite or magnesium
calcite. c
ary carbonate phase, is referred to by
some as incongruent dissolution (Turner
Kinetics also are important in this
system. Under natural conditions, if the
Styles of Diagenesis.
From the foregoing, it is clear that mete-
c
et al., 1986). freshwater diagenetic alteration of oric diagenesis is driven by two rock- c
Quite clearly the same reactions
could begin all over again if a new arag-
aragonite and magnesiumcalcite to cal-
cite were governed solely by equilib-
water reactions, one involving con-
gruent dissolution and generally water- c
onite crystal were introduced. The-
oretically, the same beaker of water
rium processes, then ground waters
would never be very oversaturated with
controlled alteration, and the other
incongruent dissolution which is min-
c
could be used to alter large amounts of respect to calcite, whereas in reality erai-controlled. Congruent dissolution c
aragonite and magnesium-calcite to
calcite. In reality, what would happen is
they are. Also, if the kinetics of the pro-
cesses were rapid relative to the age of
means that the entire solid dissolves
and generally no solid phase is precipi- c
that the ions from the aragonite and
magnesium-calcite that do not fit into
the ground waters, all water should be
in equilibrium with calcite, but it is not.
tated atthe site of dissolution.lncongru-
ent dissolution means that part of the
c
the new precipitated calcite, especially In most instances, the waters are over- solid dissolves to leave behind a solid c
Mg2+ and Sr2+, would become so con-
centrated in the water as to inhibit the
saturated with respect to calcite and
just undersaturated with respect to
phase different in composition from the
original, and the reaction is usually c
precipitation of calcite. In the intermedi- aragonite (Plummer et al., 1976). Thus accompanied by precipitation of a new c
ate stages, though, because of the ris-
ing trace-element concentration in the
non-equilibrium processes such as dis-
solution, precipitation and crystal
phase (Drever, 1982; Turner etaI., 1986).
The new phase maydiffer in crystal form c
water and selective absorption on the
calcite, these elements would be parti-
growth as well as the flux of CO2 in and
out of the ground water are again
from the original but havegenerally sim-
ilar composition, like dLMC compared c
tioned into the new calcite in small but important. For example, it has been with dissolved aragonite, or maydiffer in c;
ever-increasing amounts. An analo-
gous situation exists in nature. Waters
estimated that the rate of aragonite dis-
solution in "fresh" meteoric water is
composition but essentially not in crys-
tal form, like dLMC compared with pre- c
at the recharge end of a freshwater aqui-
fer have low trace element concentra-
100 times faster than the rate of calcite
precipitation (Schmalz, 1967). Thus it is
cursor HMC, or may have both new
crystal form and new composition,
c
tions, but by the time they reach the important to remember that waters in like dolomite compared with HMC or c
distal, discharge point, because they
have taken part in so many reactions
the meteoric environment, as long as
they are still in contact with metastable
aragonite.
c
along their path, they have relatively
high trace element concentrations. Cal-
carbonates, may be several times over-
saturated with respect to calcite, not
c
cites precipitated in the distal parts of because the nuclei are not there to pre- c
the aquifer will therefore have higher
trace element concentrations com-
cipitate on, but because the processes
are slow in the time frame of water c
pared to those precipitated in the proxi-
mal part (Kinsman, 1969).
movement.
In summary, the mineral-controlled
c
An important point that must be processes involve dissolution of arag- c
remembered in all of this is that once
the aragonite and magnesium-calcite
onite and magnesium-calcite and pre-
cipitation of calcite. This new calcite, c
have all dissolved to produce new cal-
cite, the process stops. The intrinsic
called diagenetic calcite (dLMC) by
some workers, can be precipitated in
c
driving force for calcite precipitation open voids ascement between grains or c
- DISSOLUTION & PRECIPITATION ~
c
c
c
~~ ~ r ~ r: ~ ~ r: (
Ca++
ca::, ca H
,
c
DH 0
2
fS r ++@
tIl Sr++ c
i8£HC0 3 O~HCO=
3 HCO= Figure 10 Modern hard laminated caliche C
3
(e) developed on the upper part of Pleisto-
(1) (2) (3) (4) cene reef limestone, Barbados. (Scale in
em). c
Figure 9 A sketch illustrating the simultaneous dissolution of aragonite and precipitation of
calcite in a beaker of distilled water.
C
l
C
(
(
Limestones - The Meteoric Diagenetic Environment 43
C
r:
In a suite of metastable minerals, the sediments are still aragonite and permeab ility, or the presence or
( either water-controlled alteration (con- high-magnesium calcite, provided that absence of fissures and cracks . Most
o gruent dissolution) or mineraI-control-
led alteration (incongruent dissolut ion
the flow of meteoric water is slow
enough that solubility differences can
changes will not be governed by the
fabric of the limestones and so will be
c and dLMC precipitation) may be opera- make the precipitation operative. The cross-cutting or "non-fabric selective",

o tive, depending mainly on the amount


and flow rate of meteor ic water through
alteration is mineral-controlled and
might in fact be viewed as incongruent
In the following sections , we first out-
line the processes of water-controlled
() the system . The difference between diagenesis. Diagenesis of this kind may (congruent) diagenesis because they
these processes is well illustrated in often be dominant in zones of relatively are applicable to virtually all carbonates
( the vadose zone. Water coming into slow diffuse flow. in relatively high-flow systems. Next,we
contact with metastable aragon ite Because the flux of water through the describe processes that occur during
( and high-magnesium calcite directly system is such a dominant control, it mineral-controlled (incongruent) dia-
c beneath the soil profile will dissolve all
species until it is saturated, but as this
seems quite possible that both mineral-
and water-controlled alteration (incon-
genesis because they appear to be
widespread in limestones containing
() solut ion percolates downward, altera- gruent and congruent diagenesis) take metastable suites of CaCOs minerals
o tion will occur because of differing min-
erai solubilities, not changes in Peo z'
place simultaneously and side by side
in some sequences. For example, in a
where there is relatively slow, diffuse
flow of meteoric water.
But if these waters should subsequently newly exposed sequence of little-ce-

c emerge into a cave open to the atmo-


sphere, then precipitation due to
mented aragonitic and high-magne-
sium calcite sediments , relatively slow-
moving diffuse flow may occur in most
PART 1 - WATER-CONTROLLED
METEORIC DIAGENESIS
The Rock-Air Interface.
degassing and not different solubilities
will take place. In contrast, if sediments places, fostering incongruent dissolu- The limestone surface in the meteoric
in the vadose zone are entirely calcite, tion and mineral-controlled alteration , environment , whether open to the air or

o then dissolution beneath the soil and


precipitation in the cave will still occur,
but higher volume channel flow may
develop locally along incipient joints or
beneath a soil cover, is the first carbon-
ate to come in contact with acidic
o but no mineralogical changes will take
place in the bulk of the vadose zone.
root molds, such that the dissolution
there is congruent and the diagenesis
waters. Limestone surfaces forming the
upper part of the zone of infiltration are
Congruent dissolution takes place in is water-controlled. usually altered intensively and develop
both situations, in response to flow- In mineral-controlled, incongruent features that are easily discerned in
through of water in large enough vol- diagenesis, because each kind of grain outcrops, cores and thin section and so
umes to prevent oversaturation for cal- is different mineralogically, dissolution are valuable indicators of subaerial
cite at the sites of dissolution. Water- and other forms of alteration will tend to exposure. Esteban and Klappa (1983)
controlled alteration under conditions of be " fabric selective" (Choquette and havesynthesized what was previously a

o this sort might be thought of as con-


gruent diagenesis .
Pray, 1970). In water-controlled, con-
gruent diagenesis, reactions and reac-
very diverse and widespread literature
concerning these structures, and much
o Still using the vadose zone as exam-
ple, incongruent dissolution and pre-
tion rates are governed by differences in
crystal size, grain size, amount of
of the following section is condensed
from their article. They concluded that
cipitation of dLMC will take place where adsorbed organic matter, porosity and there are really two end-member diage-

o netic facies here: (1) the caliche facies


and (2) the surface karst facies . These
c diagenetic facies are not mutually
exclusive: karst and caliche may co-
exist at anyone time and overlap in any
one area. Whereas karst can develop
under all climatic conditions, caliche is
attribu table to a generally semi-arid cli-

c matic reg imen . Before outlining the


attributes of these two facies, it should
be stressed that many subaerial
(
exposure surfaces may not contain any
l' diagenetic features, so the absence of
such features in the rock record does
not necessarily mean that the limestone
was never subaerially exposed.

CALICHE
Caliche (or calcrete or duricrust) is that
carbonate-Iithified port ion of the soil
I' ,
profile developed commonly, but not
exclusively, on carbonate sediments
Figure 11 Ancient caliche (C - between arrows) illustrating good alveolar texture , and rocks (Figures 10 and 11). Because
developed in the Carboniferous Newman Limestone, Kentucky. (Scale in em). caliches are accretionary and thus
c
44 Diagenesis Geoscience Canada Reprint Series 4 c
c
commonly preserved in the rock record, soil cover, there is a series of thin, com- replacement of roots by calcite in the
c
they have been intensively studied over monlyfriable,horizontaltosub-horizon- form of root molds, casts of tubules , c
the last twenty years.
Caliche zones range from centi-
tal plates or sheets which are separated
from one another but join and bifurcate
concretions or actual petrification -
are a diagnostic fabric of the caliche c
metres to metres in thickness and may
be complex in the extreme, with part of
laterally. This zone, which generally
grades down into nodular calcrete, may
profile. Roots both contribute to the for-
mation of platy calcrete and leadto brec-
c
the profile resulting from alteration of be several metres in thickness. ciation . This brecciation, which also c
the underlying limestone, part from
precipitation of new calcite and much
Caliche nodules (glaebules of soil ter-
minology) range from silt to pebble size
may be due to expansive crystallization ,
results in teepee and pseudo-anticline c
from a combination of both sets of pro-
cesses. Characterized by such features
and from spherical to irregular or cylin-
drical in shape, and may be isolated or
structures.
Included in many calcrete profiles are
c
as irregular, often laminated crusts, coalesced in arrangement. Thesestruc- black pebbles. The blackening may be c
rh izoconcretions, diagenetic peloids,
ooids and pisoids, breccias, clotted
tures, which are commonly concentric-
ally laminated, have been called caliche
due either to trapped organics within
crystals (Ward et al., 1970), metallic c
micritic and chalky carbonate, leached
and vuggy porosity and microborings
ooids, pseudo-ooids, oollths, peloids,
pellets, pelletoids, pisolites , coated par-
oxides precipitated on fungal hyphae
(Esteban and Klappa, 1983) or fires
c
and iron oxide, these horizons com- ticles, and, more recently, have been (Shinn and Lidz, 1988). c
monly stand out in a sedimentary se-
quence. Because their features are
included by Peryt (1983) under the term
vadoids.
Petrography. The petrographic
appearance of caliche is best described
c
similar to some formed in the marine Chalkycaliche is often well developed as messy. The wide variety of precipi- c
environment, however, they are often
overlooked (James, 1972; Read, 1976).
and may be up to one metre in thick-
ness, but is generally absent in areas
tates are reviewed by Chafetz et al.
(1985). Predominant fabric is a clotted c
Lithologies. As with other soils,
modern caliche is vertically zoned and
where the rocks have high initial poros-
ity. The white- to cream-coloured unce-
peloidal micrite with microspar-filled
channels and cracks. Grains and frag-
c
upward is composed of four rock types:
(1) massive chalky carbonate, (2) nodu-
mented carbonate is composed of silt-
sized calcite grains, commonly micro-
ments of limestone are separated from
thesurroundingmatrixbycircumgranu-
c
lar and crumbly carbonate, (3) irregular spar, with scattered nodules . lar cracks due to shrinkage and expan- (
plates and sheets, and (4) a compact
crust or hardpan. The position and
The transition zone down into the host
carbonate is characterized by strong evi-
sion . Fragments of original limestone ,
or individual grains if a relatively young
c
development of these lithologies in a dence of in-place alteration and replace- carbonate sediment, may be coated c
vertical sequence is highly variable
(Figure 12),but the massive chalky car-
ment of the original carbonate. Fossils,
for example, are often preserved but
with micrite laminations, which in turn
may be connected by thin laminations c
bonate most commonly is found at the
base, grading downward into underly-
embedded in calcified host material, or
coated with calcite laminations. If
bridging grains. A complete spectrum of
partly replaced (micrit ized) particles to
c
ing rocks or sediment. developed on bedded carbonate , altera- completely altered grains may be vis- c
The caliche hardpan, usually cream
to brown in colour, may range from 1 mm
tion takes place preferentially along bed-
ding and joint planes. This basal zone
ible. Replacement of some grains and
not others commonly results in a "float- c
to over a metre in thickness, is com-
posed of microcrystalline to crypto-
may be absent or metres in thickness.
Because roots may penetrate any of
ing texture" of particles in a micrite
matrix.
c
crystalline calcite, and ranges from the zones, rhizoconcretions - features Voids in the caliche profile often dis- C
structureless to horizontally laminated. formed by the precipitation around or play an alveolar texture (Figure 11),or a
E
Thicker hardpan generally is brecciated .. ~ o~
C
~?~Y
and exhibits dissolution and precipita- VARIATIONS
tion features, pisoids and rhizoconcre-
CALICHE C
tions. The upper surface ofthe hardpan
PROFILE l(}\tJ'
in semi-arid climates commonly is colo-
nized by lichens which may cause tex-
C
tural and fabric changes as deep as C
2 cm below the surface, producing
spongy, microscopic or micritic layers HARDPAN c
composed of organic-rich and organic-
poor mm laminations. Thus, the fabric
PLATES &
CRUSTS - - -
i e
of the hardpan may resemble that of a
~~~~~~~.
0

nm c
stromatolite and, in fact, Klappa (1979)
has called these structures "lichen stro-
LIMESTONE - - - ~ ! c
matolites". Criteria that can be used to OR - (
differentiate calcrete crusts from SEDIMENT
marine stromatolites have been out-
lined by Read (1976).
c
Beneath the hardpan or, if the hard-
(
Figure 12 Sketch of a caliche (calcrete) profile showing all the elements (left) and some of the
pan is not developed, directly beneath observed variations from various modern examples (right). c
c
c
r:
Limestones - The Meteoric Diagenetic Environment 45
r:

r:
network of anastomosing micrite walls zone and just above because there the cess beneath tropical soils, dissolution
100-150 JLm across inside cylindrical to sea spray supplies carbonate to the duetoother acids, such asfulvic,crenic,
irregular holes. Some open voids may crust , enabling precipitation to continue sulphuric and nitr ic, is also significant,
be floored with geopetal crystal silt at a more rapid rate; as would be but unlike the reactions associated with
(Dunham, 1969) which filters into cav- expected , the calcite there has a higher carbonic acid, many of these reactions
ities from the chalky zone . In other MgCOs content (James, 1972). In some are irreversible. The style of develop-
instances, the rock has a more vermicu- areas, such as the shoreline along the ment also depends a great deal on the
lar texture, or dense networks of micrite southern Persian Gulf where virtually porosity and permeability of the lime-
tubules and rods in a micr ite matrix the only source of water is sea spray, stone itself, with surface features
yielding a spaghetti-like texture. caliche crusts and pisolites develop but developed best on well-lithified lime-
In addition to micrite, needle fibres of are composed of Mg-calcite and arag- stones.
calcite a few microns to tens of microns onite (Scholle and Kinsman, 1974). Regardless, it is clear that climate is a
long are common . They may be a ran- In summary, the caliche zone is a major controlling factor in the develop-
domly oriented mesh (the " Iublinite" of diagenetic soil profile which involves ment of karst. Surface alteration at high

o
r:
soil science) and occur in voids within
the hardpan; they may form platy hori-
alteration of original limestone or sedi-
ment and precipitation of new carbon-
latitudes or altitudes is restricted to
slowly developed karst. In temperate or
zons or nodules; or they may be tangen- ate, both of which are modified or partly Mediterranean-type climates, karst and
tial with the needle-shaped crystals controlled by plants of various types. calcrete are common, but their develop-
o arranged in a band. This assemblage, which changes char- ment is seasonal. In general, deserts
Another distinctive caliche precipi- acter with time , is probably the most display poor karst and in semi-arid
tate is Microcodium or elongated to obscure and confusing of all diagenetic regions caliche is common. But, in re-
o petal-shaped calcite prisms or ellip-
soids or bell-shaped clusters which
zones.
Calcrete may be locally transitional
gions of high rainfall, karst forms a fan-
tastic array of towers, jagged ridges,
o Klappa (1978) proved to be calcified into terra fossa and similar soils (Gold- hogbacks, canyons and sinkholes
o mycorrhizae (soil fungi and cortical
cells of higher plant roots).
hammer and Elmore, 1984; Wright and
Wilson, 1987). Detailed geolog ical
which, together with extensive vegeta-
tion, make such regions pract ically
Variations. Depending upon the study ofthese featu res isjust beginning . impenetrable to surface travel and
length of exposure and climate, the cali- Ancient caliche. There are few well- poorly known.
che profile will change with time. Follow- documented examples of caliche in the Even though surface karst is most
o ing the development of weathered
detritus and a protosoil by the coloniza-
rock record (Estebanand Klappa, 1983),
and none from the Early Paleozoic.
intense in the humid tropics in areas of
substantial relief, in the past most car-
o tion by lower plants (lichen, fungi, algae, bonate platforms were exposed as vast

o bacteria), the caliche profile becomes


differentiated into two separate hori-
SURFACE KARST
Surface karst or exokarst, because it is a
flat plains. just above sea level with little
relief. Such a platform today in the Nul-
zons; water percolation and plant roots dissolution and not an accretionary larbor Plain in southern Australia (oneof

o generate the upper transition zone; pre-


cipitation of calcite forms the chalk
phenomenon , is difficult to recognize in
the rock record. In vertical section, it is
the world's largest karsts, ca. 100,000
km 2 ) which, because of the semi-arid
o zone. As accumulation of CaCOs con-
tinues, a point is reached where soil-
represented only by irregular bedding
contacts, and so only on well-exposed
climate, is heavily mantled with cal-
crete, exhibits minimal solution sculp-
or:
forming organisms can no longer main-
tain viability so that soil-forming pro-
bedding planes can the style be deter-
mined with any confidence. Paleokarst
ture and contains less than a score of
caves that reach to the water table and
....... cesses decrease and cementation and has only recently been recognized by relatively few shallow caves (Jennings,
r hardpan formation increase, fossilizing sedimentologists (James and Cho- 1971). Other level karst plateaus, such
the profile. Finally, the profile is so quette , 1988),although there is awealth as the Yucatan Peninsula (Stringfield
"'o"" Iithified that it is just another limestone of information about modern karst in the and LeGrand, 1974) or Bahama Banks,

o and the process begins again, a proto-


soil forms and plant roots penetrate the
geomorphological literature (Jennings,
1971; Sweeting , 1972; Jakucs, 1977;
because they are in a rainy climate,look
like Swiss cheese from the air,with innu-
o hardpan, leading to brecciation and
rhyzoconcretions.
Ritter, 1978).Karst occurs in all modern
climates, is the result of normal and
merable dolines or sinkholes (Figure
13). On the ground, the limestone is
...... Seminiuk and Searle (1985)differen- biogenic corrosion, and is slow under fluted or pitted by solution sculpture and
r tiate between vadose or rhizoconcre- arctic conditions but extremely rapid in dotted with small, solution basins (Bour-
tionary calcrete and ground-water cal- the tropics. The process of dissolution rouilh, 1974).
crete (massive, mottled, laminar) in the takes place both on bare rock and Surface karst features , from a practi-
zone of capillary rise just above the beneath soil, but generates somewhat cal standpoint, can be subdivided into
water table. different features under the two condi- small-scale solution sculpture or fea-
As with the other features described tions . Corrosion is especially active tures smaller than a metre in size which
in this article, there is a gradation from beneath soil and intensive in the humid can be seen in outcrop-size exposures,
the wholly meteoric formation of caliche tropics because of high temperature and large-scale features tens of metres
inland to a transition zone along the and increased vegetal litter and soil. to kilometres in size which, although
shoreline. It is common to find the hard- Although biogenic corrosion by car- sometimes seen in outcrop, are better
est crusts developed in the supratidal bonic acid is the most important pro- thought of as karst landforms.
(
46 Diagenesis Geoscience Canada Reprint Series 4 C
C
Solution Sculpture. These dis- Solution basins (kamenitza or faces (Figure 17). They can develop as
C
solution or corrosion features, devel- kamenica) are small, flat-bottomed rainwater collects in small depressions, (
oped either beneath a soil or on bare pans or basins often exhibiting over- beneath humus patches or in the inter-
rock, are generally called "karren" in hanging edges which characteristically tidal zone through the combined action
(
the English and German literature, or develop on horizontal limestone sur- of mixing corrosion and bioerosion. (
"Iapies" in the French and eastern
European literature. These features (
have a wide variety of shapes, and as
B6gli (1980, p. 53) succinctly states, C
" the multiplicity of possible karren
forms makes a morphological system
C
endless". Nevertheless, there are a C
number of common, recurring shapes
(
which are outlined below and dia-
grammed in Figure 14.As ageneral rule, (
the sculptures tend to be sharp and
jagged on exposed rock, but rounded if C
below a soil cover.
(a) Small karren: In temperate cli-
C
mates bare limestone surfaces are gen- (
erally smooth (although the larger-scale
sculptures may be sharp edged), but, in C
tropical climates or where there is rain-
splash and mist, the rock surface is
C
textured by tiny, slightly elongate , cup- C
like pits generally less than 3 cm in
diameter called "cockling", which inter- C
sect at knife-sharp edges and give the (
rock a crinkly or cindery appearance
(Figure 15). In tropical regions, a similar Figure 13 Areal photograph of large sinkholes, several hundred metres in diameter, (
texture of black-coated , jagged pinna- developed in Pleistocene limestone, Andros Island, TheBahamas, and now filled with water or
cles, marked by delicate, lacy dissec-
vegetation. (
tion, has been called "phytokarst" (Folk
SURFACE SOLUTION SCULPTURE (KARREN) (
et al., 1973) because of the intensive
activity of endolithic microflora in its (
formation. These smallest of features FLUTES GROOVES HEEL-PRINTS
can form very quickly, in as little as four C
years. They are especially characteris-
tic of limestones with good intergranular
C
porosity and are well developed in the C
intertidal and supratidal zones. (
(b) Medium-sized karren : These
slightly larger features on bare rock (
develop in the form of solution runnels
and solution pans. Two of the most dis- C
tinctive forms are solution flutes (
(rillenkarren) or razor-sharp finely chis- BASINS OR PANS CLiNTS & GRIKES ROOTS
elled runnels (Figure 16) and solution- (
grooves (rin nenkarren) or slightly larger
runnels with rounded furrows, both of
(
which develop on slopes of well-
cemented hard limestones. All of these -~- E
forms develop quickly and may reach C
lengths of metres in the tropics . These
may be straight on steep surfaces or
(
meandering on flattish surfaces. On (
more horizontal surfaces,hee/-printkar-
ren (frittenkarren), in the form of cres- C
centic steps, are more common. Figure 14 Sketches of different types of surface solution sculpture .
(
C
(
C
(
r:
Limestones - The Meteoric Diagenetic Environment 47
r

o
r-
/

(
( Figure 15 Syngenetic phytokarst charac-
terized by sharp irregular cockling and
o numerous irregular pores in Pleistocene

r. limestone, Andros Island, The Bahamas.


(Arrow points to hammer for scale).

o
o
c
o
o
o
o
o
o
o Figure 16 Ancient rillenkarst (Late Devo-
nian - Early Mississippian) developed on
o Ordovician limestone, western Newfound-
land (scale in em). The sculpted runnels are
o partially to completely filled with light grey

o Mississippian limestone.

o
o
o
o
o
o
o
o
r
,.

Figure 17 Modern solution pans (kame-


nitza), developed on Pleistocene lime-
stones, Bermuda and partially filled with
modern carbonate sand. (Scale bar in 2 cm
divisions).
c
48 Diagenesis Geoscience Canada Reprint Series 4 c
(

(c) Large karren: Once covered by soil cover or subsurface dissolution and lution or precipitation takes place. Con-
c
soil, increased corrosion tends to either gradual subsidence or collapse. sequently, this zone is relatively "inac- c
smooth all edges and points, remove
small karren forms and widen and
Breccias that fill collapse dolines are
characterized by mixed soils and
tive". Reaction does take place, how-
ever, if the limestone grains are extrem- c
deepen pre-existing features (Figure
18). The general term rundkarren is
speleothems together with the v-shape
of fallen overlying beds.
ely small and so reactive, or if mixing of
vadose seepage and vadose flow
c
applied to these features, which range The other large-scale features, such occurs, or if large cavities open to the c
from wavekarren or wavy surfaces like
corrugated tin in temperate climates to
as cenotes, cockpits, mogotes, uvalas,
karst valleys and poljes, are more in the
atmosphere are encountered, or if there
are changes in temperature. c
cavernous karren in the tropics. realm ~f geomorphology, and excellent Conversely (Figure 19), if the sedi- c
Forms that seem to develop best
under these conditions are clints and
summaries of these landscapes can be
found in general texts 'o n karst (e.g.,
ments are composed of a mixture of
aragonite, magnesium-calcite and cal- c
grikes (f1achkarren) or flat-topped
blocks (clints) bounded on all sides by
Jennings, 1971; Sweeting, 1972;
Jakucs, 1977; Bogli, 1980).
cite, each with a different solubility, then
this is a zone of intensive activity (see c
solution-widened joints (grikes) which part 2 of this discussion). c
are rectangular to diamond-shape in
plan. While most workers (e.g., Sweet-
SUBSURFACE KARST
Many characteristics of dissoiutional
Under conditions of vadose flow, the
system is effectively open to CO2 and c
ing, 1972; Bogli, 1980) think that these
develop beneath soil, Purdy (1974) sug-
cave systems in carbonate rocks are
discussed in detail by Ford (1988).
the aggressiveness of the waters after
initial dissolution is governed by the
c
gests that they may also develop on The Vadose Zone. diffusion rate of CO2 across the water- c
bare rock surfaces. At joint intersec-
tions, cylindrical pits several metres
The zone of inflitration is dominated by
processes of intensive physicochemi-
air interface. If the channels are large,
rapidly flowing water may be aggressive c
deep may be produced, which may
evolve into solution pipes or potholes.
cal and biological corrosion related to
intensive organic activity (Esteban and
to depths of 100 metres or so (Thrailkill,
-1968). Dissolution also occurs, when
c
As the grikes widen with time, the sur- Klappa, 1983)::Vertical.caves- are ' pro- - vadose seepage and vadose flow meet, c
face passes through a phase referred to
as kluftkarren to a stage of solution pin-
nounced .here. iand collapse breccias
may be common. Precipitates are usu-
by mixing corrosion.
Many caves found in the vadose c
nacles (spitzkarren) or assemblies of ally fine grained (moonmilk) and/or zone are due to dissolution at perched c
upward-pointing pyramidal or projec-
tile-shaped bodies of rock separated by
globulites (popcorn).
As the CO 2-rich acidic waters emerge
water tables or are relic water-table
caves abandoned when the water c
interconnected clefts or basins. While
these pinnacles may develop beneath
from below the soil they dissolve car-
bonate quickly, become saturated, and
level dropped. It is clear that some
caves, however, particularly those c
soil-cover inland, they also form on bare lose their aggressiven!3ss within a few strongly elongated vertically, form in the c
rock and on coastal carbonate rocks in
the intertidal zone and higher.
decimetres of. the soil -zone. Once the
waters -are saturated -in -an -all-calclte
vadose zone itself, either to survive
- unchanqed orto be modified by phreatic c
In addition to the soil, the roots of
plants and trees in the tropics etch tor-
carbonate host rock, no further disso- processes.
c
tuous single and branching chan nels in
the rock (hohlkarren) that may reach
c
depths of 25 metres. Locally, the chan- C
nels may criss-cross the limestone so
densely as to turn it into something
E
resembling a sponge, in places with C
more than 75% pore space. In four to
ten years, for example, a hairline crack C
can be turned into a rock channel of arm
or thigh thickness (Jennings, 1972). In
C
Pleistocene carbonates, the complex C
interrelationship between karst and
caliche is well demonstrated by com- c
mon pipes which owe their origin to root
corrosion but are lined by calcrete and
e
filled with rhyzoconcretions, formed by c
organically-induced precipitation.
Karst Landforms. The most wide- c
spread of these larger features are do- c
lines or sinkholes which may be funnel-
to bowl- to flat, dish-shaped structures, c
metres to kilometres in diameter and up
to 100 metres deep (Figure 13). They
Figure 18 Ancient ;undkarst developed on Ordovician limestone: the depressions are filled
by light grey Mississippian limestone (arrows), western Newfoundland. (Scale bar in 2 em
c
owe their origin to dissolution beneath a divisions). c
c
c
r:

Limestones - The Meteoric Diagenetic Environment 49

The Water Table. Dissolution. Most dissolution corrosion. It is here that many caves are
o
o
This realm, including the base of the
vadose zone, the water-table surface
occurs at or below the water table, in the
phreatic part of this realm .
formed. Phreatic water movement is
generally horizontal and the origin of the
and the upper part of the phreatic zone , (a) Processes: If the system is en- waters may be allochthonous, from out-
is one of intense chemical activity, per- tirely subterranean, closed to outside side the local area . Since the level of the

o haps more intense than anywhere else


in the shallow subsurface.
air, then this region where vadose and
phreatic waters mix is a level of intense
water table varies seasonally, the water
table may rise into the vadose zone

o METEORIC DIAGENESIS
during times of flood, resulting in a
whole zone of caves at this level.
o EFFECT OF (b) Features: There area wide variety
of dissolution features, such as pas-
ORIGINAL CARBONATE MINERALOGY

o
o
---I
CALCITE
Mg-CALCITE
ARAGONITE
CALCITE
sages, chan nels and shafts (Figure 20),
which can be related to both the type of
water flow and lithology (Bagli, 1980;
Ford, 1988). Smaller cave karren are
I
o w
NO EXTENSIVE
superimposed on the larger cavities.
The walls and ceilings may be smooth or
o
(I)
g
c
ALTERATION ALTERATION
wcN
pockmarked with corrosion pockets,
dimples and pits, or textured by rills and
>
grooves similar to surface karst and

t
DISSOLUTION & PRECIPITATION

o WCA WCA~
~~:r-<~~!(.::..-(-W-C-A-)-1WATER TABLE f---:(::-M-C--A"'-)--='!.4~.Yl~~
especially common where vadose
waters emerge. Pendants of relic lime-
o MINOR
DISSOLUTION
EXTENSIVE
DISS. & PRECIP.---r--,·
stone in the form of cones of rock may
hang down from the ceiling or protrude
o (
NON-FABRIC )
"SELECTIVE
( FABRIC & )
~~~cM~~C
up from the floor.
Scallops or crescentic, shell-shaped
: : ",::':".". dissolution features can form on the
"/=!-- DISSOLUTION DISSOLUTION
surface where a stream flows over lime-
(W C A) (W C A)
stone, but are particularly common in
o NO NO caves. The crests in these features lie

o ALTERATION ALTERATION transverse to flow and the steeper


slopes face downstream.
o Figure 19 A sketch illustrating the different diagenetic processes that affect a carbonate
Precipitation. Most precipitation,
but not all, takes place in the meteoric
composed 0.' calcite (sediment or limestone). versus one composed of a mixture of magne- part of this realm, in the upper parts of
sium-calcite. aragonite and calcite. Water-controlled diagenesis (WCA) is driven by evasion caves and cavities above the water table.
and Invasion of CO2 while mineral-controlled diagenesis (MCA) is driven by differences In (a) Processes: Regardless of the
o CaC03 mineral solubility. mineralogy of the sediment or rock, if
the system is ventilated with atmo-
o spheric air, the reverse occurs. High
Peo, vadose waters emerging at the top
of water-table caves equilibrate with
low-Peo, atmospheric air, degas and
o precipitate carbonate. Exactly the same
phenomenon occurs as springs emer-
o ging from a hillside precipitate traver-

o tine (Julia, 1983; Chafetz and Folk,


1984). Flowing waters in the cave are
also at equilibrium with atmospheric air,
and so precipitation only occurs be-
e cause of vanattons in temperature and
o turbulence.
It is a paradox that once caves are
open and can be visited by geOlogists,
the processes which formed them
largely have ceased, and they are in the
process of being decorated by various
precipitates (Thrailkill, 1976; Moore and
Sullivan, 1978).
Figure 20 Large dissolution cavities (ca . 1.5 m in diameter) excavated into Permian carbon-
ates, Carlsbad Caverns. New Mexico - note the lack of decoration.
c
50 Diagenesis Geoscience Canada Reprint Series 4 c
c
(b) Features: Subterranean precipi- growing surface. This two-stage process thought to form at the water surface c
tates can be subdivided into two types:
(1)calcareous tufa - soft porous rock to
leadstofrettedcrystal boundariesand not
to straight ones, as might be expected
because of CO2 diffusion into the air.
These may sink or may aggregate into
c
which plants contribute significantly,and from competitivegrowth of large crystals. small rafts. Cave pearls (concentrically c
(2) calcareous sinter (speleothems) -
nonporous, crystalline, hard limestone.
Those crystals in speleothems with para-
axialboundariesareinterpretedto bedue
laminated pisoids) form in pools of mov-
ing water or splash pools. c
The most common tufa is moonmilk, to precipitation during episodes of cave Plant life in caves has important geo- c
which is composed of microscopic car-
bonate crystallites or lublinite (random
flooding. The variety of fabrics are
reviewed and illustrated by Chafetz et a/.
logical implications. As caves lack light,
heterotrophic bacteria (including ac- c
needle crystals); although plastic and
containing from 35% to 75% water
(1985) and Gonzalez and Lohmann
(1988).
tinomycetes or mold-like filamentous
bacteria), algae and fungi as well as
c
when precipitated, upon drying it turns In addition to these deposits in the chemo-autotrophic bacteria are the c
into a powder. Plants playa significant
role in the precipitation by removing
vadose part of the cave, bars of sinter
called rimstone form on the cave floor,
most common forms . In addition to their
contribution to the formation of moon- c
CO2 from the water, and the resulting
crystallites are enmeshed in a net of
where water from a pool flows over an
obstruction as a thin film. When it flows
milk, these organisms result in the pre-
cipitation of other minerals. The black,
c
filaments from bacteria, actinomycetes over this rim, there is an increase in the sooty coating on cavewalls and pebbles c
and algae.
Sinter is precipitated either from thin
loss of CO2 and calcite is precipitated.
Most precipitation in pools or beneath
is a variety of manganese minerals
whose precipitation is aided by spe- c
films of water flowing over the rock or in
pools of water. Precipitation from water
the water table in the phreatic part ofthe
zone, however, is different. Because
cialized bacteria. On the other hand,
chemo-autotrophic iron bacteria, which
c
films results in crystals that grow out- there is no bounding surface, crystals obtain N2 from the air and carbon from c
ward from the rock surface for only a
short distance, with growth terminated
grow out into the water equally in all
directions as true crystals with scaleno-
iron carbonates, liberate ferrous iron,
which is oxidized to give a red colour to c
at the air-water interface (Figure 21). As hedral terminations (Figure 21). The cave sediments. ~
a result, the outer surface of the calcite largest crystals grow in the quietest The Lenticular Zone.
is smooth, with scalenohedral termina- water; the more the water flows, the Carbonate-water interaction in this c
tions never developing. This style of
precipitation is typical of the vadose
more numerous the calcite nuclei are
and the closer the calcite crystals stand,
shallow phreatic setting is poorly under-
stood because it is inaccessible, and
c
part of the cave, and forms flowstone and in rapidly moving water, rounded conclusions must be drawn from the- c
and dripstone (Figure 22).
Dripstone ranges from draperies to
surfaces like cauliflower, composed of
innumerable tiny crystals, can form.
oretical calculations and laboratory
experimentation (Plummer, 1975) and c
"soda-straws" to stalagmites and sta-
lactites to helectites. Deposition starts
The seed crystals for precipitation are data from wells (Back et a/., 1979).
c
from a drop of water on the ceiling, with c
precipitation beginning at the area of
attachment. Since CO2 is given off from c
the surface of the drop, precipitation
starts there, causing a ring of calcite.
c
Ring is added to ring to form a tubular
structure - the "soda straw". Water
flowing as a film over the exterior sur-
) c
c
SC~LLOPS
face of the soda straw deposits a second
. / c
type of calcite which constructs the
familiar conical or candle-shaped form . ) DRI~STONE c
This outer coating is most commonly
composed of elongate calcite crystals
HELECTITES 6 b c
which, in sections cut normal to the sta-
lactite long axis, have their long and
FLOWSTONE
----~..,;;;:~ / -.:.. 0 c
optic axes radially disposed. Some of
~

c
the growth surfaces are discernible by
bands which contain abundant impuri- CAVE e
ties. In an effort to reconcile the growth PEARLS (
of large crystals with a complex internal
fabric from a thin film of water, Kendall SCALLOPS c
and Broughton (1978)suggest that pre-
cipitation takes place initially from thin
COLLAPSE
BRECCIA c
water films in the form of tiny crystallites c
which grow syntaxially. The columnar
crystals form by a process of syntaxial Figure 21 A sketch illustrating the styles of precipitates (sinter) formed above and below the c
coalescence immediately behind the water table in a cave open to the atmosphere.
c
c
c
G
C Limestones - The Meteoric Diagenetic Environment 51
-,

r: Dissolution. There is a brackish SYNGENETIC KARST stone and is a distinctive trait of these
zone of mixing at the base of the fresh- The rock-air interface in metastable car- early caves. Once welliithified into cal-
r water lens. Theoretical calculations bonates is particularly susceptible to cite limestone, the full specturm of karst
and observations, especially near the alteration because of the generally features may develop.
r shoreline, from Yucatan (Back et al., porous nature of the sediments. The

c 1979, 1986; Hanshaw and Back, 1980)


and Bermuda (Palmer, 1984) indicate
that this mixing zone between fresh and
sediment surface hardens almost in-
stantaneously as a thin, millimetre-
thick crust of altered grains cemented
PALEOKARST
Numerous examples of ancient karst,
ranging in age from Precambrianto Cre-
(
marine waters is dominantly one of cor- by calcite. This grey crust also contains taceous, are documented in the compi-
c rosion and porosity formation. It is sig-
nificant to note that corrosion becomes
algae and fungi and develops within
months to years in quarries and new
lation by James and Choquette (1988).
Choquette and James (1988), recog-
C' more intensive when fresh and hyper- road cuts. The porous natureofthesedi- nize3typesof paleokarst: (1) depositional
,.' saline waters mix (Plummer, 1975). ments also aids in the rapid and deep paleokarst, formed at the top of metre-
Since the saturation state is dependent development of caliche, particularly in scale shallowing-upward sequences,
o upon so many factors, however, in some
areas of the Florida aquifer mixing does
semi-arid climates.
In spite of the often poorly consoli-
(2) local paleokarst, generatedwhenpart
of a carbonate shelf or platform is
not result in undersaturation. dated nature of metastable sediments exposed by local tectonism or small
In areas far removed from the effect of during early phases of meteoric diagen- drops in sea level, and (3) interregional
seawater, Jakucs (1977)has noted that esis, karst processes are ongoing. The paleokarst, related to major eustatic-
caves are common at the base of the products have been called syngenetic tectonic events and commonly defining

r lenticular zone (see Vernon, 1969, for


examples in the Florida aquifer) and has
karst (Jenn ings , 1971) because they
develop during lithification. Not all karst
sequence boundaries.
Since karst is a dissolution pheno-
ascribed their formation to hydrostatic features develop, however. Solution menon, a major problem is recognizing
corrosion, but some of this may be due sculpture is minor, except where cal- when dissolution occurred (Wright,
to mixing of fresh waters from the upper crete is exposed directly to rainwater. 1982), i.e. , whether the features ob-
phreat ic and more stagnant and saline Solution pipes are common, espec ially served were formed soon after deposi-
waters from the lower phreatic. those associated with roots, but the tion, or are the result of present pro-
Precipitation. There is consider- familiar solution features along joint cesses, or were formed at some un-
able confusion about calcite precipita- intersections are missing . Caves are known time. Particularly troublesome
tion in the lenticular zone. From the well developed, generally due to lateral is intrastratal or subjacent corrosion,
above, it appears that corrosion is the dissolution at the water table and minor which forms in the subsurface along
dominant process in calcite limestones . vertical dissolution. Because excava- lithologic boundaries and creates fea-
Hanor (1978) has proposed several pro- tion accompanies lithification and the tures that resemble surface karst and
cesses to promote degassing and so surrounding poorly lithified sediments could be mistaken for such. The surest
precipitation near the area of outflow, are inherently weak, roof collapse way of confirming that the feature is
but there does not seem to be much dominates more of their history than is fossil is to find skeletons or calcretes
suggestion of widespread prec ipitation . characteristic in consolidated lime- cemented onto, or borings penetrating
into, the paleosurface. Other criteria
that might be useful in certain casesare
suggested by Read and Grover (1977)
and Wright (1982). On a smaller scale,
there is a problem in the differentiation
of paleokarst surfaces and stylolites

o (Walkden, 1974).

o PART 2 - MINERAL-CONTROLLED
METEORIC DIAGENESIS
o This diagenesis can be seen going on
today or, at least, inferred to havetaken
place recently in Holocene and Pleis-
tocene carbonates in numerous warm,
r sunny places, and so is exceptionally
well documented. The reader is referred
to excellent recent reviews by Bathurst
(1980), Longman (1980) and Fliigel
(1982) for additional information .
The Process.
The commonstagesbywhich metastable
carbonatecomponentsalterto calciteare
Figure 22 Dripstone curtains about 1 m in length decorated by cave popcorn, Carlsbad now well known (Friedman, 1964; Land,
Caverns, New Mexico - arrows point to water droplets. 1967; Purdy, 1968; Matthews, 1974). Soon
c
52 Diagenesis Geoscience Canada Reprint Series 4 c
c
after meteoric waters begin percolating dence of a limestone in different parts of with either water or air or both,with water c
through a sediment , small elongate or the meteoric diagenetic environment. just wetting the grain surfaces. This, and c
equidimensional calcite crystals pre-
cipitate as cement on grain surfaces.
Many examples of these cements are
illustrated in Bricker (1971), Halley and
the fact thatvadosepercolationof wateris
not uniform, results in cements that typ- c
They grow equally on magnesium-cal-
cite or aragonite particles and earlier
Harris (1979), and Jones et a/. (1984);
their main attributes are outlined below.
ically show quite irregular distribution .
Inoutcrops or subsurface cores of Pleis-
c
submarine cements, giving the sedi- Vadose cements. These precipi- tocene limestones it is common to see c
ment some coherence . The next step,
which occurs as more cement is being
tates grow from void walls into poresthat
mayat different times be completelyfilled
relatively well cemented areas only
millimetres away from areas that are c
precipitated , is the start of alteration of
magnesium-calcite components to cal- SHALLOW DEEPER SHALLOW MIXED-WATER c
cite bydissolution of Mg-calcite and rep- VADOSE PHREATIC TRANSITION
I I
c
recipitation of calcite on a microscale I I c
(Turner et al. , 1986).By now, most parti- I I

cles are coated with a rind of calcite


cement which may constitute up to one-
CALCITE CEMENT IN MACROPORES
I I c
quarter of the rock volume. It is at this I
I
c
stage that aragonite alteration usually
begins, either dissolving to form molds c
or altering to calcite across an alteration
front with much textural preservation.
c
Dissolution of aragonite produces cop- en
zt-
c
ious quantities of CaCOa to be precipi-
tated locally as cement both inside and
c~
a:: CJ ARAGONITE I ."':".~.::f::L''....L.LCL.!.J.W-'~~. I c
between particles and in new holes cre-
CJ W (GRAINS & MARINE . .. .
~! :: CE~~~~)
CALCITE CEMENT IN MOLDS
»:'<'::'::- ':'.:.'.:'.:.':':..:.''.'-:. '::: c
ated by aragonite dissolution. By the
time all aragonite has gone , the sedi- a .'. .
_
~ I .. '
. , .:"
'. ' LOW-Mg CALCrtE (NEOMORPHIC) ' ' . '
Mg-CALCIT~ . . . I • • • • • . •
:"1'" .: : .-
: c
c
' . . . . . . . ." • • : • • • . • . '" .' .
ment has generally been transformed
into hard calc ite limestone (Figure 23).
~ CIll ~~I~~. ~ ~r'~.I~~ . ~!-~.'. :'.'.... '.: '.'.'.'.' .:.,:'.'.:..:'. :.'.1: . -:: . ' '. '. '.':
In this system, it seems that almost all - - - BURIAL-DIAGENETIC STAGE ----~ c
the cement needed for lithification can
be derived locally from aragonite dis- Figure 23 Idealized diagenetic evolution of an aragonite and magnesium-calcite sediment c
solution. So, in spite of wholesale fabric
rearrangement, there may be only
as it passes through meteoric diagenetic zones , in a terra in of low to moderate rainfall . Inferred
changes in the trans ition at the base of the lenticular zone are based on calcite saturation c
minor net loss of carbonate and just a relationships suggested in Figure Z
c
change in the style of porosity, from (", d\. -o o--.I-0v c
intergranular to moldic.
METEORIC CEMENTS ~~IQ.A,Jb"
Cementation.
By the term "cement" we mean here the
c
growth of precipitated calcite into origi-
VADOSE ZONE PHREATIC ZONE
c
c
~
nal pore space, either between grains
or inside grains, or into holes newly cre-
ated by the dissolution of aragonite.
Techniques for differentiating cement
c
from neomorphic or altered pre-existing c
precipitates are outlined by Bathurst
(1975, p. 416-439) and Dickson (1983).
MENISCUS ,
./)
VADOSE
ISOPACHOUS c
Among the more useful criteria, al- ~~ SILT c
~~
' ). r
though neither is foolproof, are (1)
increase in crystal size away from the
substrate and (2) development of sea-
lenohedral terminations directed away
EPITAXIAL
e
from the nucleation surface or sub- STALAGTITIC t .:'- . \ l
strate. Even these criteria are best
(
checked in fossil limestones by staining MICRITE
and cathodoluminescence for the pos-
sibility that the crystals are neomorphic
.. / ENVELOPE C
(e.g., Bathurst, 1983).
Vadose and phreatic cements gener- Figure 24 The different types of cement prec ipitated in the vadose (left) andphreatic (right)
ally have differing morphologies and so
(
parts of the meteoric diagenetic environment. Epitaxial cements on echinoderm particles may
can provide a useful guide to the resi- be precipitated in either zone.
C
C
C
(
(
Limestones - The Meteoric Diagenetic Environment 53
r

uncemented. Although some cements partly filled pores and so have men- if cementation is prolonged and pores
may be in layers of equal thickness iscus or pendant shapes (Figure 24). are filled, these characteristic shapes
around pore walls (precipitated when Crystals in these settings rarely have are usually lost. In our experience, epi-
the pores are filled with water), more good terminations (Figure 25). Men- taxial overgrowth cements also develop
commonly cements reflect growth out- iscus and pendant cements are excel- here, particularly on echinoderm grains
ward to capillary water-air interfaces of lent criteria for vadose precipitation, but and some benthic foraminifer tests. It
also seems that some early cements in
this zone become detached from pore
ceilings and fall to the bottom of the
pores forming geopetallayers of vadose
crystal silt (Dunham , 1969).
Phreatic cements. Pores in the
phreatic zone, unlike those in the
vadose, are always filled with water,and
so crystals can grow unimpeded except
by intercrystalline competition. Thus
cement rinds formed here, at least inthe
shallow lenticular phreatic, are either
well developed isopachouslayers of cal-
cite crystals around pore walls (Figure
24) or blocky calcite (Figure 26). As a
general rule, crystals are somewhat
larger than in the vadose zone and epi-
taxial growth on echinoderm particles is
more rapid. These cement morphol-
ogies are, unfortunately, not restricted
to this zone and form in deeper burial
and cold water marine settings. So
shape alone is not a reliable criterion.
Staining. A useful technique for dif-
ferentiating separate stages of cement
precipitation and determining cement
Figure 25 Pore-rounding cements, probably of vadose origin, in ooid grainstone. The morphologies is staining with an acid
arrows show location of meniscus-style cement borderingpartly filled interparticle pores. 5te .
solution of potassium ferricyanide,
Genevieve Formation, Bridgeport field, southeastern Illinois. (Width of photograph is 0.5 mm).
which imparts a blue stain to iron-rich
( calcites (Dickson, 1966; Lindholm and
Finkleman, 1972). Since the vadose
zone is an air-water system, conditions
there are generally oxidizing, so that
any iron is in the ferric state (Fe3 +) and
can not be incorporated into calcite. As a
result, vadose calcite cements are iron-
poor. On the other hand,phreatic waters
are often reducing, and so iron is in the
ferrous state (Fe2 +) and can be incorpo-
rated easily into the calcite lattice , with
the result that phreatic cements are
commonly slightly iron-rich. There are,
however, some caveats to this concept:
first, a source of iron must be present;
--. second, perched water tables are com-
mon in the vadose zone; third, not all
phreatic waters are reducing; and
fourth, many ferroan calcite (and dolo-
mite) cements form in the deep subsur-
face, below the lenticular zone. Conse-
quently, the interpretation of the stain
should be used with caution, remember-
Figure 26 Partially to completely dissolved ooids with some aragonite remaining which are ing that the lack of an iron-rich calcite
surrounded by medium crystalline phreatic calcite cement. (Photomicrograph, partially cement does not preclude the pos-
polarized light, is 2.5 mm across). sibility that it is phreatic in origin.
c
54 Diagenesis Geoscience Canada Reprint Series 4 c
c
Cement stratigraphy. Identifi- appears that even before the skeleton seawater contains negligible iron,
c
cation of stages of cement precipita- loses much MgC03 , calcite cement is grains with excellent fabric preserva- c
tion can be a powerful tool in ascertain-
ing the sequence of diagenetic environ-
precipitated into these small intragranu-
lar pores.
tion but composed of iron-rich calcites
must, at some stage, have altered in c
ments through which a limestone has
passed (Figure 27). In some areas,
A potentially useful technique for dif-
ferentiating between original magne-
contact with phreatic or deep subsur-
face waters. As calcite is stable and
c
such stages have been found to be sium-calcite and calcite components in should not alter, these iron-rich calcite c
systematically arranged and correla-
table over tens of kilometres through
the fossil record, since both display
excellent microstructure, has been sug-
grains must have been magnesium-eal-
cite originally.The converse, however,is c
tens of metres of limestones (Meyers,
1978; Meyers and Lohmann, 1984).
gested by Richter and FOchtbauer
(1978). Since calcite precipitated from
not true, as magnesium-calcite grains
altered in the vadose zone would also
c
This "cement stratigraphy" (Meyers, c
1974), also discussed in Choquette and
James, this volume, can be best
CEMENT STRATIGRAPHY c
unravelled by using a combination of
staining and cathodoluminescence.
c
Alteration of Magnesium-Calcite c
Components.
On the modern sea floor, particles and
c
cements are composed of micritic and c
fibrous magnesium-calcite crystallites
(Folk and Land, 1975). As outlined c
above, magnesium-calcite, because of
its generally greater solubility in dilute
c
waters, begins to alter to calcite before c
aragonite, very soon after percolating
waters have entered the sediment. c
Because the change does not involve
a modification of the original crystal ha-
c
bit, textural changes that accompany al-
1.
2.
MARINE
VADOSE
1. BEACHROCK
2. VADOSE
c
teration to calcite are invisible with the
light microscope (Figure 28). There is, 3. DEEP PHREATIC 3. DEEP BURIAL c
however, dissolution-reprecipitation,
and under the SEM it is clear that micro- Figure 27 A sketch illustrating t wo different examples of cement stratigraphy.
c
metre-size crystallites undergo slight c
enlargement (Towe and Hemleben,
1975; Oti and Muller, 1984). Regardless, c
the precise crystal orientation of crys-
tals is preserved, which is especially
c
evident in echinoderm tests . c
Skeletal magnesium-calcite is het-
erogeneous, divided into domains
c
having different levels of MgC0 3 c
(Moberly, 1970; Blake and Peacor, 1981;
Turner et et., 1986). Although the c
replacement process is not precisely
known, magnesium calcites do dissolve
c
incongruently, probably reflecting the (
greater solubility of the MgC03 phases
(Schroeder, 1969). Thus, it is probable c
that the MgC03-rich domains dissolve
first and calcite is simultaneously pre-
e
cipitated. Under the SEM the new cal- c
cite can be seen to have grown epi-
taxi ally on adjacent calcite surfaces, c
preserving the original crystallographic (
orientation (Benson and Matthews,
1971). Consequently, the resultant cal- Figure 28 Pleistocene limestone (Bermuda) in which the Mg-calc ite grains (Foramin ifera- C
cite component is partly original and left, lower right, centre) are now calcite while the mollusc (centre) is still aragonite: the
partly diagenetic. Most particles, how- isopachous cement rind is probably phreatic. (Photomicrograph, partially polarized light, is
l.
ever, are somewhat porous, and it 2.0 mm across). C
C
C
c
c Limestones - The Meteoric Diagenetic Environment 55
('
(
be iron-free calcite. In add ition, some and finally d issolves the crystals however,suggest that underdeep burial
o aragonites calcitize with considerable
iron incorporation (Sandberg and Hud-
altogether (James, 1974). This dissolu-
tion may begin at one point and expand
cond itions an d/or later fltiSfilng by
waters in ne~s.ur.fac.e-emlimen1s....-. -
C) son, 1983), but the replacement tex- outward or it may proceed from nu- some original low-magnesium calcite~
( tures are coarsely crystalline. merous starting points. may dissolve selectively, leaving molds
Alteration of Aragonite Components. From a geological viewpoint, it is the (Donath et al., 1980 ; James and Klappa,
( Aragonite is volumetrically more abun- way in which the subsequent calcite 1983; Sandberg, 1983). This may be due

c dant than magnesium-calcite in most


modern shallow-water, low-latitude car-
precipitation takes place that is impor-
tant (Sandberg, 1965), and two styles
to subtle differences in crystal size, con-
tained organicmatter ordomainsof unre-
( bonate sediments (e.g., most ooids, are common (Figure 29): placed calciteof low,but notlowest, mag-
gastropods, codiacean algae , dasyclad (1) Macroscale: In some cases the nesium content (e.g., 4-10 mole%).
( algae and corals are aragon ite). Particle whole component - grain, fossil or (2) Microscale: In other examples,
and cement habits range from micro- cement - dissolves away, leaving a dissolution of aragonite takes place
crystalline to platy to acicular to fibrous, hole that mayor may not be filled with simultaneously with precipitation of cal-
o though most modern marine cement
maybe acicular. Unlike magnesium-cal-
calcite cement (Figure 26). This is pro-
bablythe single most important process
cite on the opposite side of a water film
nannometres to micrometres in thick-
c cite, the change from aragonite to cal- creating small-scale porosity in the ness (Wardlaw et al., 1978), and the
o cite involves a wholesale crystallo-
graphic change from orthorhombic to
meteoric environment. The mold may
be filled quickly by cement in the mete-
basic structure of the original compo-
nent is partially retained (Figure 30) -
o hexagonal and the resultant process is oric zone or may remain open during that is, the resulting "calcitized " arag-

o one of complete dissolution of aragonite


and precipitation of calcite.
burial to be filled much later by deep
subsurface cements, brines or even
onite is generally a mosaic of calcite
crystals which cross-cut original fabric,
o Aragon ite dissolution is controlled
by the microfabric of the particle, skele-
hydrocarbons .
A note of caution! In our experience,
with the former structure outlined by
relics of organic matter and other insol-
ton or cement. It begins in areas with the magnesium-calcite grains in the mete- uble material (James, 1974; Pingitore,

o highest organic content or smallest


crystal size, then proceeds to etch
oric environment do not generally dis-
solve to form molds (but see Schroeder,
1976). This process generally is called
neomorphism. In some instances, re-
o along intercrystalline boundaries com-
monly yielding a "chalky" aragonite,
1979, for such an example). Recent
studies of pre-Pleistocene limestones,
placement is incomplete and tiny crys-
tallites of aragonite remain as relics
o entombed in the new calcite (Sandberg
et al., 1973; Sandberg and Hudson,
1983). Also, because of the fine scale
o and the microenvironment in which
alteration takes place, the concentra-
o tion ofSr2+ mayquickly rise inthis water

o film and so be partitioned back into the


new calcite in relatively large amounts
o /Jtr,~
JffY' 6' t vi"
(rarely, up to almost 1%; Davies, 1977).

o DISSOLVED
_0
""""~/p.um.e-
Because fine-scale replacement re-
suits in calcitized components that
o CALCITIZED clearly resemble their aragonitic pre-

~ ~
cursors, interpretation of original arag-
o onite mineralogy in ancient limestones

o STAYS OPEN FILLED PHREATIC VADOSE


is often difficult. Sandberg (1983) sug-
gests a range of criteria that may be
o i- -!- -!- -!-
used with increasing levels of confi-
dence to confirm original aragonite min-
o MOLD CEMENT-RLLED
MOLD
POOR
PRESERVATION
GOOD
PRESERVATION eralogy (Table 1).
It appears possible that this process
G may operate in slightly different ways in
8 the vadose and phreatic zones (Pingi-
tore , 1976). Aragonitic components
r
altered in the vadose zone tend to have
fabric-selective mosaics with relatively
MACROSCALE MlCROSCALE small crystal sizes, show excellent
ALTERATION ALTERATION replacement, and contain some organic
residue. The resulting calcites have a
Figure 29 A sketch illustrating the different ways in which an original aragonite skeleton may relatively low Mg2 + and high Sr2+ con-
be changed during meteoric diagenesis. If dissolved, a moldis formed which may later be filled tent. Aragonite components that have
by cement. If calcitized, some relics of shell structure (often including aragonite relics) remain changed in the phreatic zone reportedly
in the replacement calcite. The best preservation generally occurs in the vadose zone. show poor preservation in coarse,
c
56 Diagenesis Geoscience Canada Reprint Series 4 c
c
C
C
C
C
('

C
C
(

C
C
C
C
C
C
C
C
C
C
C
C
C
Figure 30 A Pleistocene gastropod in cross-section (Strombus gigas) wh ich is partially aragon ite andpartially altered to calcite (C); the lower C
part of the photograph is enlargedatthe leftillustrating excellentreplacement of aragonite (A) bycalcite (C) with the or iginal fabric now entombed
in new calcite as relic organ ic material and inclusions. C
C
C
C
Table 1 Aragonite Replacement Criteria C
1. PRESERVATION OF ARAGONITE
a. with aragonite relics
C
2. COARSE" CALCITE MOSAIC ,
b. no aragonite relics but ~ <-
IRREGULAR CROSS-CUTIING ::::i
STRUCTURE (AS SHOWN BY ORGANIC
high Sr ' iii
<: C
RELICS OR FLUID INCLUSIONS) { c. no aragonite relics, and
low Sr '
::::i
w
II: c
3. CEMENT-FILLED MOLDS
" relative to original aragonite
o
Z
u;
e
-c (
n.b. 2b, 2c and 3 are strengthened for cements if external morphology shows large ~
square-ended crystals. ~ \.
Criteria, in order of increasing reliability, for determining original aragonitic nature of C
calcitized components (after Sandberg, 1983). Although useful alone, they are best utilized
in conjunction with observations on the whole spectrum of preservation styles within a C
single limestone.

(
C
(
c
( Limestones - The Meteoric Diagenetic Environment 57

c
c cross-cutting mosaics and have rela- Importance of Grain Size. The importance of grain size or crys-
o tively high Mg2+ contents and low Sr2+ Most of the processes and products out- tal size is well illustrated in the common

o values. These differences are thought


to result from alteration across a film of
lined above have been worked out from
Pleistocene and Holocene calcarenites
phenomenon of micrite envelopes
(Bathurst, 1966;Alexandersson, 1972).

o water micrometres thick in the vadose


zone but across a chalky zone in the
because of their convenient grain size
and pore diameters. Likewise, grainy
On the sea floor, the outsides of carbon-
ate particles, such as bivalve shells,
phreatic zone. In the phreatic, because rocks should be looked at first in ancient commonly are bored byendolithic algae
the skeleton is surrounded by water, limestones to establish the general dia- whose vacated microborings are filled
( calcite continues to grow into a void, genetic sequence. When considering by microcrystalline aragonite or magne-
( whereas in the vadose zone the voids the full spectrum of carbonate sedi- sium-calcite cement, forming an "envel-
may be filled with air. These changes ments, however, it is clear that grain size ope" of finely crystalline carbonate.
o imply that alteration in the vadose zone
can be viewed as somewhat closed,
plays an important role. Mudstones, for
example, because of their small grain
When these grains come in contact with
meteoric waters the small crystals inthe
whereas phreatic calcitization takes size, alter much more rapidly than do envelope, because of their tiny size,
o place in a more open system.
This process is also viewed as oc-
contemporaneous calcarenites. Even
in calcarenites, the finer grained layers
alter quickly to calcite (more quickly if
magnesium-calcite than if aragonite),
curring in a "two-water system" are commonly cemented first, probably before the aragonite of the bivalve
(Pingitore, 1982), with (1) a small because the finer grained layers hold begins to dissolve. So for a time the
amount of slow-moving water at the dis- water longer by capillary action (Evans bivalve is still aragonite while the envel-
c solution- reprecipitation interface
which exchanges with (2) a large vol-
and Ginsburg, 1987).Such preferential
cementation of calcarenites is impor-
ope is calcite. Eventually the shell may
be leached away and only a thin micro-
ume of faster-moving water percolating tant because subsequent water move- crystalline rind is left outlining the
or flowing through the rock or sedi- ment is preferential through channels bivalve mold.This mold isthen filled with
ment. Water at the interface can be and voids around the cemented layers, calcite cement (Figure 24). If it were not
o considered an almost closed system leading to rapid porosity enhancement for the difference in grain size, miner-

o which is, in turn, connected by diffusion


to a large open reservoir.
The alteration of aragonite skeletons
and beginnings of karstification.
The alteration of polymineralic muds
in the meteoric environment is difficult
alogy, or relative resistance to dissolu-
tion (if both aragonite), and thus dif-
ferent alteration rates, all would have
to calcite also results in changed to study because oftheirsmall grain size been dissolved together and there
o petrophysical characteristics. In corals, and propensity for rapid alteration. would be no record of the presence of

c for example, calcitization leads to an


overall decrease in porosity, mainly
Recent studies utilizing SEM (Steinen,
1978,1982;Lasemi and Sandberg, 1984)
bivalve shells.
At the other end of the spectrum,
o because of precipitation of calcite
cement into pores, but an increase in
indicate that the same processes occur
as in calcarenites. Plio-Pleistocene
large whole aragonitic fossils (gastro-
pods, bivalves, corals) alter more slowly
C permeability because of changes in mudstones formed from aragonite-rich than sand-size aragonite particles, and
pore-aperture size (Pittman, 1974). muds are composed of both micrite and it is not uncommon to see partly altered
G Alteration of Calcite Components. microspar (sensu Folk, 1965) and corals surrounded by well-cemented,
o Biogenic components composed of cal-
cite, such as brachiopods, some
appear to be the end result of concur-
rent aragonite calcitization and pore-
but porous, calcite limestone containing
molds of smaller aragonite grains.
o bryozoans, planktonic foramininfers
and layers in some molluscs, appear to
filling cementation. The neomorphic
calcite exhibits aragonite pits and relics
Diagenesis in Vadose versus
Phreatic Settings.
remain unaltered under most meteoric on polished and etched surfaces and The style of and relative rates of sedi-.
o conditions. It should be remembered,
however, that these particles are not
the rocks have been called ADP (arag-
onite-dominated precursor) mudstones
ment alteration in the vadose and phre-
atic zones have been studied on rela-
o pure crystalline calcite, but are com- by Lasemi and Sandberg (1984). The tively large oceanic islands mantled

o posed of calcite, organic templates,


usually small crystallites, and numer-
cement regions are commonly com-
posed of several crystals in which each
by Pleistocene carbonates (Bermuda:
Land, 1970; Plummer et al., 1975;
c. ous micropores. Thus, they are more
soluble than the new diagenetic calcite.
continues into adjacent relic-rich neo-
morphic calcite as minute examples of
Jamaica: Land, 1973b; Barbados:
Steinen and Matthews, 1973). These
C. 0
So, once all aragonite and Mg-calcite "cross-cutting mosaics" observed by results can be used in a general way to
components have altered to calcite, the Pingitore (1976)in calcitized corals. This approximate conditions on larger car-
( limestone is composed of original cal- process transforms carbonate mud with bonate platforms. Studies on small
l cite particles and less soluble diage-
netic calcite components. A second
50% to 70%. porosity into mudstone
with commonly less than 5% porosity.
Holocene sand cays (e.g., Joulters
Cay: Halley and Harris, 1979) probably
(
stage of alteration, affecting only these These mudstones contrast with better reflect conditions of ephemeral
original calcite elements may then take COP (calcite-dominated precursor) exposure of small portions of plat-
place in deeper parts of the meteoric mudstones, which are mostly micrite forms. Two examples of vadose versus
environment (AI-Aasam and Veizer, composed of crystals with no relics or phreatic alteration are outlined in Fig-
1986a, b) or in the burial setting (Cho- pits, and are from more ancient ures 31 and 32.
quette and James, this volume). limestones.
c
58 Diagenesis Geoscience Canada Reprint Series 4 c
c
Suspicion that sediments continu- different, then mixing is likely to result little vadose flow, only seepage. Al-
c
ously in contact with meteoric waters in in dissolution, as in a wholly calcite though sediments are only in the ini- c
the phreatic zone alter more quickly
than those in the vadose zone, where
system.
Meteoric diagenesis on small islands
tial stages of alteration, several trends
are nonetheless evident. The main c
water flow is ephemeral, is borne out by
studies on the larger islands. Waters in
or sand cays with only local aquifers
appears somewhat different. Diagene-
point is that on small islands the rates of
diagenesis above and below the water
c
these large phreatic lenses not only per- sis throughout is very rapid in the best table do not appear to be much different . (
colate down from the vadose zone, but
also arrive at the water table directly
studied example, Joulters Cay (Halley
and Harris, 1979), but this may be due
In both cementation is patchy, but oolite
is more friable below the water table c
from lakes, swamps, rivers, and via
vadose flow through fissures. Because
partly to the high aragonite content of
the sediments (almost all ooids). An
than above because precipitated calcite
is a true "cement" in the vadose zone,
c
the phreatic waters are from different
sources, their chemistries and mineral
important difference from large islands
is that all the waters pass downward
forming an "onion skin" on the grains
and concentrating as a meniscus at
c
(
saturations show considerable tem- through the vadose zone before they grain contacts . In contrast, calcite in
poral variation. In some areas, it is reach the water table and there is the phreatic zone is precipitated as c
estimated that the bulk of the water in
the phreatic lens is not from vadose PETROGRAPHY GEOCHEMISTRY c
seepage but from vadose flow or lakes,
rivers and bogs. Thus, the phreatic
CAUCHE MARINE c
waters should be of different composi- 0/00
LEVELS
o + c
tion than the overlying vadose waters
and, because of mixing, the water table c
should be a level of considerable chemi-
cal activity.
c
Mg++-I I c
I:
Sediments composed of metastable
carbonates seem to alter rapidly in the
phreatic zone. Those areas studied to VADOSE c
date display both cementation and dis-
solution that result in extensive lithifica-
Sr+++--
I I
c
tion and in abundant aragonitic fossil
I I c
molds as well as calcitized skeletons.
There is no clear information about
I c
where in the phreatic zone grains alter
most quickly or in what manner, or I I c
whether all parts are affected equally. I I c
However, Longman (1980) has outlined a
hypothetical sequence of alteration for I I c
this zone, which remains to be tested.
PHREATIC
I I c
In any case , because of these dif-
ferences a common situation in Pleis- I I c
tocene carbonates is for sediments in
the vadose zone to be poorly lithified
I I c
and still mainly metastable, while the
same sediments in the phreatic zone
c
are calcite limestone, with a striking
MARINE
c
mineralogical discontinuity developed
at or near the water table.
c
It is not clear whether dissolution or c
precipitation will prevail in the phreatic
zone during these early stages of dia-
Figure 31 A sketch illustrating a hypothetical core through an ooid grainstone shoal
exposed to meteoric diagenesis under semi-arid conditions, resulting in a caliche profile.
c
genesis because the processes depend
upon so many factors. If, for example,
Sediments below the mixing zone are saturated with marine pore waters and essentially
uncemented. The geochemical curves are based on results one might obtain from "bulk"
e
vadose waters several times oversatu- analyses. The limestone was originally composed of aragonite ooids, hence the high initial
Sr2+ and low Mg2+ concentrations. Stabilization is essentially complete in the freshwater
c
rated with respect to calcite because of
abundant dissolution of aragonite are phreatic zone.
(
A Pa/eoexposure Surface - caliche crust, partial conversion of ooids to calcite micrite,
mixed with phreatic waters that are just
saturated with respect to calcite, and needle and other calcite cements, gravity effects, vadoids. C
PC0 2 levels in the waters are not too
B Vadose zone - conversion of ooids to calcite with mostly good preservation, meniscus and
gravity calcite cements.
l
different, then cementation can occur at
least adjacent to the water table . If, on
C Freshwater Phreatic Zone - extensive dissolution (fabric selective). calcitization, iso-
pachous calcite cement.
l
the other hand, PC0 2 levels are very o Mixing Zone - preservation of aragonite ooids, poor induration, some rhombs of low to C
high magensium-calcite.
C
C
c
c Limestones - The Meteoric Diagenetic Environment 59
c
c
o scattered rhombs all over the grain sur-
faces and not necessarily at grain con-
tacts . The most intensively cemented
sand cay, whereas stabilization will pro-
bably take some 100,000 to 1,000 ,000
years on Bermuda and along the coast-
Cementat ion of limestones by CaC03
in mixing zones may not be extensive. In
very young Holocene sediments (ca.
(J zone is right at the water table . Cemen- line of South Australia (Reeckmann and 1,000 years old) beneath south Joulters
( tation decreases with depth in the phre- Gill, 1981). Cay on Northeastern Great Bahama
atic zone as the proportion of seawater The Freshwater-Seawater Mixing Zone. Bank, for example, there is virtually no
( increases. The possibil ity that dolomite may form cementation at all below the freshwater
( Interestingly,calculations suggest that in miXing zones has provoked consider- phreatic lens. Minor amounts of low-Mg
at the currentrate all the sediment will be able interest in the hydrology, chemistry calcite cement have been found in
( stabilized 16 calcite within 10,000 to and mineralogy of such zones (see Mor- paleo-mixing zones on Barbados (Ben-
20,000 ye~rs on this small carbonate row, th is volume) . son, 1973; Steinen, 1974), northern
( Jamaica (Land, 1973a, b), and a coastal
( area of Grand Cayman Island (Moore,
PETROGRAPHY GEOCHEMISTRY 1973). Coastal mixing zones are, in a
o sense, involved in the formation of

o MARINE
LEVELS
beachrock (discussion in James and
Choquette , this volume), but CO 2
o o + degassing in these zones, rather than

o ® /
/
/
mixing effects , may be mainly respon-
sible for CaC0 3 cements there (Hanor,
o S
/
I 1978).
There is considerable evidence that
o Mg++ ,
~I
I dissolution is important in mixing zones.
Non-fabric selective dissolution occurs
0_ VADOSE /: I along some 150kilometres of the north-
o "" I I
eastern Yucatan coast, apparently in a
coastal mixing zone (Back at al., 1978,
o l{}.1J I ~ h?-f ~ I
I/v e:r Id--v I /
1979, 1984), producing a striking scal-
loped morphology and related collapse
(
(-1- features (Figure 33). Mixing corrosion

: I
I I
PHREATIC I I

o : I
I I

MARINE

o
Figure 32 A sketch illustrating a hypothetical core through a reef limestone exposed to
meteoric diagenesis in a warm , moderately humid climate . Subaerial exposure produced a
corroded fractured surface karst. Sediments below the mixing zone are saturated with marine
l pore waters. The geochemical curves are based on results one might obtain from "bulk "
analyses . The limestone was originally composed of coralline algae (A, magnesium-calcite),
l bivalves and corals (8 and C, aragonite). Stabilization is mostly complete in the freshwater
phreatic and the offset of the 5' 3C profile at the water table is due mostly to precipitation of
diagenetic calcite cement. Figure 33 An oblique areal photograph of
A Pa/eoexposure Surface - dissolution and fracturing, geopetal vadose sediments, good the coastline at Caleta XelHa, Quintana Roo,
skeletal preservation. Yucatan Peninsula Mexico. The irregular
B Vadose Zone - mostly good preservation though skeletal aragonite is calc itized, minor coastline is the result of dissolution of Pleis-
development of molds and matrix vugs. tocene limestone along joints by brackish
C Freshwater Phreatic Zone - extensive dissolution , prolonged flushing, non-fabr ic selec- groundwaters which are undersaturated
tive voids, some calc itization and calc ite cement precipitation (black = porosity) . because of mixing fresh water and seawater.
D Mixing Zone - not exposed to meteoric waters, aragonitic fossils may be calcitized, The waters come to the surface in this
magnesium content of coralline algae high in lower part, dissolution likely in upper part (dilute locality at the irregular area about 200 m
pore waters). across marked by the arrow.
(

60 Diagenesis Geoscience Canada Reprint Series 4 C


C
on a large scale has probably occurred and geographic extent have been docu- 17). ThislossinSr2+ and Mg2+ is appar-
C
along the base of the vast freshwater mented in some widespread conti- ently reversed with passagethrough the C
lens in parts of the south Florida aquifer nental-coastal aquifers (e.g., the South mixing zone (Wagner, 1983) , which
(Vernon , 1969), and distributions of Florida aquifer: Back and Hanshaw, appear to be particularly well defined by C
caves in limestones beneath large downward increases in Mg2+ content.
oceanic islands, such as Bermuda, sug-
1970).
The curve in Figure 8, illustrating the Below the water table, beyond the
C
gest that brackish waters may have had effect of mixing fresh and seawater, is reach of oxygenated water, metals that C
a part in their origin (Palmer, 1984) . plotted for calcite only. Other minerals can exist in lower oxidation states such
Where CO 2 is not a major factor show the same effect, but have different asMn 2+ andF&+ become available for C
and fresh water and seawater mix saturation indices. Thus, there is a por- incorporation into diagenetic calcite (
according to the error function relation- tion of the curve (or percentage of sea- (C02+ and Ni2+ also may playa role
ship described earlier, it seems likely water in the mix) where waters are satu- here) , result ing in an overall net C
that dissolution is favoured in the rated or oversaturated with respect to increase in these elements with pro-
upper, more dilute reaches of the mix- calcite, yet undersaturated with respect gressive burial Meyers and Lohmann C
ing zone (see Figure 3), as might be
expected from Figure 8, and that
to aragonite - a situation which would
lead to aragonite alteration. Along parts
(1984).
The level of cathodoluminescence
C
CaCOa precipitation (and dolomite for- of the Yucatan coast, for example, the (Cl) varies sharply among growth C
mation?), if significant, should take critical mixture appears to be between zones in crystals of carbonate cement
place in the lower reaches of this zone. 50% and 60% seawater (Back et aI., (see Machel, 1985, for detailed discus-
C
Where calcite is the cement precipi- 1986). sion). As illustrated in Figure 34 , vadose C
tated, in metastable limestones it might It is likely that the rock record will be cements show little or no Cl because
be expected to become more Mg-rich found to contain more examples of dia- vadose waters normally are well oxyge- C
downward in the mixing zone. This Mg- genesis and cement stratigraphies nated, so that neither Fe2+ or Mn2+
rich fingerprint should not be preserved imprinted by local and regional mixing exist. Below the water table oxygena-
C
long or deeply into the sublenticular zones. tion and Eh decrease rapidly, so in the C
phreatic realm, however, unless by such shallow lenticular phreatic zone Cl is
features as microdolomite inclusions GEOCHEMICAL ASPECTS OF both present and highly variable, but is C
(Meyers and Lohmann, 1978). It is
attractive to interpret as products of mix-
METEORIC DIAGENESIS
Minor Elements. Dissolution of arag-
essentially nil (dark) in the deeper phre-
atic zone. Variability can best be
C
ing-zone precipitation those calcite onite (at whatever scale from micro to attributed to fluctuations in supply of C
cements which have these inclusions, macro) releases strontium (Sr2+) and activator ions (mainly Mn2+) and sup-
are clearly not synsedimentary marine other less abundant trace cations to the pressor ions (mainly F& +) and to varia- C
in origin , and are spatially associated
with identifiable phreatic cements.
surrounding pore waters ; incongruent
disssolution of Mg-calcite releases
tions in water flux in response to either
seasonal or longer cycles; these fluctu-
C
Meyers and Lohmann (1984) argue per- Mg2+ . The result in the carbonates is a ations are greatest in near-surface C
suasively for precipitation of these in- net decrease in both Sr2+ and Mg2+ hydrologic regimes, particularly, the
clusion-rich cements from regionally either with accompanying passage vadose. Phreatic-zone Cl, first identi- C
extensive transition zones, and it is true
that modern brackish mixed-water
through the vadose and freshwater
phreaticzones, or during continued res-
fied by Meyers (1974) in a landmark
study, has since been described in
C
zones with comparable distributions idence in either zone (Figures 16 and many parts of the Phanerozoic (e.g.,
E
l
C
C
C
c
e
(
(
C
Figure 34 (Left) two stages of cementation in an Early Cambrian grainstone: V, vadose pendulous cement; P, phreatic blocky calcite (plane
(
polarized light).
(Right) cathodoluminescence, vadose cement has irregular trace element content, phreatic cement is two-staged; p,.dark and bright \-
luminescent zones, probably shallow phreatic; P 2 , dull luminescence, probably deep phreatic. (Photo width is 5 mm).
C
C
C
c
c Limestones - The Meteoric Diagenetic Environment 61

C'
c. Grover and Read, 1983; James and Although the tempo of research on and oxygen isotopes within the near-
o Klappa, 1983 ; Meyers and Lohmann,
1984). Cathodoluminescence is a
minor elements in carbonate diagene-
sis is increasing (see discussions by
surface meteoric. At present, our knowl-
edge of carbonate-ion isotopic com-
o powerful tool for deciphering of ten-
complex cementation histories, par-
Brand and Veizer, 1980 ; and Lohmann,
1983, 1988), our understanding of the
positions diminishes with increasing
depth below subaerial exposure sur-
( ticularly where CL zones can be cali- behav iour of these elements even in the faces, even in Holocene and Pleisto-
c brated with minor-cation compositional
data . Mussman et al. (1988), for exam-
near-surface meteoric environment is
still fragmentary and evolving . In gen-
cene carbonates. The profiles in Fig-
ures 31 and 32 typify fairly well the kinds
( ple, have utilized these techniques to eral terms, however, the profiles in Fig- of stratigraphic distributions of carbon-

c interpret the depth to which meteroic


fluids were important diagenetic agents
ures 31 and 32 appear to be reasonable.
Stable Isotopes.
ate 51 3C and 51 80 in young Pleistocene
sequences. In these profiles, the pat-
c below the Middle Ordovician, post- Considerably more is understood about terns are emphasized rather than abso-

c Knox interregional unconformity in the


Appalachians.
the distribution and diagenetic "behav-
iour" in carbonates of stable carbon
lute values, and it is clear that with varia-
tions in absolute composition these
patterns are valid for many, if not most,
+6 limestones SUbjected to near-surface
c AVG 0 0 OF I
18 meteoric diagenesis at least as far back

o CALC ITE PPT'D


IN OPEN METEORIC' ®
in geologic time as Late Paleozoic. The
profiles are based on a series of recent
o +4 PORE-WATER SYST I INCREASING
METEORIC EFFECTS
studies (e.g., Magaritz, 1975, 1983;
Allan and Matthews, 1977, 1982;
o Q If MARINE Salomons et ei. , 1978; Videtich and Mat-
+2
AVG"O I3C - t;~-,I4ilIjj_~~, SEDIMENTS thews, 1980; Wagner, 1983). The gen-
eral subject of 51 3C and 5180 isotopic
MARINE SEDS
o ~w
z~
compositions and isotope geochemis-
try has been ably summarized by others
o o w~
::Eo::
(e.g., Bathurst, 1975; Hudson, 1977;
Veizer, 1983) and a lucid view of princi-
OW ~~
w~
-2 <
~~
~I
ss s
~-~
~~CJ
~ ,14J ples is provided by Lohmann (1983,
1988).
With sound petrographic work, it
(J)~ s s» is possible to interpret isotopic signa-

©
~g <---~
-4 C
c>z
0::
~
,..g/B
,..
tures of meteoric diagenesis with a
high degree of accuracy, provided
z- '<C otJ l4J
-W iil4J~ that one can get an estimate of the origi-
(J)u ~o nal marine 513 C and 5180 of a limestone
<z §iil4J
-6 Ww o'<CC) or limestone sequence prior to altera-
0:::;) o~~
u....J ~'<C tion. This can be done, as numerous
~u. OCJ~ studies (e.g., Lohmann , 1984; Given
Z , .........1.1'1
-8 and Lohmann, 1985) have convincingly
demonstrated, by taking the "heaviest"
PLEISTOCENE composit ions in a linear, covariant
COMPOSITIONS CALCITE PRECIPITATED series of values determ ined for those
-10 @ BARBADOS IN CALCITE & SOIL marine components that show the least
evidence of alteration. Such compo-
@ BERMUDA PROFILES
nents might be well-preserved brachi-
-12 opods (calcite originally) or marine radi-
-10 -8 o +4 axial cement, or originally aragonitic
rudists in which critera from Table 1 in-
l dicate good preservation following
Sandberg (1983). The covariant trend
Figure 35 A diagram showing isotopic compositions and trends in metastable carbonates approach, illustrated in Figure 35, has
where mineraJ-controlled alteration takes place in a meteoric system capped by a caliche-soil been used by Lohmann (1983) and
profile. The covariant trend (A) has as end member marine sediments (seawater) and 13C_ others to estimate orig inal marine
enrichedpore waters; diagenetic calcites precipitatedin a marine-meteoric mixing zone might
CaC0 3 compositions with apparent
have compositions along such a trend. If no caliche-soil profile existed, alteration of marine
accuracy. These graphs were presented
sediments might follow the trend shown by the top arrow gently down to the left (B). The long
vertical trend (C) would apply to rock-water interaction beneath a caliche-soil profile in the in the first of this servies of re views (see
shallow vadose, where 613C becomes heavier downward as "rock" CO~- overpowers soil James and Choquette, this volume).The
COz while 6180remains the same, as shown in Figures 31 and 32. The data fields are from Gross need for a " marine baseline" is critical
(1964) andAllan and Matthews (1977, 1982). The trends are in part based on interpretations by in older Paleozoic limestones - and
Hudson (1977), Lohmann (1982, 1983), and Magaritz (1983). possibly Cretaceous limestones -
c
62 Diagenesis Geoscience Canada Reprint Series 4 c
c
where original 01ac and 01eO of marine ence of isotopically "light" (1aC-poor) positions through the meteoric are
c
sediments and cements appear to have carbon. Calcites precipitated in caliche much less variable than carbon-isotope
values. The 01eO values of carbonates
c
been several per mille "lighter" than in
the present-day ocean (James and Cho-
and soil profiles - in hardpans, nodules
and associated vadoids - are typically in caliche and soil profiles are much like c
quette, 1983,Figs. 20 and 21). Contrary -7%0 to -13%0 in Recent and Pleistocene those of carbonates in the rest of the
to earlier ideas that this isotopic "light- profiles, changing downward within a vadose zone and the lenticular phreatic
ness" was the result of more prolonged few centimetres to metres at most to (except for the evaporation effect men- c
diagenetic alteration in older Pleisto-
cene limestones, it now appears that
values of -2%0 to -4%0, which are typical
for the rest of the vadose. The "light"
tioned earlier), generally -2%0 to -6%0 in
young Cenozoic carbonates. c:
real, non-linear variations in the com-
position of seawater through Phaner-
compositions reflect contributions of
CO2 from decaying organic matter to
Covariant trends of 01ac and 01eO
should also be displayed by CaCOa
c
ozoic time are represented. vadose pore waters seeping down- cements precipitated from mixtures of c
The range, and more significantly the
pattern, of carbon and oxygen isotope
ward or being drawn upward to evapora-
tion throughout the caliche-soil profiles
marine and fresh meteoric waters, as in
a mixing zone. The "end members" can c
compositions found in many Cenozoic (for discussion of these effects see be identified most clearly if they are c
limestones in shallow meteoric settings
- where limits of present-day or former
Rightmire and Hanshaw, 1973;Hudson,
1977; Allan and Matthews, 1982;
original marine CaCOa and carbonate
precipitated in a caliche or soil profile c
vadosezones, phreatic lenses and even
mixing zones can be determined with
Lohmann, 1983, 1988). Deeper in the
vadose, dissolved CO2 in pore water
(Figure 35). In progressively more
altered carbonates below profiles of this
c
increasing confidence - also occur in
many Phanerozoic limestones. Ranges
rapidly equilibrates isotopically with the
marine carbonate sediment through
kind (Figures 31 and 32), one often sees
an inverted "J" or "L" shaped trend, as
c
in fossil limestones are usually smaller which it is percolating. pointed out by Lohmann (1982, 1983),
(
because of the damping effects of later
burial cements or other forms of altera-
Speleothems, however, do not have
the same isotopic signature as vadose
Magaritz (1983) and AI-Aasam and
Veizer(1986).This kind oftrend on cross
c
tion, but patterns are similar. cements, generally because of kinetic plots is a result of the extremely "light", c
The general tendency in stratigraphic
profiles through young metastable car-
isotopic fractionation during rapid
degassing. Both 01ac and 01eO are
1aC-impoverished CO 2 supplied to
near-surface pore waters by decaying c
bonate sequences in near-surface
meteoric environments is for carbon-
enriched (Hendy, 1971; Lohmann, 1988;
Gonzalez and Lohmann, 1988).
organic matter, as noted earlier, and
the differences in rates at which pore
c
isotope compositions to vary consider- Oxygen in the CaCOa-H 20-C02 sys- waters equilibrate isotopically with the c
ably down through the vadose, par-
ticularly within short distances (metres
tem can come from the minerals, the
water and lor the gas, but in reality con-
host CaCO a sediments and rocks
through which they pass. Where organic c
or less)of subaerial exposure surfaces;
then to stabilize and remain relatively
tributions from dissolved CO2 are min-
iscule compared to contributions from
matter did not exist or was very sparse at
the surface, so that a caliche or soil pro-
c
constant through the shallow phreatic; the water and from host sediment or file did not develop, a "J"-shaped trend c
and finally to change through the mixing
zone toward marine or nearly marine
limestone. Thus oxygen-isotope com- will not be expected to develop.
c
values. Oxygen-isotope compositions c
show little variation through the vadose
and shallow phreatic except in the mix- c
ing zone where they become heavier,
enriched in 1eO because of preferential
c
loss of 160 by surface evaporation. c
Lohmann (1988) has called this invar-
iant 01eO value, when preserved in car- c
bonate precipitates, the meteoric cal-
cite line, which is likely to be unique for
c
each sequence and locality studied. c
These general relationships are shown
in Figures 31 and 32. Although the rela- c
tionships were recognized first in Pleis-
tocene sequences, they are commonly
e
preserved in Phanerozoic limestones
(Allan and Matthews, 1982)where they
c
may have value for signalling the pre-
(
sence of ancient subaerial surfaces. c
In the CaCOa-H 20-C02 system car-
bon comes almost wholly from the origi- Figure 36 Hard Pleistocene reef limestones overlying softOligocene chalks, Barbados. The c
nal carbonate and CO2 gas. Carbon-
isotope variability in near-surface
Pleistocene limestone hardened quickly in the meteoric environment because it was com-
posed of metastable minerals. The chalk remained soft because it was originally, and still is,
c
vadose zones is due mainly to the influ- composed of calcite. c
c
c
c
c Limestones - The Meteoric Diagenetic Environment 63

c
c- DIAGENESIS OF STABLE tionally well preserved. There is some by James and Choquette, this volume).
o CARBONATE (CALCITE)
SEDIMENTS
calcite cement, precipitated mostly as
epitaxial overgrowths on coccoliths and
If meteoric diagenesis, or more prop-
erly, the lack of meteoric diagenesis of
( It is clear that the extensive alteration echinoids. This minor cement is likely chalk, is any guide, then the subaerial

c and cementation of metastable carbon-


ate sed iments is driven by the co-ex is-
derived from the very smallest, super-
soluble particles . Compared with the
exposure of sediments in the lower and
middle Paleozoic, for example, should
c tence of different minerals with different
solubilities. But what about carbonate
metastable suites just described, these
sediments are virtually unaltered! The
leave little discernible evidence in the
form of diagnostic cement, signs of fab-
( sediments that are mostly calcite? We contrast is probably nowhere better dis- ric-selective dissolution, or geochem-
cannot, unfortunately, make a direct played than on the island of Barbados ical signatures. Since there were likely
comparison because shallow-water where soft Oligocene chalks directly some aragonitic components in these
C' Neogene carbonate sediments are usu- underlie hard, Pleistocene reef lime- calcite sediments, there was probably
a little cementation , but very little.
ally a mixture of minerals, but we can stones and, even though the permeabil-
( lookat deep-water chalks (Cretaceous- ity of the chalk is much less than that of Instead, the signature would be more in
o Recent) to gain some insights. These
sediments are , or were , composed
the reef limestone, both have been
exposed to percolating fresh waters for
the form of surficial karst, etc. These
conclusions have yet to be tested
almost entirely of calcite skeletal ele- nearly the same length of time, about against the rock record.
ments originally, with relatively few 500 ,000 years (Figure 36). It is impor-
( aragonite bioclasts. Exposures of Cre- tant , however, to note that in spite of the CRITERIA FOR THE RECOGNITION
o taceous chalk are widespread in north-
west Europe. Where these sediments
fact that the chalks are soft, they com-
monly exhibit deep surficial weathering
OF THE PRODUCTS OF METEORIC
DIAGENESIS
( have not been affected by deep burial or and solution cavities, to an extent remi- In summary, it is often possible to recon-

o percolation of hot waters they are


extremely soft, with over 40% porosity,
niscent of calcite limestones.
This striking difference becomes
struct whether a given stratigraphic unit
has resided in a vadose or phreatic zone
o and have altered relatively little despite
70 to 90 m.y. of shallow burial and pro-
extremely important if the composition
of carbonate 'sediments in the past was
(or both) , either from field relationships,
from petrographic features seen at
o longed exposure. The chief alteration is at times different from those of today, scales ranging from hand specimen to

o the loss of organic matter, aragonite and


opaline silica. Calcite fossils are excep-
and dominated by calcite constituents
(see discussion of sea-floor diagenesis
the light and scanning-electron micro-
scopes or, in some cases from geo-
c. chemical information. Careful petro-
graphic observation, aided by analysis
( Table 2 Some features helpful in identifying former vadose and of cathodoluminescent zonation and
phreatic diagenetic zones. cement chemistry, can make possible
detailed reconstructions of residence
VADOSE OR in a succession of diagenetic environ-
PHREATIC RELIABILITY ments. Many of the petrographiccriteria
MEGASCOPIC have been distinguished in very young
( Holocene and Pleistocene carbonates,
Calcrete, soil-zone features, root casts, often- V
complex travertine-filled fractures but are commonly preserved in the older
stratigraphic record. Large-scale fea-
Speleothems V tures of karst terrains are being applied
Stratified/laminated sediment in larger cavities P 2 with increasing success to the fossil .
(vadose sediment often inclined) record (James and Choquette, 1988)
Trains of horizontally elongate large solution P 2 and a great deal is now known about
cavities (may cross-cut structural dip) the kinds, if not always the origins, of
features formed in the vadose zone. The
Doninantly vertical solution cavities P 2
criteria outlined in Table 2 are often
MICROSCOPIC helpful in both distinguishing and identi-
fying the interface or transition zone
Preserved needle-fibres, flower spar, fungal V between vadose and phreatic zones in
sheath & related near-surface cements the fossil record . Many of these criteria
Meniscus cement V are quite reliable. Others are less so,
Gravity cements (micro-stalactite, -stalagmite) V either because they may be produced
in both zones near the water table, or
Isopachous cements" P 2 because they may originate in other
depositional-diagenetic settings , such
• 1 is more reliable than 2. as beachrock where gravity cements
•• May be difficultor impossible to distinguish from isopachous cements of submarine,
are well known.
sea-floororigin (see James and Choquette, 1983).
The complexities of overprinting in
this realm are well illustrated in nu-
merous studies (Heckel, 1983; Roehl
c
64 Diagenesis Geoscience Canada Reprint Series 4 c
c
over precipitation , and both fabric- Geochemical profiles in metastable
c
and Choquette, 1985).Atthesame time,
we now understand the main processes selective and non fabric-select ive fab- limestone beneath a karsted surface, c
and products well enough so that for-
ward modelling of meteoric diagenesis
rics should occur. Caves and solution-
enlarged fractures should be very
outlined in part in Figure 32, ideally may
resemble those in the right portion of c
in specific settings is being proposed extensive (Figure 37), stabilization to Figure 38. Because of high-volume flow
(Matthews and Frohlich, 1987). calcite limestone rapid, and vadose flow
dominant over seepage. Congruent
in the phreatic zone, substantial effects
can be seen in compositional profiles. c
THE EFFECTS OF CLIMATE
Since water and temperature are the
meteoric diagenesis is dominant. For the 0'3C and 0'80 profiles in the
c
two most important extrinsic factors in CLiMATE & METEORIC DIAGENESIS c
the processes of meteoric diagenesis,
climate - particularly the availability of ARID SEMI-ARID c
meteoric water - influences both the
intensity and rate of carbonate altera-
c
tion (Figure 37). The effects are strong- c
est in the vadose zone.
Under hot , arid desert conditions c
both karst and calcrete may develop, c
butslowly and intheformofthin profiles ;
likewise, alteration in the vadose zone
VADOSE
c
is slow. Thus, carbonates exposed for
extended periods under these condi- WATER c
tions mayshow little or no effect of mete-
oric diagenesis. In the phreatic zone,
TABLE b-=- :P~/-~~ 7'-l
c
alteration may be more extensive. PHREATIC CALCITE c
Water flow in the phreatic is likely to be
slow because of limited recharge .
CALCITE
c
Cementation may be limited and poros- c
ity and permeability high. There are few
case studies, however, and so clear Figure 37 A diagram illustrating the effects of different climates on a series of metastable c
information is lacking .
If the climate is warm and semi-arid,
carbonates of the same age and composition. The geochemical profiles in Figure 38 apply
largely to semi-arid and wet (high rainfall) situatio?s.t\l,J ,J\.v{·
c
caliche should be both thick and exten- .Y\ EJ"')
y9 .J'\~~ /:<t
P ~l' c
sive, with surface karst also present
locally. Alteration in the vadose zone
SEMI ARID
depletion ~(--~) enrichme
Of \y _\ \,.3\
I .oJ..,..r<-~
HUMID
depletion ~(--~) enrichment
c
is relatively rapid and is dominantly in-
congruent, if the mineralogies are ~===:::::::=====::::=~~r=:~~~::::t~UBAERIA;:;r-;-~
-...!:6~18;0~;1~3:===:;~=~;~~~u~~:=1 c
metastable. Alteration is most gener-
EXPOSURE
SURFACE c
ally fabric-selective, and replacement of
original aragonite textures is good. Min-
VADOSE c
eralogical changes have been dis-
cussed earlier and diagrammed in Fig- 1
r - --,l---,l--~l----j
WATER
TABLE - 1 1 \ c
c
1 1
I I I I I I
ure 23. Geochemical changes, also r 11<) PHREATIC I I I
discussed earlier and outlined in part in
Figures 31 and 32, seem to follow the
I
I 1
I I I

,I-- ,.L---!-,--+---'t----l
1 I
TOP OF c
general direction shown , with slight
abrupt offsets at the water table if the
\ \ 1:3/
\
\
'\
MIXING
ZONE
\
\
-,
\ c
phreatic and vadose zones behave as
\ \
)<
/
'\
\
c
somewhat separate systems (Wagner,
1983). Changes are rapid in the vadose
Figure 38 Stratigraphic patterns of geochemical profiles in a sequence of initially aragonite
and magnesium-calcite limestones beneath a subaerial exposure surface, under arid or semi-
c
and very subdued or essentially nil in
the phreatic. Caves are rare and small ,
arid conditions (left) and humid conditions (right). Open arrows show dominant directions of
groundwater movement. Offsets in isotopic composition, cation concentrations and cath-
e
and movement of ground water in the odolum inescence (Lum, mainly reflecting Mn z + if FeZ+ is not excessive) occur at the water (
vadose is mostly by vadose seepage.
Under warm and rainy conditions
table because the vadose and phreatic zones behave as more or less separate hydrologic
systems , particularly in the humid setting where water is greater in the phreatic and water c
(subtropical to tropical), although mod-
chemistry is affected by other recharge sources as well. In the ertd-semi-eria setting there is
upward enrichment in Sr z + , MgZ + , and 18 0 in the shallow vadose due in part to upward c
ern diagenetic changes are difficult to
determine because of extensivevegeta-
movement of vadose pore waters in response to high surface evaporation " wicking effect':
Profiles for the phreatic and mixing zone are similar in both situations. The profiles are
c
tion and rugged karst topography, sur-
face and subsurface karst should be
somewhat modified from Wagner(1983). They were developed from data from boreholes in the c
extensive, dissolution would prevail
Pleistocene of Barbados (see text) and from profiles of various ancient stratigraphic
sequences beneath subaerial exposure surfaces (Allan and Matthews, 1982; Wagner, 1983). c
c
c
c
C' Limestones - The Meteoric Diagenetic Environment 65

C
C phreatic there may be an offset toward PC02 levels were higher than those that were available to be altered. As
pointed out by Lowenstam (1963) and
C heavier compositions if cementation by
calcite has been slight , or offset toward
today, and an "icehouse" mode when
they were more like the modern atmo- Wilkinson (1979), the mineralogical
C. lighter values if meteoric calc ite cemen- sphere (Fischer, 1981). During the composition of shallow-water skeletons
tation has been extensive . Dissolution greenhouse mode, meteoric waters , has varied through geologic t ime.
C of aragonite and magnesium alteration with increased PC02, would have been Although the trends are not yet firmly
of Mg-calcite may be so extensive in the established, first-order variations seem
C vadose zone that greatly enriched pore
more aggressive than they are today.
clear (Figure 39). In general, sediments
How this would be reflected in the rock
C waters lead to enrichment of Sr2+ and record is difficult to assess. In areas of on modern and Cenozoic shallow plat-
Mg2+ in diagenetic calcite. forms are or were mostly aragonite and
C In summary, in warm climates the
thin soil cover, or at times when soils
were poorly developed, increased sim- magnesium-calcite, whereas those in
( supply of meteoric water is important in ple corrosion would lead to more exten- similar Mesozoic settings were about
determining the rate, intensity and even sive surface karst. Intuitively, one feels equally aragonite and calcite (either
( direction of diagenetic alteration. Varia- high-magnesium and low-magnesium).
that there should be more extensive
o tions in rainfall may be substantial
across the larger oceanic islands that
karst development during these times, In contrast, sediments in the middle and
early Paleozoic were mostly calcite
o rise some hundreds of metres above
yet most extens ive dissolution occurs
beneath a soil and not on bare rock. So (except perhaps for the earliest Cam-

o sea levelbecause of rain shadow effects


and are generally even greater across
the effect should be most noticeable in
areas where there is little soil develop-
brian). The history of the mineralogy of
non-skeletal particles seems more
( large land masses. ment, or at times when soils were poorly complex (Sandberg, 1983), and varied
in an oscillating fashion. Because the
o LARGE-SCALE VARIATIONS
developed.
Changes in the Biosphere. style of diagenesis is partly dependent

o THROUGH GEOLOGIC TIME


It is common practice to extrapolate the
Terrestrial: Weathering effects and
the generation of CO2-charged waters
upon sedimentary mineralogy, those
sediments with abundant aragonite will
o processes and products of meteoric
diagenesis observed today to the fossil
are heavily dependent upon the pre-
sence and evolution of higher plants.
have undergone the most extensive
alteration and have been cemented
record. As emphasized by James and Although land plant fossils are known most in the meteoric environment. Con-
r: Choquette (this volume) , however, from the early Paleozoic, theywere not a versely, those predominantly calcite
there have been changes in the nature significant part of the terrestrial land- and Mg-calcite sediments will be little
of the atmosphere and biosphere scape until Devonian time, but were affected and illustrate features because
through geologic time which may have widespread by the early Mississippian . of water-controlled alteration. These dif-
C profoundly influenced the style of Thus, even though soils may have ferences are well demonstrated byany-
meteoric diagenesis (Figure 39). one who has marvelled at the superb
l Changes in the Atmosphere.
existed in the early and middle Paleo-
preservation of early Paleozoic fossils,
o It now seems probably that there have
been variations in atmospheric PC02
zoic, they would have been close to the
protosoils of today, dominated by algae
and lichens , and unlike the complex
yet struggled to discern the nature ofthe
numerous recrystallized and partially
C through the Phanerozoic. The atmo- biogenic profiles in true soils. dissolved skeletons in Cenozoic lime-
stones (Figure 40). It often seems that
(' sphere seems to have oscillated Marine: Of equal importance is the
the older the limestone, the better the
between a "greenhouse" mode when mineralogy of carbonate sediments
(I preservation!
SEDIMENTARY MINERALOGY
Synthesis: By integrating these vari-
LANO CUMATIC METEORIC ables in a general way,wecan speculate
o
r
0
T
PLANTS

ANGIOSPERMS
EPISODES

ICE HOUSE
OIAGB4ESIS
1 T
on potential variations in diagenesis.
The Phanerozoic could be subdivided
into five periods when the effects of
100 K GREEN K
( meteoric diagenesis were probably dif-
J GYMNOSPERMS HOUSE 2 J
ferent (Figure 39).
200 'Ii 'Ii
(, I LOWER ICEHOUSE
~
1. OLIGOCENE - PRESENT. Since
300 3 conditions were similar to those today
C VASCULAR C
PLANTS and in the recent past, the present mete-
D 0 oric environment is a good guide to
6 400 S GREEN
HOUSE 4
S
rocks of this age.
0 ALGAE 0
2 . LATE TRIASSIC - EOCENE. A
500 • period when sediments had less arag-
r
C ,, LICHENS
ICE HOUSE 5
C
800 P-C , PC onite, atmospheric CO2 was higher and
there were no terrestrial grasses,
Figure 39 A plot of variations in non-skeletal mineralogy (James and Choquette, 1983; although plant cover in general was
Sandberg, 1983), skeletal mineralogy (approximated from Lowenstam, 1963; Wilkinson, 1979), extensive. The spectrum of textures and
terrestrial vegetation and atmospheric PC02 (Fischer, 1981) throughout Phanerozoic time. fabrics describedin this article shouldbe
Numbers at right indicate approximate intervals when the combined effects of these variables expected for rocks of this age, with per-
probably resulted in different styles of meteoric, particularly vadose, diagenesis. haps more obvious surface karst.
,-
c
66 Diagenesis Geoscience Canada Reprint Series 4 c
c
3. LATE DEVONIAN/EARLY It must be remembered that this Although many reactions take place c
CARBONIFEROUS - MID TRIASSIC.
During these times, the atmospheric
scheme is a generalization, a back-
ground against which to consider
in this setting, in terms, of carbonate
diagenesis two are critical: (1) a first-
c
PC0 2 was similar to that of today, plant meteoric diagenesis, realizing that local order reaction, water-controlled (con- c
cover was potentially extensive, and
sedimentary mineralogy was roughly
conditions may completely overprint
the general trends. Conversely, where
gruent) meteoric diagenesis, controlling
dissolution and precipitation in general c
the same as in younger rocks (less skel- lack of alteration or absence of mete- by invasion and evasion of CO2 from
oric diagenetic features has in the past meteoric waters; all CaC0 3 minerals
etal aragonite). Both surface karst and
calcretes probably developed com- been interpreted as lack of exposure, it including calcite are dissolved, but only c
monly at this time, with somewhat less
cementation and dissolution and so less
is also clear that exposure may have
taken place without any significant
calcite is precipitated; (2) a second-
order reaction, mineral-controlled c
fabric-selective diagenesis than in signature. (incongruent) meteroric diagenesis, c
younger rocks.
4.MID CAMBRIAN-MID DEVONIAN. SUMMARY
which affects minerals of differing sol-
ubilities; aragonite and Mg-calcite, but c
A time quite different from the recent Carbonate sediments commonly are
exposed to percolating meteoric waters
not calcite, are dissolved and new dia-
genetic calcite is precipitated. Both
c
past: atmospheric PC0 2 was relatively
high. There were no true land plants, so
at various times during their history. reactions occur concurrently when c
soils were poorly developed. Carbonate
Since they are mostly deposited in shal-
low waters, small changes in sea level,
metastable carbonates are flushed by
meteoric waters, but once the minerals c
sediments were composed mostly of
calcite. The effects of meteoricdiagene-
whatever the cause, will result in sub-
aerial exposure early in their history,
haveall changed to calcite, only the first-
order reaction continues and much of
c
sis at this time were probably minimal
and confined to surface and subsurface
either immediately after deposition or the meteoric environment becomesdia- c
karst, non-fabric-selective alteration,
little cementation, little or no caliche
after shallow burial. Once they are
exposed, a predictable hydrologic regi-
genetically inactive.
Regardless of which reaction is pre- c
and much fabric retention.
men is established, with only minor sur- valent and what carbonate minerals are (
ficial exposure resulting in relatively present, there is a net loss of carbonate
5. LATE PRECAMBRIAN? - EARLY
CAMBRIAN. Scant evidence suggests
deep percolation of fresh water and from the system. This is best reflected c
that the atmosphere was like that of
accompanying diagenesis. Although
the occurrence of meteoric diagenesis
in a variety of karst-related features.
Atthe sametime, soil-related processes c
today in terms of Pco 2 and sedimentary
mineralogy was like that in the middle
can be established from textural and
fabric criteria, pinpointing specific
form a variety of very distinctive caliche
carbonates which, because they are
c
Paleozoic, but that there were poor zones of alteration is difficult because, accretionary, are preserved and are c
soils. Again much karst, and little or no
caliche were developed, but some fab-
with time and fluctuating sea level, the
zones migrate through the rock. Stages
extremely useful as criteria of subaerial
exposure. If the exposed sediments are c
ric-selective alteration. Cementation of alteration are thereby superimposed composed of metastable carbonates, a c
would have been the most significant
results of meteoric diagenesis.
or early stages of diagenesis are oblite-
rated by later ones.
specific, predictable series of changes
takes place, and lithification is achieved c
c
c
c
c
c
c
c
c
e
c
(
C
l
Figure 40 (Left) Ordovician limestone with all the fossils, trilobites (T), brachiopods (B), and bryozoans (C), preserved because they were
originally calcite. C
(Right) Pleistocene limestone illustrating porosity developed by dissolving stick-corals (C) and gastropods (G).
C.
(

C
(
( Limestones - The Meteoric Diagenetic Environment 67

c
C' by precipitation of cements with distinc- REFERENCES Esteban, M. and Klappa , C.F., 1983, Sub-

o tive structures which are preserved in


ancient limestones . Concomitantly, General References
aerial exposure, in Scholle, P.A.,
Bebout , D.G. and Moore , C.H., eds.,
CJ because the process of alteration These articles and books address various
aspects of meteroic diagenesis and
Carbonate Depositional Environments:
American Associat ion of Petroleum
involves dissolution and precipitat ion,
together cover most of the topics discussed Geolog ists, Memoir No. 33 , p. 1-54.
there is important cation and isotopic
in this paper . A beautifully illustrated, up to date refer-
exchange with meteoricwaters,leading
C' generally to lower Mg2+ and Sr2+ con-
ence synthesizing much of our under-
Allan, J.A. and Matthews, A.K., 1982, Iso- standing of surficial diagenesis .
( tents and higherFe2+ , Ca2 + and Mn2 + , tope signatures associated with early Folk, A.L., 1973, Carbonate petrography in
as well as depletion in both 513C and meteoric diagenesis : Sedimentology, the post -Sorbyian age, in Ginsburg,
/) 1 8 0 , compared with the original v. 29, p. 797-817. A.N., ed., Evolving Concepts in Sedi-
c sediments.
The intensity of meteoric diagenesis
A good discussion of the theory behind
and examples of isotop ic variations dur-
mentology : Johns Hopkins University,
Studies in Geology, v. 21, p. 118-158.
( is dependent not only upon where in the ing meteoric diagenes is. A succinct essay presenting, amongst
Bathurst, A.G.C ., 1975, Carbonate Sedi- other things, an outline of the processes
environment changes have take place,
( ments and their Diagenesis: Elsevier and products during subaerial diagene-
but also upon the residence time in any
Scientific Publishing Co., Amsterdam , sis of metastable carbonates.
particular zone . Climate is also an 658 p. Halley, A.B. and Harr is, P.M., 1979, Fresh-
important factor in vadose alteration . Bathurst, R.G.C., 1980, Lith ification of car- water cementation of a 1,000 year old
The processes and products of mete- bonate sediments: Science Prog ress oolite: Journal of Sedimentary Petrol-
o oric diagenesis described in this article
cannot be applied equally to carbonates
Oxford, v. 66, p. 451-471.
These two references are the best syn-
ogy, v. 49, p. 969-988 .
One of the few studies to integrate
o of all ages. Changes in the biosphere theses of information concerning the petrographic, geochemical and hydro-

o (vary ing skeletal mineralogy and


changes in terrestrial vegetation) and
alteration of metastable carbonates in
the meteoric environment.
graphic data in the study of the early
diagenesis of metastable carbonates.

o the atmosphere (varying Peo.) through


Bathurst, A.G.C., 1986, Carbonate diagen-
esis and reservoir development: con-
James , N.P. and Choquette , P.W., 1988,
eds., Paleokarst: Springer-Verlag, New

o geologic time will have had a profound ,


but as yet uncertain, effect on the style
servation , destruction and creation of
pores : Colorado School of Mines Quar-
York, 421 p.
A series of 18 papers covering all major

o and intensity of freshwater diagenesis .


Finally, when examining any lime-
terly, v. 81, No.4, p. 1-24.
A succinct review of meteoric and other
aspects of karst and paleokarst, exam-
ples range in age from Precambrian to
c stone outcrop it should be remembered
that this rock is now in the meteoric
diagenesis , focussed on the evolution of
porosity.
modern.
Longman, M.W., 1980, Carbonate diage-
Bagl i, J., 1980, Karst Hydrology and Physi- netic textures from near-surface diage-
environment and many of the fabrics
o and textures present may be the result
of very recent processes!
cal Speleo logy: Springer-Verlag, Berlin,
285 p.
netic environments: American Associa-
tion of Petroleum Geologists, Bulletin,

o ACKNOWLEDGEMENTS
A text devoted to the processes of karst
formation: a good single source outlining
basic concepts of rock-water inter-
v. 63, p. 461-487.
A useful summary of the processes and
products of meteoric diagenesis of meta-
We thank many colleagues who offered actions. stable carbonates, a good place to begin.
o suggestions and guidance during the
preparation of this manuscript: W. Back,
Bricker, O.P. , 1970, ed ., Carbonate
Cements: The Johns Hopkins Press,
Matthews, A.K., 1974, A process approach
to the diagenesis of reefs and reef-asso-
R.G.C. Bathurst , N. Chow, M. Coniglio, Baltimore, MD, 376 p. ciated limestones , in Laporte, L.F., ed.,
This book conta ins a suite of papers on
o D.H. Craig, A. Desrochers , J.A.D .
Dickson, D. Haywick, J. Kennard, K.C. meteoric diagenesis with excellent
Aeefs in Time and Space: Society of
Economic Paleontolog ists and Mineral-

o Lohmann, R. Reeder, P. Sandberg, L.


Vacher, P. Wagner and B.H. Wilkinson .
illustrations of different types of meteoric
cements.
ogists, Special Publication No. 18,
p.234-256.

o N.P. James acknowledges the Natural


Sciences and Engineering Research
Chafetz, H.S., Wilkinson , B.H. and Love,
K.M., 1985, Morphology and composi-
A useful paper describing many of the
principles of meteoric diagenesis using
( tion of non-marine cements in near-sur- the Pleistocene of Barbados as an
Council of Canada for ongoing financial face settings, in Schne idermann, N. and example.
c support. Harr is, P.M., eds. , Carbonate Cements:
Society of Economic Paleontologists
Matthews , R.K., 1987, Eustatic controls on
near-surface carbonate diagenesis:
C and Mineralogists, Spec ial Publication
No. 36 , p. 337-348 .
Colorado School Mines Quarterly, v. 82,
No.1, p. 17-39.
l A good review of some of the cements Outline of the dynamics of meteoric dia-
precipitated in the meteoric environ- genesis with several examples to illus-
C ment, with excellent photographs. trate the principles.
l Choquette, PW. and Pray, L.C., 1970, Geo-
logical nomenclature and classificat ion
Plummer, L.N., 1975, Mixing of sea water
with calcium carbonate groundwater, in
of porosity in sedimentary carbonates: Whitten, E.T.H., ed., Quantitative Stud-
American Association of Petroleum ies in the Geological Sciences: Geologi-
Geologists, Bullletin, v. 54, p. 207-250. cal Society of American , Memoir 142,
An outline of the basic concepts of fabric- p.219-236 .
selective and non-fabric selective altera- A discussion of the chemical basis for
tion of carbonates. many of the concepts of freshwater-sea-
water mixing.
c
68 Diagenesis Geoscience Canada Reprint Series 4 c
(

Plummer, L.N., Vacher, H.L., Mackenzie, Manhe im, F.T. , 1967, Evidence for sub - Runnells , D.D., 1969, Diagenesis of chemi-
c
F.T., Bacher, O.P. and Land, L.S., 1976,
Hydrogeochemistry of Bermuda: A case
marine discharge of water on the Atlan-
tic continental slope of the southern
cal sediments and the mixing of natural
waters: Journal of Sedimentary Petrol-
c
history of groundwater diagenesis of
biocalcarenites: Geological Society of
United States and suggestions for fur-
ther research : New York Academy of
ogy, v. 39, p. 1188-1201.
Schmalz, R.F., 1967, Kinetics and diagene-
c
American, Bulletin , v. 87, p. 1301-1316. Sc ience , Transact i o ns, v. 29 , sis in carbonate sediments: Journal of (
An integrated study of groundwater geo-
chemistry of an island where many of the
p.839-853 .
Smith, 0.1., Atkinson , T.C. and Drew, D.P.,
Sedimentary Petrology, v. 37, p. 60-68.
Walter, L.M. and Morse, J,W., 1984, Magne-
sian calcite stabilities : a reevaluation:
c
principles of metastable carbonate die- 1976, The hydrology of limestone ter- C
t.....
genesis were worked out. ranes, in Ford, T.D. and Cull ingford, Geochimica et Cosmochimica Acta ,
Sweeting , M.M ., 1972, Karst Landforms :
Macmillan Publishing Co. Ltd., London ,
C.H.D., eds., The Science of Speleol-
ogy: Academic Press Inc., New York,
v. 48, p. 1059-1069.
Walter, L.M and Morse, J.W., 1985, The dis-
C
362 p.
A classic text discussion of the complete
593 p.
Todd, D.K., 1980, Groundwater Hydrology:
solution kinetics of shallow marine car-
bonates in seawater: a laboratory study :
C
spectrum of karst features. John Wiley and Sons, New York, 535 p. Geoch imica et Cosmochimica Acta , C
Thrailkill,J ., 1968,Chemical and hydrologic Vacher, H.L., 1974, Groundwater hydrology v. 49, p. 1503-1513.
factors in the excavation of limestone of Bermuda : Government of Bermuda, C
caves: Geological Society of America, Public Works Department, Hamilton, Modern Caliche
Bullet in, v. 79, p. 19-46. 87 p. C
A very readable outline of the principles
of carbonate dissolution and cave
Vacher, H.L., 1978, Hydrology of Bermuda-
significance of an across-the-island
Coniglio, M. and Harrison, R.S ., 1983,
Holocene and Pleistocene caliche from
C
formation.
Thraikill, J., 1976, Speleothems, in Walter,
variation in permeability: Journal of
Hydrology, v. 39, p. 207-226.
Big Pine Key Florida: Bulletin of Cana-
dian Petroleum Geology, v. 31, p. 3-14 .
C
M.R., ed., Stromatolites: Elsev ier Pub- Wheatcraft, S.W and Buddemeir, R.W., Harrison, R.S., 1977, Caliche profiles, indi- C
lishing Co., Amsterdam, p. 73-86. 1981, Atoll island hydrology: Groundwa- cators of near-surface subaerial diagen-
A well-illustrated paper describing the ter, v. 19, p. 311-320. esis Barbados, West Indies: Bulletin of C
different types of sinter. White, WB., 1969, Conceptual models for Canadian Petroleum Geology, v. 25,
carbonate aquifers: Groundwater, v. 7, p.123-173. C
Hydrology of Carbonate Terranes p. 15-21. James , N.P., 1972, Holocene and Pleisto-
cene calcareous crust (caliche) profiles ;
C
Bear, J., 1979, Hydraulics of Groundwater:
McGraw-Hili Inc., New York, 569 p.
Dissolution and Precipitation
(see also sections on geochemistry and
criteria for subaerial exposure: Journal
of Sedimentary Petrology, v.42,
C
Bear,J. and Todd, O.K., 1960,The transition freshwater-seawater mixing) p.817-836 . C
zone between fresh and salt waters in Klappa , C.F., 1978, Biolithogenesis of
coastal aquifers: Water Resources Cen- Badiozamani , K., 1973,The dorag dolomiti- Microcodium - elucidation: Sedimen- C
terContribution No. 29, Hydrau lic Labo- zation model- application to the middle tology, v. 25, p. 489-522.
ratory, University of California, 156 p. Ordovician of Wisconsin: Journal of Klappa , C.F., 1979, Lichen stromatolites - C
Back, Wand Hanshaw, B.B., 1970, Com-
parison of chemical hydrogeology of the
Sedimentary Petrology, v.43 ,
p.965-984.
criterion for subaerial exposure and a
mechanism for the formation of lamina r
C
carbonate peninsulas of Florida and
Yucatan: Journal of Hydrology, v. 10,
Drever,J.I., 1982,The Geochemistry of Nat-
ural Waters: Prentice-Hall, Englewood
calcretes (caliche): Journal of Sedimen-
tary Petrology, v. 49, p. 387·400.
C
p.330-368. Cliffs, NJ, 388 p. Peryt, T.M., 1983,Coated Grains: Springer- C
Back, W. and LaMoreaux, P.E., 1983, eds., Folk, R.L., 1974, The natural history of crys- Verlag, Berlin , 655 p.
V.T. Stringfield Symposium - Processes talline calc ium carbonate - effect of Read, J .F., 1974, Calcrete depos its and C
in Karst Hydrology: Journal of Hydrol- magnesium content and salinity: Jour- Quaternary sediments , Edel Province ,
ogy, v. 61, p. 1-355. nal of Sed imentary Petrology, v. 44, Shark Bay, Western Australia, in Logan, E
Buddemeier, R.W. and Oberdorfer, J.A. ,
1986, Internal hydrology and geochem-
p.40-54.
Folk, R.L. and Land, L.S., 1975, The MgfCa
B.W., ed., Evolution and Diagenesis of
Quaternary Sequences , Shark Bay,
C
istry of coral reefs and atoll islands: key
to diagenetic var iations, in Schroeder,
ratio and salinity: two controls over crys-
tallization of dolomite: American Asso-
Western Australia : American Associa-
tion of Petroleum Geologists, Memoir
C
J.H. and Purser, B.H., eds., Reef Dia- ciat ion of Petroleum Geologists, Bul-
letin , v. 59, p. 60-69.
22, p. 250-280.
Read, J.F.,1976,Calcretes and theirdistinc-
C
genesis: Springer-Verlag , New York,
p.91 -111. Haner, J.S., 1978,Precipitation of beachrock tion from stromatolites, in Walter, M.R., C
Davis, S.N. and DeWiest, R.J.M., 1966,
Hydrogeology: John Wiley and Sons,
cements - mixing of marine and meteoric
waters vs. CO2-degassing: Journal of
ed. , Stromatolites: Elsevier, Amster-
dam, p. 55-71. c
New York, 463 p.
Fetter, C.W., Jr., 1980, Applied Hydrogeol-
Sedimentary Petrology,v. 48, p. 489-501.
Kinsman, D.J.J., 1969, Interpretation of
Reeves, C.C., 1976,Caliche - origin , classi-
fication, morphology and uses :
e
Estacado Books, Lubbock, TX, 233 p.
ogy: Merrill and Company, Columbus , Sr2 + concentrations in carbonate miner-
\~
Ohio, 488 p. als and rocks: Journal of Sedimentary Robbin , D.M. and Stipp, J.J., 1979,Deposi-
Johnson , R.H., 1983, The saltwater-fresh- Petrology, v. 39, p. 486-508 . tional rate of laminated soilstone crusts , (
water interface in the Tertiary limestone Plummer, L.N ., Wigley, T.M.L. and Par- Florida Keys: Journal of Sedimentary
aquifer, southeastern Atlantic continen- khurst, D.L., 1979, Critical review of the Petrology, v. 49, p. 175-181. C
tal shelf of the U.S.A.: Journal of Hydrol- kinetics of calcite dissolution and pre- Shinn , E.A. and Lidz, B.H., 1988,Blackened
ogy, v. 61, p. 239-251. cipitation, in Gould, R.F., ed., Chemical limestone pebbles: fire at subaerial C
Kohout, FA , 1960, Cyclic flow of salt water
in the Biscayne aquifer of southeastern
Modeling in Aqueous Systems: Ameri-
can Chem ical Society, Symposium
unconformities, in James, N.P. and Cho-
quette, P.W, eds., Paleokarst: Springer- C
Florida: Journal of Geophysical Series No. 93, p. 537-577. Verlag, New York, p. 117-131. (
Research, v. 65, p. 2133-2141.

c
(
c: Limestones - The Meteoric Diagenetic Environment 69

r:
c Scholle , P.A. and Kinsman , D.J.J., 1974, Karst in General Back, W., Hanshaw, B.B. and Van Oriel,
r Aragon ite and high magnesium calc ite J.N., 1984, Role of groundwater in shap-
ing the eastern coast line of the Yucatan
c caliche from the Pers ian Gulf - a modern
analog forthe Perm ian of Texas and New
Bagli, J., 1980, Karst Hydrology and Physi-
cal Speleology: Springer-Verlag, Berlin, Peninsula, Mexico, in LaFleur, R.G., ed.,

c Mexico: Journal of Sedimentary Petrol-


ogy, v. 44, p. 904-916.
Ward WC ., Folk , R.L. and Wilson , J.L.,
285 p.
Jakucs, L., 1977, Morphogenetics of Karst
Regions: John Wiley and Sons, New
Groundwater as a Geomorphic Agent:
Allen & Unwin lnc ., Winchester MA,
p. 157-172.
C' 1970, Blackening of eolinite and caliche York, 284 p. Ford , D.C. and Ewers , R.O., 1978, The

c adjacent to saline lakes Isla Mujeres,


Quintana Roo Mexico: Journal of Sedi-
James, N.P. and Choquette, P.W, 1988,
eds., Paleokarst: Springer-Verlag, New
development of limestone cave systems
in the dimensions of length and depth :
( mentary Petrology, v. 40, p. 548-555. York, 421 p. Canad ian Journal of Earth Sciences,
Watts , N.L., 1980, Quaternary pedogenic Jennings , J.N., 1971, Karst: The M.I.T. v. 15, p. 1783-1799.
(. calcretes from the Kalahari (southern Press , Cambridge, MA, 252 p. Ford, D.C., 1988, Characteristics of dlssolu-
Africa) mineralogy genesis and diagen - Ritter, D.F., 1978, Process Geomorphology : tional cave systems in carbonate rocks ,
esis: Sedimentology, v. 27, p. 661-686. WC. Brown , Dubuque, Iowa, p. 465-511 . in James, N.P. and Choquette , P.W ,
Sweeting, M.M., 1972, Karst Landforms : eds ., Paleokarst: Springer-Verlag, New
( Ancient Soils and Caliche Macmillan Publishing Co. Ltd., London, York, p. 25-57.
362 p. Hanshaw, B.B. and Back, W., 1980, Chemi-
( Adams, A.E., 1980, Calcrete profiles in the cal mass-wasting of the northern
o Eyam Limestone (Carboniferous) of Der-
byshire petrology and regional sign ifi-
Surface Karst Yucatan Peninsula by groundwater dis-
solution : Geology, v. 8, p. 222-224.
o cance : Sedimentology, v. 27,p. 651-660 .
Bernouilli , D. and Wagner, C.W , 1971, Sub-
Allen , J.R.L., 1982 , Sedimentary Struc-
tures: their character and physical
Kendall , A.C. and Broughton, P.L., 1978,
Origin of fabrics in speleothems com-
( aerial diagenesis and fossil caliche in basis: Elsevier, Amsterdam, p. 222-251. posed of columnar calcite crystals: Jour-
the Calcare Massiccio Formation Bourrouihl, F., 1974, Donnees geomorph- nal of Sedimentary Petrology, v. 48 ,
(Lower Jurassic central Appen ines , ologiques sur la reg ion de Fresh Creek, p.519-538.

o Italy) : Neues Jahrbuch fOrGeologie und


Palacntoloqie, Abhandlungen, v. 138,
lie d'Andros (Bahama): Marine Geology,
v. 16, p. 213-235.
Chafetz, H.S. and Folk, R.L., 1984, Traver-
Moore, G.W. and Sullivan, G.N., 1978,
Speleology: Cave Books , St. Louis, Mis-
souri , 150 p.
p.135-149.
Esteban, M., 1976, Vadose pisolite and cali- tines : depositional morphology and the Palmer, A.N., 1984, Geomorphic inter-
che: American Association of Petroleum bacterially constructed constitutents : pretation of karst features, in LaFleur,
Geologists, Bulletin , v. 60, p . 2048- Journal of Sedimentary Petrology, v. 54, R.G ., ed. , Groundwater as a Geo-
2057. p.289-317. morph icAgent:Allen &Unwin, Winches-
Goldhammer, R.K. and Elmore, R.D., 1984, Folk, R.L., Roberts, H.H. and Moore, C.H., ter, MA, p. 175-209.
Paleosols capp ing regressive carbon- 1973, Black phytokarst from Hell Cay- Plummer, L.N. , 1975, Mixing of seawater

o ate cycles in the Pennsylvanian Black


Prince Limestone, Arizona: Journal of
Sedimentary Petrology, v. 54, p . 1124-
man Islands: Geological Society of
America, Bulletin , v. 87, p. 2351-2360.
Julia, R., 1983, Travertines , in Scholle, P.A.,
with calcium carbonate groundwater, in
Whitten , E.T.H., ed., Quantitative Stud-
ies in the Geological Sciences : Geolog i-
1137. Bebout, D.G. and Moore , C.H ., eds ., cal Society of Amer ica, Memoir 142,
o Harrison, R.S. and Ste inen, R.P., 1978,Sub-
aerial crusts, caliche profiles and brec-
Carbonate Depositional Environments:
American Association of Petroleum
p.219-236.
Thrailkill , J., 1968, Chemical and hydrolog ic
o cia horizons, comparison of some Geologists, Memoir 33, p. 64-73. factors in the excavation of limestone

o Holocene and Misissippian exposure


surfaces Barbados and Kentucky: Geo-
Purdy, E.G., 1974, Reef configurations ,
cause and effect, in Laporte, L.F., ed.,
caves: Geological Society of America,
Bulletin , v. 79, p. 19-16.

o log ical Society of America, Bulletin,


v. 89, p. 385-396 .
Reefs in Time and Space : Soc iety of
Economic Paleontologists and Mineral-
Thrailkill, J., 1976, Speleothems, in Walter,
M.R., ed., Stromatolites: Elsevier Pub-

o Walls, R.A ., Harris, W.B. and Nunam , WE.,


1975, Calcareous crust (caliche) profiles
og ists , Special Publication No . 18,
p.9-77.
Iishing Co ., Amsterdam, p. 73-86 .
Vernon, P.O ., 1969, The geology and hydrol-
o and early subaerial exposure of Carbon-
iferous carbonates, northeastern Ken-
Str ingfield, Y.T. and LeGrand , H.E., 1974,
Karst hydrology of northern Yucatan
ogy associated with a zone of high per-
meab ility (Boulder Zone) in Flor ida :
c tucky: Sedimentology, v. 22, p. 417·440.
Wright, V.P., 1984, The significance of nee-
Peninsula, Mex ico , In Weldie , A.E., ed.,
Field Seminar on water and carbonate
Society of Mining Engineers, Preprint
69-AG-12: Geochimica et Cosmochim -
c. dle fibre calcite in a Lower Carbonifer-
ous paleosol: Geological Journal, v. 19,
rocks of the Yucatan Peninsula, Mexico:
New Orleans Geological Soc iety,
ica Acta, v. 40, p. 989-995 .
Wigley, T.M.L. and Plummer, N.L., 1976,
C' p.23-32. p.26-44. Mixing of carbonate waters: Geochimica
Wright, V.P., 1986, ed., Paleosols: their rec- et Cosmochimica Acta, v. 40, p. 989-
6 ognition and interpretation : Blackwell Subsurface Karst 995.
C. Scientific Publications, London.
Wright, V.P. and Wilson, R.C.L., 1987, A terra Back, W., Hanshaw, B.B ., Pyle , T.E ., Paleokarst
( rossa-like paleosol complex from the Plummer, L.N. and Weidie , A.E., 1979,
r Upper Jurass ic of Portugal: Sedimen- Geochemical significance of ground- Cherns, L., 1982, Palaeokarst, tidal erosion
'-.. tology, v. 34, p. 259-274. water discharge and carbonate solut ion surfaces and stromatolites in the Silurian
to the formation of Caleta Xel Ha, Quin- Eke Formation of Gotland, Sweden: Sedi-
tana Roo, Mexico: Water Resources mentology, v. 29, p. 819-833.
Research, v. 15, p. 1531-1535. James, N.P. and Choquette, P.W., 1988,
eds., Paleokarst: Springer-Verlag, New
""-.. York,421 p.
r:
c
70 Diagenesis Geoscience Canada Reprint Series 4
c
c
c
Kobluk, D.A., Pemberton, S.G., Karolyi, M.
and Risk, M.J., 1977, The Silurian-Devo -
Dickson, J.A.D., 1966, Carbonate identi-
fication and genesis as revealed by
Blake, D.E and Peacor, D.R., 1981, Bio-
mineralization in crino id echinoderms: c
nian disconformity in southern Ontario:
Bulletin of Canadian Petroleum Geol-
staining: Journal of Sedimentary Petrol-
ogy, v. 36, p. 491-505.
characte rization of crinoid skeletal ele-
ments using TEM and STEM analysis: c
ogy, v. 25, p. 1157-1186.
Read, J.E and Grover, G.A., Jr., 1977, Scal-
Dickson, J.A.D., 1983,Graphical modelling
of crysta l aggregates and its relevance
Scanning Electron Microscopy III ,
p, 321-328. c
loped and planar erosion surfaces: Mid- to cement diagnosis: Royal Society of Macqueen, R.W., Ghent, E.D. and Davies, (
dle Ordovician limestone, Virginia: anal- London , Philosophical Transactions , G.R., 1974, Magnesium distribution in
ogues of Holocene exposed karst ortidal v. A309, p. 465-502 . living and fossil specimens of the echi- (-
rock platforms: Journal of Sedimentary Dunham, A.J., 1969, Early vadose silt in noid Peronella lesceuric Agassiz, Shark
Petrology, v. 47, p. 956-972. Townsend Mound (reef), New Mexico, in Bay, Western Australia : Journal of Sedi- C
Walkden, G.M., 1974, Palaeokarstic sur- Friedman , G.M. , ed., Depositional mentary Petrology, v. 44, p. 60-69.
faces in upper Visean (Carboniferous) environments in carbonate rocks: asym- Moberly, R., 1970, Microprobe study of dia- C
limestones of the Derbyshire block, posium: Society of Economic Paleon- genesis in calcareous algae: Sedimen-
England: Journal of Sedimentary Petrol- tologists and Mineralogists, Spec ial tology, v. 14, p. 113-123. C
ogy, v. 44, p. 1232-1247. Publication No. 14, p. 182-192. Plummer, L.N. and Mackenzie , ET., 1974,
Wright , V.P., 1982, The recognition and Evans, C.E. and Ginsburg, R.N., 1987, Predicting mineral solubility from rate C
interpretation of paleokarsts, two exam-
ples from the lower Carboniferous of
Fabric-selective diagenesis in the late
Pleistocene Miami Limestone: Jour-
data , application to the dissolut ion of
magnesium calcites: American Journal
C
south Wales : Journal of Sedimentary
Petrology, v. 52, p. 83-94.
nal of Sedimentary Petrology, v. 57,
p.311-318.
of Science, v. 274, p. 61-83.
Richter, D.K. and FOchtbauer,H., 1978,Fer-
C
Folk, A.L. and Land, L.S., 1975, Mg/Ca ratio roan calcite replacement indicates for- C
Mineral-controlled Meteoric Diagenesis - and salinity: two controls over the crys- mer magnesian calcite skeletons : Sedi-
Overview tallization of dolomite: American Asso- mentology, v. 25, p. 843-861, C
ciat ion of Petroleum Geologists, Bul- Schroeder, J.H. , 1969, Experimental dis-
Friedman, G.M. , 1964, Early diagenesis letin, v. 59, p. 60-68. solution of calcium, magnesium and C
and lithification in carbonate sediments :
Journal of Sedimentary Petrology, v. 34,
Jones, B., Lockhart, E.B. and Squair, C.,
1984, Phreatic and vadose cements in
strontium from recent biogenic car-
bonates: a model of diagenesis : Jour-
C
p.777-813 .
FIOgel, E., 1982, Microfacies Analysis of
the Tertiary Bluff Formation of Grand
Cayman Island , British West Indies: Bul-
nal of Sedimentary Petrology, v.39 ,
p. 1057-1073.
C
Limestones: Springer-Verlag, Berlin, letin of Canadian Petroleum Geology, Towe, K.M. and Hemleben, C., 1976, Dia- C
633 p. v. 32, p. 382-397. genesis of magnesian calcite evidence
Gavish, E. and Friedman, G.M., 1969, Pro- Lindholm, A.C. and Finkleman , A.B., 1972, from miliolacean foraminifera: Geology, C
gressive diagenesis in Quaternary to Calcite staining: semiquantitative deter- v. 4, p. 333-339 .
late Tertiary carbonate sediment - mination offerrous iron: Journal of Sedi- Turner, J.V.,Anderson, T.E , Sandberg, P.A. C
sequence and time scale : Journal of
Sedimentary Petrology, v. 39, p. 980-
mentary Petrology, v. 42, p. 239-242.
Meyers, W.J., 1974,Carbonate cement stra-
and Goldstein, S.J., 1986, Isotopic,
chemical and textural relations during
C
1006.
Harrison, A.S., 1975, Porosity in Pleisto-
tigraphy of the Lake Valley Formation
(Mississippian) Sacramento Mountains ,
the experimental alteration of biogenic
high-magnesian calcite : Geochim ica et
C
cene grainstones from Barbados, some New Mexico: Journal of Sedimentary Cosmochimica Acta, v. 50, p. 495-506. C
preliminary observations: Bulletin of Petrology, v. 44, p. 837-861,
Canadian Petroleum Geology, v. 23, Meyers, W.J., 1978, Carbonate cements - Aragonite Alteration C
p.383-392. their regional distribution and inter-
Land, L.S., 1967, Diagenesis of skeletal car- pretation in Mississippian limestones of Assereto , R. and Folk, R.L., 1980, Diage- C
bonates : Journal of Sedimentary Petrol-
ogy, v. 37, p. 914-930.
southwestern New Mexico: Sedimen-
tology, v. 25, p. 371-400.
netic fabrics of aragonite, calcite and
dolomite in an ancient peritidal-spelean
C
Purdy, E.G., 1968, Carbonate diagenesis -
an environmental survey: Geologica
Oldershaw, A.E. and Scottin, T.P., 1967, The
source of ferroan and non-ferroan cal-
environment Triassic Calcare Rosso,
Lombardia, Italy: Journal of Sed i-
C
Romana, v. 7, p. 183-228. cite cements in the Halkin and Wenlock mentary Petrology, v. 50, p. 371-395. C
Thorstenson, D.C., Mackenzie, F.T. and Limestones: Geological Journal, v. 5, Bathurst, R.G.C., 1964,The replacement of
Ristvet , B.L., 1972, Experimental p.309-320. aragonite by calcite in the molluscan C
vadose and phreatic cementation of Schroeder, J.H. , 1973, Submarine and shell wall, in Imbrie, J. and Newell, N.D.,
skeletal carbonate sand: Journal of vadose cements in Pleistocene Ber- eds ., Approaches to Paleoecology : C
Sed imentary Petrology, v. 42 , p. 162- muda reef rock: Sedimentary Geology, John Wiley and Sons, New York ,
167. v. 10, p. 179-204. p.357-376.

Magnesium-Calcite Alteration
Carlson, W.D., 1983, The polymorphs of
CaC0 3 and the aragonite-calcite trans-
e
Cementation

Bathurst, A.G.C. , 1983, Neomorphic spar Benson, L.V. and Matthews, R.K. , 1971,
formation , in Reeder, R.J., ed., Carbon-
ates : mineralogy and chem istry :
c
versus cement in some Jurassic Electron microprobe studies of mag- Reviews in Mineralogy, v. 11, p. 191-226. l.
grainstones : significance for evaluation nes ium distribution in carbonate Davies, G.A. , 1977, Former magnesian cal-
of porosity evolution .and compaction: cements and recrystallized skeletal cite and aragonite submarine cements
(
Journal ofthe Geological Society, v. 140, grainstones from the Pleistocene of in Upper Paleozoic reefs of the Cana-
p.229-237. Barbados , West Indies: Journal of Sedi- dian arct ic - a summary : Geology, v. 5, <-
Bricker, O.P., 1971, ed., Carbonate Ce- mentary Petrology, v. 41, p. 1018-1025. p. 11-15. (
ments: The Johns Hopkins Press, Bal-
timore, MD, 376 p. C
C
C
(
( Limestones - The Meteoric Diagenetic Environment 71
(
(
Donath, FA, Carozzi, A.V., Fruth, L.S., Jr. Fine-Grained Sediments Reeckmann , S.A. and Gill, E.D., 1981, Rates
c and Rich, D.W , 1980, Oomold ic poros ity
experimentally developed in Miss is- Alexandersson , T., 1972, Micri tization of
of vadose diagenesis in Quaternary
dune and shallow marine calcaren ites,
o sipp ian ool it ic limestone: Journal of
Sed imentary Petrology, v.50 ,
carbonate part icles : processes of pre-
cipitation and dissolution in modern
Warrnambool, Victoria, Australia: Sedi-
mentary Geology, v. 30, p. 157-172.
( p. 1249-1260. shallow water marine sediments : Bul- Steinen , R.P. and Matthews , R.K., 1973,
James , N.P., 1974, Diagenesis of sclera e- letin of Geological Institute , Uppsala , Phreatic vs. vadose diagenesis - stratig-
( tinian corals in the subaerial vadose v. 3, p. 201-236. raphy and mineralogy of a cored bore-

c environment: Journal of Paleontology,


v. 48, p. 785-799.
Bathurst , R.G.C., 1966, Boring algae , mic-
rite envelopes and lith ification of mol-
hole on Barbados , WI.: Journal of Sedi-
mentary Petrology, v. 43, p. 1012-1020.
( Martin, G.D., Wilkinson, B.H. and Lohmann, luscan biosparites: Geological Journal, Steinen, R.P., 1974, Phreatic and vadose
K.C., 1986, The role of skeletal porosity in v. 5. p. 15-32. diagenetic modification of Pleistocene
c aragonite neomorphism - Strombus and
Montastrea from the Pleistocene Key
Bathurst, R.G.C., 1971, Problems of lithifi-
cation in carbonate muds: Geologists'
limestone, petrographic observations
from the subsurface of Barbados,
C- Largo Limestone, Florida: Journal of Sedi- Assoc iation , Proceed ings , v.81 , West Indies: American Associat ion of
mentary Petrology, v. 56, p. 194-203. p.429-440. Petroleum Geolog ists, Bullet in , v. 58,
O Mazzullo, S.J., 1980, Calcite pseudospar Harris, P.M., Halley, R.B. and Lucas, K.J., p. 1008-1024.
replacive of marine acicular aragonite 1979, Endolith microborings and their Videtich, R.P. and Matthews, R.K., 1980,
and implications for aragonite cement preservation in Holocene-Pleistocene Origin of discontinuity surfaces in lime-
o diagenesis: Journal of Sed imentary
Petrology, v. 50, p. 409-423.
(Bahama-Flordia) ooids : Geology, v. 7,
p.216-220 .
stones: isotopic and petrographic data,
Pleistocene of Barbados, West Indies:
o Pingitore, N.E., 1976, Vadose and phreatic Folk, R.L., 1975, Some aspects ofrecrystall- Journal of Sedimentary Petrology, v. 50,

o diagenesis: processes,products and their


recognition in corals: Journal of Sedi-
mentary Petrology, v. 46, p. 785-1006.
ization in ancient limestones, in Pray,
L.C. and Murray, R.C., eds., Dolomitiza-
tion and Limestone Diagenesis : Society
p.971-981.

Diagenesis in the Freshwater-Seawater


C) Pingitore, N.E., 1982, The role of diffus ion of Economic Paleontologists and Miner- Mixing Zone

o during carbonate diagenesis: Journal of


Sedimentary Petrology, v. 52, p. 27-41.
alogists, Special Publication No. 13,
p.14-48. Back, W, Hanshaw, B.B., Pyle, T.E. and
o Pittman , E.D., 1974, Porosity and per-
meability changes during diagenesis of
Lasemi, Z. and Sandberg, P.A., 1984,Trans-
formation of aragonite-dominated lime
Weidie, A.E., 1976, Hydrologic study of
Caleta Xel Ha, Quintana Roo, Mexico, in
o Pleistocene corals , Barbados West
Indies: Geological Society of America ,
muds into microcrystalline limestones :
Geology, v. 12, p. 420-423.
Weidie, A.E. and Ward, WC ., eds. ,
Yucatan Guidebook : New Orleans Geo-
o Bulletin, v. 85, p. 1811-1820.
Sandberg, P.A., 1983,An oscillating trend in
Steinen, R.P., 1978, On the diagenesis of
lime mud : scanning electron micro-
logical Society, New Orleans, LA,
p.244-258.
(.I Phaneorozoic non-skeletal carbonate scope observations of surficial material Back, W., Hanshaw, B.B. , Pyle, T.E.,

o mineralogy: Nature, v. 305, p. 19-22.


Sandberg, P.A., 1985, Aragonite cements
from Barbados, WI.: Journal of Sedi-
mentary Petrology, v. 48, p. 1139-1148.
Plummer, L.N. and Weidie, A.E., 1979,
Geochem ical sign ificance of ground-
o and their occurrence in ancient lime-
stones , in Schneidermann , N. and
Steinen, R.P., 1982, SEM observations on
the replacement of Bahamian arago-
water discharge and carbonate solut ion
to the formation of Caleta Xel Ha, Quin-
o Harr is, P.M., eds., Carbonate Cements :
Society of Economic Paleontologists
nitic mud by calcite : Geology, v. 10,
p.471-475 .
tana Roo, Mex ico : Water Resources
Research, v. 14, p. 1521-1535.
o and Mineralogists, Special Publication Wiggins, W.D., 1986, Geochemical signa- Back, W.,Hanshaw, B.B., Herman, J.S. and

o No. 36, p. 33-58.


Sandberg, P.A. and Hudson, J.D., 1983,
tures in carbonate matr ix and their rela-
tion to deposition and diagenesis , Penn-
Van Driel, J.N., 1986, Differential dis-
solut ion of a Pleistocene reef in the

o Aragonite relic preservation in Jurass ic


calcite-replaced bivalves : Sedimen-
sylvanian Marble Falls Limestone ,
central Texas: Journal of Sedimentary
ground-water mixing zone of coastal
Yucatan, Mexico : Geology, v.14 ,

o tology, v. 30, p. 879-892 .


Sandberg, P.A., Schneidermann , N. and
Petrology, v. 56, p. 771-783. p. 137-140.
Beach, D.K., 1982, Depositional and diage-
o Winder, S.J ., 1973, Aragonite ultra-
structure relics in calcite-replaced
Vadose versus Phreatic Diagenesis netic history of Pliocene-Pleistocene
ca rbonates of northwestern Great
Pleistocene skeletons : Nature, v. 245, Benson, L.V., 1974, Transformation of a poly- Bahama Bank, evolution of a carbonate
p.133-134. phase sedimentary assemblage into a platform, Unpublished Ph.D. thes is ,
( Schroeder, J.H ., 1979, Carbonate diagene - single phase rock - a chemical approach : University of Miami, Coral Gables, FL,
sis in Quaternary beachrock of Uyombo, Journal of Sedimentary Petrology, v. 44, 447 p.
l Kenya: sequences of processes and co- p. 123-136. Benson, L.V., 1973, Electron microscope
r existence of heterogen ic products : Buchbinder, L.G . and Friedman , G.M ., stud ies of carbonates, Unpublished
Geolog ische Rundschau , v. 68, p. 894- 1980, Vadose, phreatic and marine dia- Ph.D. thesis, Brown University, Provi-
919. genesis of Pleistocene-Holocene car- dence , RI, 180 p.
Wardlaw, N., Oldershaw, A. and Stout, M., bonates in a borehole · Mediterranean Hanshaw, B.B., Back, W. and Deike, R.G.,
1978,Transformation of aragonite to cal- coast of Israel: Journal of Sedimentary 1971, A geochemical hypothesis for dolo-
cite in a marine gastropod: Canadian Petrology, v. 50, p. 395-409. mitization by groundwater: Economic
Journal of Earth Sciences, v. 15, Land, L.S., 1970, Phreatic versus vadose Geology, v. 66, p. 710-724.
p. 1861-1866. meteoric diagenesis of limestones: evi- Harr iss, W.H., 1971, Groundwater - carbon-
dence from a fossil water table: Sedi- ate rock chemical interactions: Bar-
mentology, v. 14, p. 175-185. bados, West Indies: Unpublished Ph.D.
thesis, Brown University, Providence,
RI, 348 p.
72 Diagenesis Geoscience Canada Reprint Series 4

(
Land, L.S., 1973a, Holocene meteor ic dolo- Brand, U. and Veizer, J., 1980, Chemical Lohmann, K.C., 1982, Inverted " J" carbon
mit ization of Pleistocene limestones,
North Jamaica: Sedimentology, v. 20,
diagenesis of a multicomponent car-
bonate system -1. Traceelements: Jour-
and oxygen isotopic trends - a criterion
for shallow meteoric phreatic diagene-
C
p.411-422. sis (abstract): Geological Society of
(
nal of Sed imentary Petrology, v. 50,
Land, L.S., 1973b, Contempo raneous dolo- p. 1219-1236. America, Abstracts with Program, 1982,
mitization of Middle Pleistocene reefs by Brand, U. and Veizer, J., 1981, Chemical p.548. C
meteoric groundwater, north Jamaica:
Bulletin of Marine Sc ience, v.23,
diagenesis of a multicomponent car-
bonate system - 2. Stable isotopes: Jour
Lohmann, K.C., 1983, Unravelling the dia-
genetic history of carbonate reservoirs, C
p.64-92. na l of Sed imentary Petrology, v. 51, in Wilson , J.L. , Wilkinson, B.H. and
Major, R.P., 1984, The Midway Atoll coral p.987-997. Lohmann, K.C., eds., New Ideas and
cap-meteoric diagenesis , amplitude of Choquette, P.w" 1978, Recent calcareous Methods for Exploration for Carbonate c
sealevel fluctuations, and dolomitiza-
tion, Unpublished Ph.D.thesis, Brown
crusts (caliche) on Isla Mujeres, Quin-
tana Roo, Mexico - insights from isotopic
Reservoirs - notes for a short course:
Dallas Geological Society. c
University, Providence, RI, 133 p.
Meyers , w». and Lohmann , K.C. , 1978,
composition, in Ward, W.C. and Weidie,
A.E., eds., Carbonate Rocks and Hydro-
Lohmann, K.C., 1988, Geochemical pat-
terns of meteoric diagenetic systems c
Microdolomite-rich syntaxial cements :
proposed meteoric-marine mixing zone
logy of the Yucatan Peninsula, Mexico:
New Orleans Geological Society,
and their application to studies of paleo-
karst, in James, N.P. and Choquette, c
phreatic cements from Mississippian
limestones, New Mexico: Journal of
[Guidebook for Field Trip 2], New
Orleans, LA , p. 171-190.
P.w" eds., Paleokarst: Springer-Verlag,
New York, p. 58-80 .
c
Sedimentary Petrology, v. 48, p. 475- Dansgaard, W., 1964, Stable isotopes in Magaritz, M., 1975, Sparitization of pelleted c
488.
Moore, C.H., 1973, Intertidal carbonate
precip itation : Tullus, v. 16, p. 436-468 .
Galimov, E.M., 1966,Carbon isotopes of soil
limestone - a case study of carbon and
oxygen isotope composit ion: Journal of c
cementation, Grand Cayman, West
Indies: Journal of Sedimentary Petrol-
CO2 : Geochemistry International, v. 3,
p.889-897.
Sedimentary Petrology, v. 45, p. 599-
603. c
ogy, v. 43, p. 591-602.
Pierson , B., 1983, Cyclic sedimentation ,
Galimov, E.M., 1967, Isotopic composition of
carbon in gases of the crust: Geological
Magar itz, M., 1983, Carbon and oxygen
composition of Recent and ancient c
limestone diagenesis and dolomitiza- Review, v. 11, p. 1092-1104. coated grains, in Peryt, T.M., ed., Coated (
tion in UpperCenozoiccarbonatesofthe Gonzalez , L.A. and Lohmann, K.C., 1988, Gra ins: Springer-Verlag , Heidelberg,
southwestern Bahamas, Unpublished Controls on mineralogy and composi- p.27-37. c
Ph.D. thesis, University of Miami , Coral
Gables, FL, 295 p.
tion of spelean carbonates: Carlsbad
Caverns, New Mexico, in James, N.P.
Magaritz, M., Kaufman, A . and Yaalon,
D.H., 1981, Calcium carbonate nodules c
Ristvet, B.L., 1971, The progressive diage-
netic history of Bermuda : Bermuda Bio-
and Choquette, P.w" eds., Paleokarst:
Springer-Verlag, New York, p. 81-101.
in soils - 18 0 /160 and 13C/12C ratios
and 14C content : Geoderma, v.25, c
logical Station for Research Special
Publication 9, p. 118-157.
Gross, M.G., 1964,Variations in the 18 0 / 16 0
and 13C/12C ratios of diagenetically
p. 1157-1172.
Meyers, W.J. and James, A.T., 1978,Stable c
Steinen, R.P., Matthews, R.K. and Sealy,
H.A., 1978, Temporal variation in geo-
altered limestones in the Bermuda
Islands: Journal of Geology, v. 72,
isotopes of cherts and carbonate
cements in the Lake Valley Formation
c
metry and chemistry of the freshwater p.170-194. (Mississippian) , Sacramento Moun- c
phreatic lens - the coastal aquifer of
Christ Church, Barbados , West Indies:
Given, R.K. and Lohmann, K.C., 1985,Deri-
vation of the original isotopic compos i-
tains, New Mexico: Sedimentology,
v. 25, p. 105-124. c
Journal of Sedimentary Petrology, v. 48,
p.733-743.
tion of Permian marine cements : Jour-
nal of Sedimentary Petrology, v. 55,
Meyers, w'J. and Lohmann, K.C., 1984,Iso-
tope geochemistry of regionally exten- c
Wagner, P.O., 1983, Geochemical charac-
terizations of meteoric diagenesis in
p.430-439.
Given, R.K. and Lohmann , K.C., 1986, Iso-
sive calcite cement zones and marine
components in Mississippian lime- c
limestone - development and appli-
cations. Part III. Mixing Zone diagene-
topic evidence of the early meteoric dia-
genesis of the reef facies, Permian reef
stones , New Mexico, in Schneider-
mann, N. and Harris, P.M.,eds. , Carbon-
c
sis, Unpublished Ph.D. thesis, Brown
University, Providence, RI, p. 123-146.
complex, west Texas and New Mexico:
Journal of Sedimentary Petrology, v. 56,
ate Cements: Society of Economic
Paleontologists and Mineralogists, Spe-
c
p. 183-193. cial Publication, No. 36, p. 223-240. c
Geochemical Aspects of Meteoric
Diagenesis
Hendy, C.H., 1971, The isotopic geochem-
istry of speleothems - 1. The calculation
Pearson , F. and Hanshaw, B.B ., 1970,
Sources of dissolved carbonate species c
Al-Aasrn, I.S. and Veizer, J., 1986a, Diage-
of the effects of different modes of for-
mation on the isotopic compos ition of
in groundwater and their effects on car-
bon-14 dating: International Atom ic c
netic stabilization of aragonite and Low- speleothems and their applicability as Energy Association, Isotope Hydrology (
Mg calcite - I. trace elements in rudists : paleoclimatic indicators: Geochimica et Proceedings Symposium, p. 271-286.
Journal of Sedimentary Petrology, v. 56,
p. 138-152.
Cosmochimica Acta, v. 35, p. 801-824.
Hoefs, J., 1973, Stable Isotope Geochem-
Rightmire, C.T. and Hanshaw, B.B., 1973,
Relationship between the carbon-iso-
e
AI-Asam, I.S. and Veizer, J., 1986b, Diage-
netic stabilization of aragonite and Low-
istry: Springer-Verlag, Berl in, 140 p.
Hudson , J.D., 1975, Carbon isotopes and
tope composition of soil CO 2 and dis-
solved carbonate species in ground-
c
Mg calcite -II. stable isotopes in rudists : limestone cement: Geology, v.3 , water: Water Resource Research, v. 9, (
Journal of Sedimentary Petrology, v. 56, p. 19-22. p.958-967.
(
p.763-770. Hudson , J.D., 1977, Stable isotopes and Salomons , w" Goudie, A. and Mook, w.G. ,
Allan, J.R . and Matthews, R.K., 1977, Car-
bon and oxygen isotopes as diagenetic
limestone lith ification: Journal of the
Geological Society, v. 133, p. 637-660.
1978, Isotopic composition of calcrete
deposits from Europe, Africa and India:
C
and stratigraphic tools - data from sur-
face and subsurface of Barbados, West
Earth Science Processes, v. 3, p. 43-57. C
Indies: Geology, v. 5, p. 16-20. C
C
C
c~
( . Limestones - The Meteoric Diagenetic Environment 73
(
(~ Veizer,J., 1983. Chemical diagenesis of car- Examples of Meteoric Diagenesis in Meyers. w.J ., 1978. Carbonate cements -
r bonates : theory and application of trace
element technique , in Stable Isotopes in
Ancient Limestones thei r regional distribution and inter-
pretat ion in Mississippian limestones of
o Sedimentary Geology: Society of Eco-
nomic Paleontologists and Mineralo-
Grover, G.A., Jr. and Read, J.F., 1978,
Fenestral and associated vadose diage-
southwestern New Mexico: Sedimen-
tology, v. 25, p. 371-400.
( gists, Short Course No. 10, p. 3-1-3-100. netic fabrics oftidal flat carbonates, mid- Roehl, P.O. and Choquette , P.w., 1985,

o Veizer, J. and Hoefs, J., 1976, The nature of


'80/'60 and '3C/'2C secular trends in
dle Ordovician, New Market Limestone,
southwestern Virgin ia: Journal of Sedi-
eds., Carbonate Petroleum Reservoirs:
Springer-Verlag, New York, 622 p.

r. sedimentary carbonate rocks: Geo-


chimica et Cosmochimica Acta, v. 40,
mentary Petrology, v. 48, p. 453-473.
Grover, G.A., Jr. and Read, J.F., 1983, Other References
( p. 1387-1395. Regional cathodoluminescent patterns,
Videtich, P.E. and Matthews, R.K., 1980, middle Ordovician ramp carbonates, Fischer, A.G., 1981, Climate oscillations in
( Origin of discontinuity surfaces in lime- Virgin ia: American Association of Petro- the biosphere, in Nitecki, M.H., ed., Bio-
stones - isotopic and petrographic data, leum Geologists , Bulletin , v.67, tic Crises in Ecological and Evolutionary
Pleistocene of Barbados , West Indies: p. 1275-1303. Time , Academic Press , New York,

c Journal of Sedimentary Petrology, v. 50,


p.971-980.
Jacka, A.D . and Brand, J.P., 1977, Biofacies
and development and differential occlu-
p. 103-133.
Lowenstam, H., 1963, Biologic problems

o Wagner, P.D. and Matthews, R.K., 1982,


Porosity preservation in the Upper
sion of porosity in a Lower Cretaceous
(Edwards) reef: Journal of Sedimentary
relating to the composition and diagene-
sis of sediments, in Donnelly, T.w., ed.,
Smackover (Jurassic) carbonate Petrology, v. 47, p. 366-382 . The Earth Sciences: University of Chi-
grainstone . Walker Creek fields , James, N .P. and Klappa , C.F., 1983 . cago Press, Chicago, p. 137-195.
o Arkansas, response of paleophreatic
lenses to burial processes: Journal of
Petrogenesis of Early Cambrian reef
limestones: Journal of Sedimentary
Wilkinson , B.H., 1979, Biomineralization ,
paleo-oceanography and the evolution
C. Sedimentary Petrology, v. 52. p. 3-18. Petrology, v. 53, p, 1051·1096. of calcareous marine organisms: Geol-

o Diagenesis of Calcite Sediments


Harris, P.M., 1983,ed., Carbonate buildups-
a core workshop: Society of Economic
ogy, v. 7, p. 524-527.

o Hsu, K.J. and Jenkyns, H.C., 1974, eds.,


Paleontologists and Mineralogists, Core
Workshop Number 4, 461 p.
o Pelagic Sediments : on Land and under
the Sea: International Association of
Heckel, P.H., 1983, Diagenetic model for
carbonate rocks in midcontinent Penn-
o Sedimentologists, Special Publication
No.1, 447 p.
sylvanian eustatic cyclothems: Journal
of Sedimentary Petrology, v.53,
Scholle, P.A., 1977, Chalk diagenesis and its p.733-761.
relation to petroleum exploration: Oil Matthews, R.K. and Frohlich, C., 1987, For-
Originally published in
from chalks, a modern miracle?: Ameri- ward modeling of bank-margin car- Geoscience Canada v. 11 Number 4

c can Association of Petroleum Geolo-


gists, Bulletin, v. 61, p. 982-1010.
bonate diagenesis : Geology, v. 15,
p.673-676.
(December 1984)
Revised 1988
o
o
o
o
o
'-'
CJ
o
C
8
r:
(
74 Diagenesis Geoscience Canada Reprint Series 4 c
c
(
(
c
C
C
c:
'-,.

c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
Scalenohedral calcite crystals and micrite with etch patterns following a carbonated-brine flooding experiment in the c
laboratory. Note that calcite crystal faces are etched in a rhombic staircase fashion and that crystal edges have become
rounded. Small scattered particulate material coating the sample was released from the rock during the reservoir c
flooding experiment. Photograph courtesy of F. Krause and S. Sayegh (University of Calgary and Petroleum Recovery
Institute, respectively). c
(
e
c
(
C
l

(
( o') ...}-I o( .~
r U' .s \
o~:. Limestones - The Burial Diagenetic Environment _, . .--'_ ~ 0- 1.. r % 75
~
rV7D).J~( ~r/ 0/ r'YOo,S.! 0) N~
->:
r • _

/0 L/VI C q,. '1 \ ~ MI ~Jb;


techniques for the study of cathodo- connotes the zon/ IMsfttPr~iJJnd
luminescence, ultraviolet fluores- water-filled pores anywhere below the
cence, stable-isotope, rare-earth and water table.
o minor-element compositions, and
microscopic fluid inclusions have made
Differences from near-surface pro-
cesses. The dominant processes,
possible the acquisition of much new ambient conditions, space and time
() information about the petrologic, min- distributions, and principal products of
eralogic and chemical changes that diagenesis in deep-burial settings are
take place in the deep-burial realm. quite different from those in near-sur-
The fundamental importance of dia- face settings. In the sea-floor environ-
( genesis in this largely occult realm in ment, cementation by aragonite and
Limestones - The
shaping the porosity, mineralogy, basic Mg-calcite is the main inorganic agent
Burial Diagenetic fabrics and numerous other features of lithification (James and Choquette,
Environment of carbonates is now clear, but many 1983)and is highly facies-specific. Lith-
aspects remain to be clarified. The ification in this setting is virtually in-
quest for a basic understanding and a stantaneous geologically, probably in-
Philip W. Choquette general theory of diagenesis in the volving time intervals on the order of
Department of Geological Sciences deep-burial setting has only begun. 101 to 104 years.
University of Colorado In the meteoric environment, the
r Boulder, Colorado 80309-250 THE DEEP-BURIAL SETTING main processes of lithification involve
Definitions. Burial diagenesis can the precipitation of calcite, impelled
Noel P. James be defined in general as any change or either by dissolution of aragonite and
Department of Geological Sciences collection of changes that takes place microdissolution of Mg-calcite (forms of
Queen's University below the zone of near-surface diagen- mineral-controlled alteration as dis-
Kingston, Ontario KlL 3N6 esis and above the realm of low-grade cussed by James and Choquette, 1984,
metamorphism (Figure 1). These limits and this volume), or by more wholesale
INTRODUCTION can vary from one sedimentary basin to dissolution and precipitation of calcite
Carbonate sediments, or the lime- another or even within a single basin. (water-controlled alteration). Be-
stones into which they may have By "near-surface" we mean at or close cause of the incongruent dissolution of
evolved, once buried below the reach of to the sea floor or in the meteoric environ- metastable aragonite and Mg-calcite
sea-floor processes or below the mete- ment, within the reach of surface-related particles and the accompanying preci-
oric environment and the sub-meteoric processes (Choquette and Pray, 1970). pitation of calcite, mineral-controlled
mixing zone, enter with progressive bur- The sub-lenticular mixing zone (see alteration redistributes porosity from
ial the "deep-phreatic" or subsurface James and Choquette, 1984) is rightly inter- and intraparticle sediment pores
burial-diagenetic realm (Figure 1). It is in viewed as part of the meteoric, although to new moldic pores, often with little net
this realm that, unless exhumed by tec- its nature and vertical as well as geo- change in percent porosity (Harrison,
tonic uplift or lowered sea level, the graphic extent are poorly known in all 1975). Water-controlled alteration, on
great majority of sedimentary carbon- but a few sub-tropical limestone islands the other hand, creates new, larger,
ates must inevitably spend most of their and a few aquifers in Cenozoic and non-selective voids or adds CaC0 3 and
geologic existence. It is here, too, that Mesozoic carbonates. Defined in this reduces porosity. Meteoric-realm dia-
the majority of carbonate sediments way, burial diagenesis is mainly a conse- genesis must involve time intervals
which escaped sea-floor lithification or quence of overburden due to burial which approximate the duration of sub-
prolonged meteoric diagenesis undergo beneat h younger strata, and of resulting, aerial exposure at unconformities; in
most of the changes that lead to their ~ h ang es ' n ~ogy, pore-water chem- Plio-Pleistocene sequences on modern
lithification and reduction of porosity. Istr, ressure, and temperature. In en- platforms glacio-eustatic unconform-
The importance of deep-burial dia- eral, it may begin at depths of a very few ities involve time intervals on the order
genesis has been recognized more metres to a few hundreds of metres of 103 to 105 years (e.g., Steinen and
widely in the last fifteen years or so, in beneath subaerial surfaces, and a Matthews, 1973; Enos and Perkins,
considerable part because of the pub- metre or so to very few tens of metres 1979; Beach, 1982); older Phanerozoic
lication of a major synthesis on carbon- beneath sea-floor surfaces. The burial- platforms contain regional and inter-
ate diagenesis by Bathurst (1971). diagenetic realm would include, for regional unconformities representing
Since that time, aspects of the subject example, the mesogenetic or "deeper time intervals up to 106 to 107 years
have been examined in a number of burial" realm of Choquette and Pray (Sando, 1974, 1985; Schlee, 1984). In
general or specific studies, perhaps (1970); the "compactional" and "ther- the deep-burial environment, far more
most notably the thoughtful works by mobaric" subsurface regimes sug- complex arrays of processes are opera-
Bathurst (1975, 1980a,b, 1984, 1985, gested by Galloway (1985) for sand- tive (Table 1). Dominant among them
1987), Schlanger and Douglas (1974), stone-shale sequences; the "deep- are physical (mechanical) compaction
Garrison (1981), Shinn and Robbin phreatic" realm of many workers; and and dewatering, chemical compaction
(1983), and Scholle and Halley (1985). for geologists in the petroleum industry (pressure-solution), cementation, sub-
During this same period, the develop- the "subsurface" in general. The term surface dolomitization, alteration of
ment and refinement of instruments and phreatic is not very useful because it hydrous minerals to anhydrous ones,
c
76 Diagenesis Geoscience Canada Reprint Series 4 (
C
C
C
MIXING
BURIAL DIAGENETIC C
-- ZONE - DOMAINS C
SHALLOW MARINE , PERITIDAL
+
AND ASSOCIATED SEDIMENTS
" ::::,
pore waters of rnult ip l e orig ins
<,
-,
,:::..-........
~
c
---=--=-
DEEP BURIAL

--
--" '"" ------
_
....
<, ~
. . . ~--
--.. _-"'......, -
<,
~

, '>'
SHALLOW BURIAL

BASINAL
SEDIMENTS
marine-derived
pore waters
c
c
c
c
. . . . ·1 · · ···
METAMORPHIC DOMAIN
...? .
---- DEEP BURIAL
c
c
Figure 1 A sketch outlining two general domains of deep-burial diagenesis. The nature and depth range of the boundary with the
metamorphic realm are poorly known. The depth is likely to range from a kilometre or less to several kilometres or more. c
c
thermally driven mineral stabilization
reactions, and alteration and matura-
c
tion of organic matter with attendant Table 1 General processes and products in the deep-burial domain. ~
production of organic acids and hydro-
carbons. An apparently common long-
Processes Products
c
term trend with burial is progressive
reduction of porosity by compaction
Physical compaction Reduced thickness , porosity and permeability;
re-oriented and commonly broken allochems ; c
and cementation , at increasing temper-
Chemical compaction
compressed textures and structures
Reduced thickness, porosity and permeability;
c
atures and pressures, in the presence
of pore waters that may become in-
stylolites and other pressure-solution
structures;
c
creasingly saline. Important changes
may occur over burial-history time
ions for new carbonate cement c
spans of 106-108 years, although the
Cementation Mosaicldrusy to very coarse or poikilotopic
calcite and saddle dolomite
c
rates of some modifications, such as
mechanical compaction , will commonly Burial dolomitization Anhedral-crystalline dolomite, generally rather c
fall off rapidly with increasing depths of
burial. Mineral reactions
coarse
Smectite to illite c
Factors Influencing Deep-Burial Gypsum to anhydr ite
Opal A and CT to quartz
c
Diagenesis.
Intrinsic factors. Among the most
Fe hydroxides to Fe oxides e
important intrinsic factors (Table 2) are
the mineralogy and the amount and
Biochemical alteration
of organic matter
Kerogen and organic acids
c
nature of the organic fraction . A sedi- Thermochemical alter- Hydrocarbons and CO2 c
ment that retains aragonite and Mg-
calcite as it goes into the deep-burial
ation of kerogen
Burial dissolution of Ca Solution porosity c
environment will have more "diage- carbonate and sulphate
netic potential " (Schlanger and Doug-
las, 1974) to generate calcite cement c
through dissolution and reprecipitation
than will a sediment composed only of
e
calcite. We know relatively little about
the mineralogy of platform limestones Intrinsic
Table 2 Principal controls in deep-burial diagenesis.
Extrinsic
c
as they leave the meteoric and sub- • Mineralogy • Temperature
meteoric mixing zones and enter the
deep-burial realm. Scholle and Halley
• Grain size and texture
• Organic matter, kerogen and hydrocarbons
• Pressure c
(1985) have argued that many platform • Early cement or dolomitization
(
limestones altered in the meteoric zone • Time
• Pore-water chemistry (
are calcite and therefore have relatively
• Porosity and permeability • Fluid Flux
low diagenetic potential like marine

(
(
G
( Limestones - The Burial Diagenetic Environment 77

c
C' chalks . However, calc ite cement of both the volume of contained pore fluid overpressured or "geopressured " and
c meteoric origin is rarely homogeneous
either isotopically or elementally, and
and the rate at which fluids are transmit-
ted, affect the speed at which diagenetic
the pore-fluid column may support part
or all of the overburden load.
c therefore must have at least some dia-
genetic potential (L.S . Land, pers.
reactions take place. In Holocene sedi-
ments, porosity is generally greater in
Abnormally high pore-fluid pressure
can be an important inhibiting factor in
( comm., 1986). In any case, many stud- fine-grained sediments such as lime burial diagenesis. It can actually " prop
( ies of Recent and Plio-Pleistocene muds than in coarser carbonate sands up" original pore spaces - either inde-
limestones have shown that minera- (Enos and Sawatsky, 1981). In the geo- pendently or in concert with early near-
c logic stabilization in meteoric water
from aragonite and Mg-calcite to low-
logic record, the highest known lime-
stone porosities (up to 80% with very
surface cementation - thereby retard-
ing or preventing physical compaction.
J
Mg calcite can take place quickly, after low permeabilities often below 1 md) are It alsocan slow or shut off the export and
( a few metres to tens of metres of burial found in some Cretaceous and Danian import of pore water and prevent any

o (e.g., Steinen and Matthews, 1973;


Steinen, 1974; Beach, 1982).
chalks (Scholle, 1977). Permeability in
limestones with interparticle porosity,
changes in the partial pressure of CO2
and other dissolved gases, thereby
o In another kind of " mineralogical"
effect, limestones that contain at least a
however - other things being equal -
is directly related to grain size, so that in
creating a pore-fluid system which is
both overpressured and static, in which
o few percent clay minerals or unstable general the coarser-grainedcarbonates both pressure-solutionand cementation

o organic matter (in addition to being fine


grained) are more susceptible than
will transmit fluids in larger volumes and
at higher flow rates.
may be sharply retarded. Feazel and
Schatzinger (1985) also have discussed
o pure limestones to physical compac-
tion, chemical compaction (pressure-
Extrinsic factors. Among the many
extrinsic factors affecting burial dia-
recentlythe retarding efects of high pore
pressure.
solution), and even spaced cleavage genesis (Table 2) it appears that pres- Many processes seem able to cause

o due to tectonically induced pressure-


solution. Furthermore, it is widely
sure, temperature, pore-water chemis-
try, and, in some settings, liquid hydro-
overpressuring of sedimentary rock
pore-fluid systems, by trapping their flu-
thought that the amount of clay and lor carbons are most important. Pressureof ids. Rapid sedimentation, as in marine
organic matter may be important. at least three kinds is applied to sedi- parts of major delta systems, can bury
Whether clay and silt content is less mentary sequences being buried: sediments more quickly than these can
than or more than about 10% appears (1) lithostatic pressure, transmitted expel connate water. Confinement of
influential in determining whether pres- through the solid framework; (2) hydro- porous carbonates beneath stratiform
sure-solution produces, respectively, static pressure, transmitted only permeability barriers such as compact-
sutured stylolites or non-sutured through the pore-system "water col- ing shales or evaporites, well-indurated
seams and fitted fabrics (R.G.C. Bath- umn"; and what Bathurst (1975) called hardgrounds, or limestones having

o urst, pers . comm., 1986).


Grain size and texture influence the
(3) linear or directed pressure. The first
two of these are induced by gravity. The
swarms of laterally extensive stylolites,
all can cause overpressuring. So also
o rates at which CaCO s components
change and sediments compact. Fine-
third is really of tectonic origin and has
been recognized increasingly in recent
can some diagenetic reactions involv-
ing clay, sulfate and silica minerals as
o grained and poorly sorted sediments years as a major cause of spaced cleav- discussed next under "Temperature",
o undergo neomorphic and solution-
precipitation reactions more rapidly be-
age in tectonized carbonates that yield
by brittle fracture. Typical hydrostatic
since these reactions add water to the
system. The generation of gases such
o cause of their larger reactive surface and lithostatic pressure gradients, as CO2 , methane and other hydrocar-

e areas; they also compact more readily


than coarse sediments, in marine pore
shown in Figure 2A, give an idea of the
pressure ranges ambient over the range
bons, and H2S at sites and in strata
where the gases cannot escape may
o waters at least, because of their greater
pore water content and potential for
of subsurface depths that have been
sampled thus far by petroleum explora-
cause overpressuring. The abrupt re-
lease of overpressure has been pro-
o particle rearrangement and reorienta- tion drilling. posed as a mechanism for producing

o
r:
tion . One consequence of this is that
some sediments that were deposited
as lime muds undergo so much physi-
Pore pressure determines the effec-
tive stress on a sediment under over-
burden load, because the effective or
certain breccias apparently by dilation,
for example in thin-bedded,fine-grained
carbonates of basinal origin in the Mio-
~
cal compaction of their fine-grained net stress is the Iithostatic pressure (or cene Monterey Formation of California
(
fraction that they become "diagenetic" total load) less the pore pressure (e.g., Secor, 1965; Roehl, 1981). Our
wackestone or packstone (Shinn and (Terzaghi, 1940). Most subsurface understanding of, and ability to predict,
Robbin, 1983). strata at temperatures greater than the realms and effects of abnormally
Early-precipitated cement or early about 100°C have pore pressures high pore-fluid pressure in burial dia-
replacement dolomite formed at or not which are higher than "normal hydro- genesis of carbonates still are primitive.
far below the depositional interface will static" and would lie in the stippled A very few studies haveshownthe im-
increase the bearing strength of a sedi- area of Figure 2A. Usually the dif- portance, however, of abnormal pres-
ment so that it compacts less readily, at ferences between Iithostatic and pore- sures as co-agents (with early emplace-
least at relatively shallow depths fluid pressure are small, but under ment of hydrocarbons) in causing the
«2 km?). various conditions the pore-fluid pres- retention of unusually high porosities in
Finally, the porosity and permeability sures can become abnormally high, in some Cretaceous and early Tertiary
of a sediment or rock, which govern which case the strata are said to be chalk reservoirs in the central North
c
78 Diagenesis Geoscience Canada Reprint Series 4 c
c
Sea (Scholle, 1977; van den Bark and and eventually to hydrocarbons and cementation, and probably some bur ial
c
Thomas, 1981; Feazel et el., 1985). other organic compounds (see review dolom itization and dolomite neomor- c
Temperature appears to play at least
three roles in burial diagenesis and
by Barnes et aI., 1984). In dirty sand-
stones, the reactions in this complex
phism (xenotopic dolomite of Gregg
and Sibley, 1984) also take place. c
may be of considerable importance. series are widely thought to release The range of temperatures in sedi-
(1) The solubility of calcite and other CO2 which can combine in carboxylic mentary basins can be great, depending
carbonates - unlike that of quartz - is and other organic acids capable of dis- on the thickness of the sedimentary fill (
"retrograde" in water having dissolved solving carbonates (e.g. , Schmidt and and on the geothermal gradients (Figure
CO2 and decreases with increasing MacDonald, 1979; Hayes, 1979; Bjor- 2B), which in turn depend on ambient
temperature (Helgeson, 1969). The Iykke, 1984 ; Surdam et et. , 1984) . heat flow and on thermal conductivity
of the sediment. Gradients in most
c
decrease is linear up to temperatures
as high as 400°C and is substantial , on
Material-balance calculations have led
some workers to suggest, however, that sedimentary basins are in the range c
the order of two orders of magnitude at
anyone pressure (Bathurst, 1971). This
CO2 produced only by decarboxyla-
tion , at least in shales of the Oligocene
of 15-35°C per kilometre of depth
and 25°C/km is an often-eited normal c
relationship, although complicated by Frio Formation in the Texas Gulf Coast, value (Wood and Hewett, 1984). Gra- c
the effects of increasing pressure, indi-
cates that with increasing temperature
cannot account for most of the dissolu-
tion porosity found in associated sand-
dients can change sharplywith uplift and
passage of a sedimentarypackageinto a c
alone, calcite cement (and by inference
saddle dolomite) will be more likely to
stones; other mechanisms and/or long-
distance transport of acidic waters
nearer-surface hydrologic regime fed by
cooler meteoric waters,as has happened
c
precipitate. must also be responsible (Lundegard et in the Western Canada basin (Hitchon, c
(2) Increasing burial brings about a
series of temperature- and pressure-
el., 1984; Lundegard, 1985). Dissolu-
tion porosity of burial origin is being
1969a,b) and some other basins.
Pore-water chemistry has a variety of c
dependent mineral reactions. Some of
these release water to the surrounding
recognized increasingly in limestones
since its discovery in the early 1980s
important effects and roles in burial
diagenesis. For one thing, pore waters
c
pore fluids and result in minerals that (Moore and Druckman, 1981; Elliott, transmit, by physical fluid flow or ion (-
have higher specific gravities and
occupy less space than their precur-
1982; see also Druckman and Moore,
1985; Moore, 1985). Although the min-
diffusion, the solute ions produced by
dissolution or consumed by cementa- c
sors. These reactions include the con-
version of gypsum to anhydrite at
erai and fluid systems must be dif-
ferent, mechanisms like those invoked
tion and replacement reactions. More-
over, water chemistry seems to have a
c
around 1000 m (Murray, 1964; Kendall, for sandstones have generally been strong influence on major burial-dia- c
1984), and the conversion in some
oceanic sediments of opal-A to opal-CT
suggested for the limestones.
Interestingly, the temperature range
genetic processes . One of the most
important of these, pressure-solution c
and finally quartz within a depth range in which peak generation of hydrocar-
bons is believed to occur, 60-150oC
(chemical compaction), seems to ope- c
of about 450 to 2000 m (Isaacs, 1981)
which may correspond to temperatures (Tissot and Welte, 1980), is also the
rate less rapidly in Mg-rich (e.g. ,
marine-derived) pore water - a factor c
of 40-100 oC. These reactions involve
changes in crystal-lattice morphology
temperature range in which many other
burial diagenetic processes involving
that may be partly responsible for the
retention of high poros ity in many c
and release water of crystallization. inorganic reactions, pressure-solution, chalks (Neugebauer, 1973, 1974). c
Other reactions which release water
along with various cations are the con- A PRESSURE, bars B TEMPERATURE,oc c
version of smectite to mixed-layer clays
and finally to illite commencing at
ir-----.;.~--::..:r'---"""""-'-r--__,
4000 0 100 200 300
c
around 2000 m and 60°C in the US c
Gulf Coast (Burst, 1969; Perry and
Hower, 1970; Hower et a/., 1976; Boles
...E
10
c
and Franks, 1979),and the dehydration
of various iron hydroxides such as lim-
:z:
l-
20
...
'6 c
onite to yield hematite and free water.
Still other reactions affecting carbon-
ll.
W
a
)(

c
ates, which take place in sandstones,
include the conversion of calcic plagio-
clase to albite releasing Ca 2 + and 100
e
other divalent cations such as Sr2 + x1()3 psi OF c..
which have been used as radiogenic
tracers of burial reactions (e.g., Steu- Figure 2 Graphs showing the general ranges of pressure and temperature in the deep-
burial diagenetic realm .
c
ber and Pushkar, 1983; Moore, 1985;
Woronick and Land, 1985).
(A) Static pressure ranges. The position of the hydrostatic pressure curve varies depending C
on the concentration and density of pore waters. Most pore-fluid pressures in the subsurface
(3) Increasing temperature together would plot on curves in the stippled area. Commonly the change from normal to excessive pore- l
with burial reaction time causes the con- fluid pressure is a transition marked by more rapid increases in both pressure and (graph B).
version of sedimentary organic matter (B) Temperature ranges assuming different geothermal gradients. Most gradients are
from unstable to more stable forms 15·35°C, and most are non-linear and commonly steepen (decrease) with increasing depth. c..
t
C
c
c Limestones - The Burial Diagenet ic Environment 79

c
c: The introduction of liquid hydrocar- Processes. Physical compaction A common conclusion of experi-
c bons into the pore systems of lime-
stones during burial diagenesis ,
in marine sediments buried in marine
pore waters can be visualized as taking
ments involving compaction of muddy
carbonate sediments is that thickness
c especially if the pore walls are oil-wet,
inhibits pressure-solution and can pre-
place in three main stages which pro-
bably overlap.
reductions can be substantial and in
some cases greater than porosity
(
clude the formation of stylolites; Dun- Stage 1: Initial particle settling and reductions, especially in stage 2 com-
o nington (1967), who first suggested
these effects, also noted that the
repacking with resulting dewatering
occurs in the first metre or so of burial,
paction (Terzaghi, 1940; Hathaway and
Robertson, 1961; Fruth et al. , 1966;
c emplacement of oil in some limestone where porosities of lime muds may be Robertson , 1967; Ebhardt, 1968; Shinn
c reservoirs of the Middle East might
actually have prevented their compac -
reduced a small amount, say from
80-75% (Ginsburg , 1957; Brown, 1969;
et aI., 1977; Bhattacharyya and Fried-
man, 1979). Shinn and Robbin (1983)
( tion and created differential-compac- Schlanger and Douglas, 1974; Enos compacted modern shallow marine
tion traps for hydrocarbons. Liquid and Sawatsky, 1981). and peritidal muddy carbonate sedi-
( hydrocarbons in pores can also shut off Stage 2: Particles are rearranged ments with 47-83% initial porosity down
o or prevent cementation. This mecha-
nism has been invoked to explain dif-
and elongate grains re-oriented in
grainy sediments, while muddy sedi-
to as little as 27% (mostly 30-65%) of
their orig inal thickness, with final
o ferences in extent of pressure-solution ments are compacted with continued porosities reduced to 35-45%. Al-

o cementation and porosity reduction in


some chalk reservoirs in the North Sea
dewatering , until a self-supporting
"framework" is achieved at porosities
though some chem ical compaction
effects were observed in cores sub-
o (Feazel et al., 1985; Feazel and
Schatzinger, 1985).
of approximately 40%. The relative
importance of this stage of compaction
jected to the highest pressures, physi-
calor mechanical compaction was by
o is proportional to the original ratio of far the dominant process. At pressures

o PROCESSES AND PRODUCTS


In the sections that follow, we examine
lime mud to coarse silt size and larger
grains. In shallow sub-tidal sediments
of 66 to almost 1000 kg' cm·2 (933-
13,600 psi), compaction as gauged by
the common sedimentological and th is compaction often takes place thickness reductions essentially ended
geochemical processes and products within a metre or so below the sea floor ; when porosities were reduced to
o of burial diagenesis - the records of one can stand on the sediment rather 35-45%. The results of these experi-

o their passage into the deep subsurface


(Table 1).
than sink into it and one can generally
core it (L.S. Land. pers. comm., 1986).
ments indicate that carbonate sedi-
ments can compact under as little as
Physical Compaction. Stage 3: Overburden stress is ap- 100 m of overburden to one-half their
As sediments compact under load they plied at grain contacts, and is accom- original thickness, with accompanying
dewater, lose porosity, and decrease in modated by grain deformation in the porosity losses of 50-60% of original
thickness while sedimentary part icles form of either ductile squeezing or brit- pore volume.
(
and sedimentary structures are modi- tle fracturing and breakage. Lime mud Products. Sedimentological pro-
( fied and/or rearranged, depending on between framework-forming grains , in ducts of physical compaction are
how much porosity they had and shelter cavities beneath elongate parti- almost as varied as the constituents of
whether they were grain-supported or cles, or within fossils, is generally pro- the limestones (Figure 3). In mud-
( mud-supported initially. tected from compaction. supported or pelleted-mud sediments
(mudstone and wackestone) common
o features include : thinning of laminae

o DEPOSITION
PHYSICAL
between and draping over early con-
cretions (Figures 4 and 5), early-lithi-
o COMPACTION fied layers , and other hard objects ;
BURROWS
DESICCATION
CRACKS

EARLY
LITHIFIED LAYERS

FOSSILS
EARLY L1THIFIED
~:~r---.,r--.,-r='--I

~~;;~=3
~
I @)~ ~
!::~ ~ ~
• SQUASHING
squashed burrows and crumpled fe-
nestrae, gas-escape structures, and
desiccation cracks (Figure 6); shells
and other elongate grains that have
been rotated, packed more closely, or in
some instances brought into proximity
with other rigid grains against which
LUMPS OR I" _,_~
( they have been crushed (Figures 7 and
BURROWS :~ . OVERPACKING
GRAINSTONE I~ SPALLED
8); and flattened pellets or other grains
LENSES ~--- 0010 (Figure 9).
CORTEX
Physical compaction also produces
a variety of swirling structures as well
as the textural "telescoping" noted by
Shinn and Robbin (1983), converting
FRACTURED
MICRITE ENVELOPES grain-poor lime mud to wackestone or
.. GRAINS packstone (Figure 8). Physical com-
paction can close and obliterate desic-
Figure 3 Sketches illustrating features produced by physical (mechanical) compaction. cation cracks and fenestrae or birds-
eyes in peritidal sediments (Figure 6).
c
80 Diagenesis Geoscience Canada Reprint Series 4 c
Figure 4 A slab of early burial-diagenetic
c
displacive-fibrous calcite (DFC, arrows) c
developed on both sides of a mudstone bed
that was formed by coalescence of micro- c
spar concretions. The bed was thinned a
litt/e between concretions by physical com-
paction prior to formation of the DFC. From
c
(
Cambro-Ordovician Cow Head Group,
western Newfoundland (Coniglio , 1985).
Photo courtesy of M. Coniglio, published by
permission . c
c
c
c
Figure 5 A concretion formed by early-
burial microspar cementation of peloidal c
wackestone (darker) and grainstone
(lighter). The uncemented laminae to right
c
have been compacted to 36% of their thick-
ness as preserved in the concretion . Com-
c
paction was probably physical rather than c
chemical. A dilation crack (arrow), now
filled by ferroan calcite spar (black in this
picture), opened due to differential com-
c
paction of the concretion . Photo is a
(
negative print of a thin-section. Bar scale is
1 cm. From Cambro-Ordovician Cow Head c
Group, western Newfoundland (Coniglio,
1985). Photo courtesy of M. Coniglio, pub-
c
lished by permission. c
c
c
c
c
c
C
Figure 6 (A) Uncompacted supratidal
sediment from the Holocene of south Flor- E
ida (plastic-impregnated core). The open-
ings are birds-eye or fenestral pores, verti- C
cal shrinkage cracks, and burrows, and
horizontal cracks and large cavities proba-
C
bly formed artificially.
(8) Artificially compacted sediment from
C
the same core. Only the thin storm layers C
and desiccation cracks in A are clearly pre-
served. Virtually all the voids have been
squeezed shut, and the overall fabric has
been strikingly changed. From Shinn and c:
Robbin (1983). Photos courtesy of E.A.
Shinn, published by permission .
c
c
c
c
C
C
l
C
c
c Limestones - The Burial Diagenetic Environment 81
(
( ,
o
o
(
c
(
(
·0········ '. ...
. -~.'
~ --:.- ~
.
C'
C
'. ':' ~..@:.~~'. ~ ;;;2..
.. ~.: .:.f(~-~~ ... ~
o .~" . ' ..
o ~

. . .' .• f'::\ .
\!!../ .
.
o .
o
o
o
(
o Figure 8 Diagrams illustrating the trans-
formation of lime mud with sparse allochems
Figure 7 (A) Uncompacted subtidal bioclastic muddy sediment from the Holocene of to Iithified, more allochem-rich limestone, in
south Florida (plastic-impregnated core). The mollusk shells and Halimeda plates (white) lack this case wackestone, as a result of physical

o preferred orientation . (R, horizontal grass rhizomes; G, marine turtle grass.


(8) and (C) Artificially compacted sediments from the same core, under different loads.
compaction alone. Proportions of mud parti-
cles to pore space are shown schematically
Mollusk and Halimeda fragments have been reoriented and commonly broken, drape-like swirls by the dots.

o have appeared, and all of the "open " and uncalcified structures have been squeezed shut.
From Shinn and Robbin (1983). Photos courtesy of EA Shinn, published by permission.

c
o
o
o

l
l
C

Figure 9 A pisolitic grainstone that has suffered grain flattening by Figure 10 Ooids which have been squashed by physical
physical compaction, and also pressure-solution interpenetration compaction ; outer concentric laminae on the ooids to right and left of
along microstylolites now marked by dolomite rhombs and voids center are fractured and spalled. Some pressure-solution also has
(white). Bar scale is 1 mm. From the Mission Canyon Formation occurred, embaying outer laminae as in the large ooid to right of
(Mississippian), Williston Basin, North Dakota (Elliott, 1982). Photo center. Bar s..cale is 1 mm. Upper Cambrian, Port au Port Peninsula,
courtesy of IL. Elliott, published by permission. Western Newfoundland. Photo courtesy N. Chow.
c
82 Diagenesis Geoscience Canada Reprint Series 4 c
c
Organic matter is commonly squashed grained carbonate sediments is gener- noted by many workers (e.g., Hallam, c
and deformed into irregular stringers
that drape over rigid grains and look
ally related directly to the abundance of 1964; Byers and Stasko, 1978; Bathurst, c
deceptively like stylolites. Relatively
brittle laminae and thin mud-cracked
clay and organic matter so that the
relatively pure CaC031ime muds tend to
compact the least. Ricken (1987) has
1987) between percent carbonate and
amount of compaction is rigorous and
unvarying in mud-rich sediments. In
c
beds between layers of plastically com- suggested that this inverse relationship such sediments, however, particularly if
C
pacted mud may fracture and rotate r
(Figure 8).
In grain-supported clean and mud- C
dy carbonate sands (grainstone and
packstone), plastic deformation of soft
C
pellets, coated particles and skeletal C
grains is common (Figure 9). Ubiqui-
tous, however,arefractured andcrushed C
grains of various kinds such as spalled
and broken cortical layers of ooids (Fig-
C
ure 10), broken thin rinds of cement C
around grains that have been squas-
hed, crushed fossils (Figure 11), and C
fractured micrite envelopes surround-
ing grain molds. Also typical are planar
C
or curviplanar grain contacts resulting C
from plastic deformation; care must be
taken, however, to be sure these con- C
tacts are due to physical compaction (
and not pressure-solution.
Compaction of lime mud between C
grains, in sheltered patches either
beneath broad particles such as phyl-
C
loid algal plates and brachiopod valves
or inside fossils, is generally very slight,
Figure 11 Part of a crushedrugose coral, the victim ofphysical compaction of the surrounding
packstone matrix. Near-shore-marine skeletal limestone from the Mission Canyon Formation
C
so that original textures and particles (Mississippian), Williston Basin, North Dakota (Beach and Schumacher, 1982). Bar scale is C
1 mm. Thin-section loaned by D.K. Beach.
are preserved (Figure 12).
Thin ning of limestone strata by physi-
C
cal compaction itself is becoming more C
widely recognized. One ofthe more con-
vincing large-scale examples is re- C
ported by Beach and Schumacher
(1982) in the Mission Canyon Formation
C
(Mississippian) in a part of the Williston C
Basin in North Dakota. There, pisolitic
grainstones interpreted as "island C
facies" that haveopen, little compacted
fabrics are surrounded by compacted
C
marine bioclastic and peloidal wacke- C
stone and packstone. A series of iso-
pach maps suggests post-depositional, C
non-erosional thinning of the marine (
limestones by as much as 31 %, and
crushed fossils and other features (Fig-
ures 11 and 12), unaccompaniedby dis-
solution seams (to be discussed in the
e
next section), imply that physical com-
paction contributed to the thinning. Dif-
c
ferential compaction at hand-sample (.
scale has been estimated from changes
in the shapes of Chrondites and other
Figure 12 Sheltering effects in compacted shallow-marine foraminiferal-peloidal limestone. A c
burrow tubes that were cylindrical be-
whole, but broken, brachiopod shell sheltered the grain-rich sediment inside it from physical
compaction, and this sediment is now normally packed grainstone (lower right), while the same c
fore they were buried (Byers and Stas-
ko, 1978; Gaillard and Jautee, 1987;
sediment outside the shell was compacted and is overly packed packstone. Bar scale is 1 mm.
Mission Canyon Formation, Williston Basin, North Dakota (Beach and Schumacher, 1982). Thin-
c
Richen, 1987). Compaction in fine- section loaned by D.K. Beach.
c
c.
c
(
( Limestones - The Burial Diagenetic Environment 83
r
C aragon ite and Mg-calcite are abundant , Chemical Compaction source of carbonate cement in deep-
C the amount of compaction must surely
be dependent as well on the chemistry
(Pressure-solution).
Chemical pressure-solution compaction
burial diagenes is (e.g., Bathurst , 1975;
Hudson, 1975; Wong and Oldershaw,
o of the pore waters during early burial. is of great significance in carbonate 1981; Scholle and Halley, 1985). Further-
c Although the relative importance of
physical and chemical compaction is
rocks. It is known to be responsible for
reductions of bed and sequence thick-
more, it has been demonstrated that
spaced cleavage of tectonic origin in
( often difficult to assess even where the nesses in the range of at least 20-35%, folded limestones is in fact a pressure-
products of the two can be clearly iden- thickness reductions that took place solution phenomenon, and that space-
( tified (cf. Figures 3 and 13),what is now after physical compaction. Pressure- cleavage surfaces are actually stylolites
( clear is that stratigraphic thinning and solution (or pressure-dissolution) is also or non-sutured seams (e.g. , Geiser,
many smaller-scale changes produced becoming more widely recognized, 1974; Groshong, 1975a,b; Rutter, 1976,
c by physical compaction are widespread
in the carbonate rock record.
despite the common difficulty in proving
cause and effect, as an important
1983; Alvarez et al., 1976; Drexler and
Schaer, 1979; Engelder et a/. , 1981 ;
( Geiser and Sansone, 1981; Marshak and
o CHEMICAL
Engelder, 1985).
The term "chemical compaction" was
proposed by Lloyd (1977) for the loss of
COMPACTION •
o

porosity and decrease of thickness
STYLOLITES brought about in limestones by the gen-
o , . - -- - - ',
./
SINGLE
' . ( ,.
eration of " autochthonous" carbonate
cement internally through pressure-sol-
o 1"'-/1-/'-"'\,-<,'' / »>:~
f~~~~:::L,J-
/" ution. Carried to completion, cementa-

o ~~~.___
MULTIPLE
~'v.-=",'~~ tion of pores by this process should be
capable of completely occluding what-
o ~~~.~: _-- SOLUTION SEAMS ever porosity remains in the wake of

o
o
NODULES

FITTED
I :. ...
-. ~• •...-:_--~
~NOD""
MICROSTYLOLITES
physical compaction and near-surface
diagenesis. In Bathurst's (1971) words a
limestone undergoing chemical corn-
paction serves as both a donor and a
o NODULES I- - · -·..;...._~ .;, ;;..
NODULE
receptor of carbonate cement.

c ~.~ ."""'. · ·--- '~I PHYSICAL


.-
.... - COMPACTION
" MICROSTYLOLrrES
Pressure-solution and its most ob-
vious products, stylolites , have attract-
o
:;...-

r: -~._~=-= STYLOLITE ed the attentions of geologists for well


~ -- over a century, beginning apparently
o with the inquiries of Thompson (1862)
and Sorby (1879, 1908). Quantitative
Figure 13 Sketches of features produced by chem ical (pressure-solution) compaction. studies of thickness reductions due to
o stylolites were made more than a half-
century ago by Stockdale (1922, 1926),
o SOLUTION and more recently have been carried out

o
,
by Dunnington (1954, 1967), Mossop
(1972), Playford (1980), Hurley (1985),
o Bathurst (1987) and many others; our


experience and discussions with other
o geologists suggest that major thickness

o reductions also have been well docu-


mented in a large number of unpub-
o lished studies. The time and space rela-
tionships between pressure-solution ,
C physical compaction and cementation
have been examined most recently by
l Shinn and Robbin (1983), Bathurst
(1984), and Scholle and Halley (1985).
r Processes. Pressure -solution is a
'-- process wherein pressure due to load
r: or tectonic stress, transmitted to and
'-.-.'
concentrated at contact points or sur-
r:
faces between grains, crystals or larger
entities (limestone beds, for example),
Figure 14 A conceptual sketch of elements on a microscale involved in pressure-solution of increases the solubil ity of the stressed
two grains pressed together at a sutured contact. mineral(s) due to increasing elastic
c
84 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
c
c
c
c
(

C
C
C
Figure 16 Bedding-parallel stylolites
(sutured seams) in thin beds of lime
C
mudstone separated by thin shaly partings C
(lighter gray). Etched core-slab surface, bar
scale 1 cm. Ste. Genevieve Formation C
(Mississippian), Illinois Basin, Illinois.
C
C
Figure 17 Swarms of microstylolites and
non-sutured wispy seams in a wackestone G
with lenticular burrow fillings of grainstone.
Figure 15 Stylolitic contact between ooid
Bar scale is 1 em. Bajocian (Jurassic), C
grainstone above and microcrystalline
Lincolnshire, UK. Photo courtesy of R.G.C.
Bathurst, published by permission.
C
dolomite below. Finely particulate sulphides
and pyrobitumen(?) form the dark sutured C
seam. Core-slab surface, bar scale 1 cm.
Ste. Genevieve Formation (Mississippian),
C
Illinois Basin, Illinois. C
C
C
C
C
C
C
C
C
Figure 18 (lower left) Outcrop photo of C
lime wackestones that show "pressure-
solution bedding" at fissilepartings made up c
of.concentrations of microstylolites. Scale is
0.5 m long.
e
(upper right inset) Thin-section photo of (
partings in an area such as that shown by
arrow, illustrating a concentration of disso-
lution seams and microstylolites. Brachio-
c
pod shelf was broken during physical com- l
paction, then thinned somewhat by pressure
solution. Bar scale is 0.25 mm long. Visean C
(Carboniferous), Clwyd, North Wales, UK. (
Photos courtesy of R.G.C. Bathurst, pub-
lished by permission. C

c
(
c Limestones - The Burial Diagenetic Environment 85

c:
( strain , and causes dissolution at the stylolites (the " fitt ed fabrics" of Logan Recognition that non-sutured seams
o contact. The phenomenon therefore and Semeniuk (1976) and Buxton and (also called clay seams - Barrett, 1964;

o involves a change of state from solid to


liquid, creating a microscopic solution
film (Weyl, 1959;De Boer, 1977; Robin,
Sibley (1981). Some stylolites develop
select ively at contacts (Figure 15)
between beds or nodules of highly con-
horsetails - Roehl, 1967; Mossop, 1972;
wispy laminae - Lucia, 1972; wavy
laminae - Reinhardt and Hardie, 1976;
(
1978)a few water molecules thick at the trasting solubilities such as well- pseudo-stylolites - Shinn et al., 1977;
( contact. This film mayor may not be cemented oolite and microcrystalline and "microstylolites" - Wanless, 1979)

c connected with the solution-filled pore


system of the rock (Figure 14).
For CaC0 3 , because the solubility-
dolomite (e.g., Choquette and Steinen,
1980). Often they propagate most
extensively in relatively clay-free, lime
are pressure-solution features has led
to useful new classifications (Garrison
and Kennedy, 1977; Wanless, 1979;
(
product constant mudstone and wackestone, though Buxton and Sibley, 1981 ; Koepnick,
C' Ks p = [Ca 2 + l x [CO~- l they may have been initiated at clay/ 1984; Scholle and Halley, 1985), as well
increases at the locus of maximum shale partings between " clean" lime- as a more radical classification and ter-
( stress due to increased strain energy, stone beds (Figure 16). minology (Logan and Semeniuk, 1976).
o dissolution releases new ions of solute
to the solution film. This pressure-
On the other hand, non-sutured
seams (Wanless, 1979), have been rec-
The organization of pressure-solu-
tion features outlined in Figure 19 is
( induced solubility increase sets up a ognized only since the 1970s (e.g., modified from a conceptually simple

o chemical potential gradient which


declines away from the locus toward
Mossop, 1972) as features probably
caused by pressure-solution (Figure
classification by Wanless (1979). From
this way of organizing the observations
o areas of lower stress. Ions move down
this gradient by solution transfer
17). These are "wispy" surfaces that
may extend laterally a few centimetres
of many workers and from other con-
siderations, some points of interest
( (Durney, 1976)or diffusion , to be either to hundreds of metres. They are emerge as one tries to understand the

o combined and precipitated as new cal-


cite cement at nearby sites where stress
marked, like sutured seams, by con-
centrations of organic matter, clays,
origins and dynamics of pressure-solu-
tion features.
and solubility both are lower, or trans- pyrite and detrital silicates, and com- (1) Both sutured and non-sutured
ported in moving pore waters to more monly dolomite of residual or syn-stylo- seams can be either bedding-parallel
( distant sites. Each mole of CaC0 3 dis- lite origin. Non-sutured seams develop and single or multiple, or reticulate, as
o solved by this mechanism will produce a
mole of solute ions and therefore, poten-
typically in limestones (and some finely
crystalline dolomites) that have signifi-
implied in Figure 19 by the multiple sty-
lolites and fitted nodules.
tially, a mole of CaC0 3 cement. cant amounts (more than about 10%) (2) Reticulate systems of anastomos-

c The analogy is nearly exact with ice


which is gradually stressed at a contact
point , say by a metal-tipped pole: ice
of clay and silt-sized quartz and/or sev-
eral percent or more of organic matter.
Often it is difficult to be sure that these
ing microstylolites (fitted fabrics) and
non-sutured seams occur as a rule in
limestones made up of abundant rigid
dissolves at the contact and a depres- wispy to planar seams are the result of entities of sand size or coarser (the
sion forms , with an intervening film of pressure-solution rather than physical "idens" of Logan and Semeniuk, 1976).
water between metal and ice; when the compaction, and in fact very similar fea- These may be in grain-to-grain contact,
pressure is released and the metal tures have been produced experimen- like ooids and skeletal debris in poorly
o point removed, provided the air is
below the freezing temperature of
tally by physical compaction and termed
pseudo-stylolites (Shinn and Robbin,
cemented grainstones (Buxton and
Sibley, 1981; Meyers and Hill, 1983); or,
o water, ice forms again in the depres- 1983).It can be equally hard to ascertain the entities may be surrounded by

o sion. The main departure from this ana-


log of course is that in the subsurface
whether thinning and draping of lam-
inae over and under rigid nodules and
more soluble sediment, like burrow-
controlled, resistant nodules of chert or '
the pressure is usually maintained . other objects, without obvious seams of carbonate-cemented sediment in a
Products. Pressure-solution fea- residues, are due to the "non-seam dis- matrix of clayey or orqanlc-rich lime
tures are amazingly diverse (Figure 13). solution " of Wanless (1979) or to purely wackestone. Pressure-solution pre-

o Even stylolites, the most spectacular


products. vary so much in amplitude
physical compaction as noted in Shinn
and Robbin's (1983) experiments.
sumably starts at grain contacts (often
preceded by physical compaction). The
(I and in form from one occurrence to In some sequences of stratified lime- microstylolites then propagate irreg-
another that they have stimulated a stones the seams are so abundant and ularly through their host to create a
l series of elaborate classifications (e.g., closely spaced as to impart a distinct fitted-fabric network. The network style
Stockdale, 1922;Park and Schot, 1968; pseudo-bedding strikingly like deposi- is a result of a high degree of hetero-
Wanless, 1979). tional bedding , as illustrated in Figure geneity.
The common denominator of stylo- 18 (Bathurst, 1987; Simpson, 1985). (3) Bedding-parallel seams typically
lites and other sutured seams (Wanless, Bathurst (1987)has reckoned that solu- develop in well-bedded and/or more
1979) is a jagged surface, generally tion thinning along these non-sutured homogeneous limestones. The homo-
coated by insoluble clays, organic mat- seams may be comparable to the thin- geneity commonly exists either be-
ter and/or other minerals, and made up ning caused by stylolite-forming dis- cause the limestones are Iime-mud-
of interlocking pillars, sockets, and vari- solution . It would seem, therefore, that rich with few large grains, or because
ously shaped "teeth". Sutured seams there is an important, previously unrec- they are grain-rich but have been exten-
include stylolites, many microstylolites, ognized source of CaC0 3 in addition to sively cemented by calcite and thus
and networks of anastomosing micro- obvious stylolites. have less contrasting solubilities than
c
86 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
ISTYLES OF PRESSURE-SOLUTION I c
c
INON-SUTURED SEAMS I SUTURED SEAMS
c
c
BEDDING-PARALLEL
SINGLE -------
* BEDDING- PARALL EL
SINGLE I~~
< LA RGE AMPL
SM ALL AMP c
SWARMS SWARMS ~
NON -PARALLEL RETICULATE NON -PARALLEL RETICULATE
c
GRAIN -CONTACT
MULTI-GRAIN ~ -
"', -
""'"
€I>
. ' .
" GRAIN -CONTACT t
"MULTI-G RAIN t

, " NOD ULE-B OUNDING t

, stylo lites
, • microstytontes
".
-c::zm~·
c
c
c
c
t may be Med fabrics
c
Fig ure 19 Styles of pressure solution . Modified from Wanless ( 1979).
c
c
1 2 3
c
~--- - -- -- -
c
~ c
A
- - -=:, =-= ~ -..; =--- ... . -.. -"'-=-~-
c
€) - -. - .:.,: - - • ..;.;:.:.;:-::;:;:- .
........;.;... c
-- @JJ)--::~- .:::,:,,::,::::.
c
BURROWED LIM E MUDSTONE
w JORGANIC-R ICH NON ·
PARALLEL TO RETICUL ATE
MICROSTYLOLITES & SEAMS
PARALLE L TO RETICULATE
MICROSTY OliTES c
SUTURED SEAMS
c
c
B
- '-e;;==:..
~
-
c
c
c
LIME M UDSTONE w JSHALE
INTERBEDS
PARALLEL S"" ALL STYLO LITES PARAL LEL STYLOLITES &
M ICROSTY LOLITES c
c
c
c c
e
c
PACKSTONE OVE R MICROSTYLOL ITES & RET:CULA TE NETWORK OF'
MICRODOLO MITE STYLOLITES CONT ACT MICROST YLOLITES
IFITT ED F ABRIC,
c
c
Figure 20 Sketches to suggest pathways along which pressure-solution features may develop and evolve. The initial sediments (stage 1) are
assumed to have been physically compacted already, so that further compaction is entirely chemical. The microcrystalline dolom ite in Cremains
c..
essentially uncompacted. c
c
c
r
c Limestones - The Burial Diagenetic Environment 87

before cementation. Well-bedded lime multiple stylolites are initiated, some buried now under 550 m of overburden
mudstones , therefore, tend to have sty- propagate parallel as well as normal to (Choquette and Steinen, 1980). In lime-
lolites of fairly uniform ampl itudes. the direction of maximum stress, and stones of the uppermost Madison
o Rudstones commonly have stylolites
that parallel stratification but vary in
these then accommodate the stress
selectively and continue to grow at the
Group (Mississippian) in parts of west-
ern Wyoming, irregular stylolites are
their amplitudes because of grain-to- expense of the others. intensely developed in zones a few me-
grain solubility contrasts. Sequences in Factors that Influence tres to tens of metres beneath the post-
which relatively pure limestones are Pressure-Solution. Madison unconformity and rather
interlayered with organic-rich and/or The factors that determine when in a sharply diminish in intensity downward.
r clay-rich limestone intervals tend to sediment's burial history pressure- This distribution suggests that they
undergo strong compaction and intense solution will become significant, under may have been formed in a near-sur-
r:
development of stylolites in the less what conditions it will slow or cease, face meteoric zone. Thus, the sugges-

o pure intervals (e.g., Figure 18).


(4) Although recent experimental
and its role relative to physical compac-
tion and cementation , all are poorly
tion of Dunnington (1967) that pressure-
solution becomeseffectiveand stylolites
o work suggested to Baker et al. (1982)
that clays reduce the solubility of cal-
understood. What is clear is that a large
number of factors can be influential.
become abundant after burial to around
600-900 m is probably an oversimp-
o cium carbonate with which they are
admixed, a large body of field, petro-
Among these are the amount of over-
burden (Iithostatic pressure), early
lification.
Pore-Water Composition. Pres -
graphic and other observations by cementation and dolomitization, water sure-solution seems to be accele-
many other workers indicate the chemistry, water flow rates, pore-fluid rated, and physical compaction may be
opposite, namely that clays (and/or pressure, presence of liquid hydrocar- inhibited, by Mg-poor meteoric waters
o organic matter) seem in fact to be bons, CaC0 3 mineralogy, clay and as opposed to marine-derived pore

c required in order for pressure-solution


to occur. Furthermore, as just noted,
organic matter, porosity and perme-
ability and possibly temperature be-
waters. Neugebauer (1973, 1974), draw-
ing on work by Lippmann (1973) and
o many solution seams show signs of
having been initiated along clay part-
cause of its effects on carbonate min-
erai solubilities. Many of these factors
some others, concluded that high Mg2+
activities and high Mg2+ /Ca2+ ratios in
ings or clayey zones. also influence carbonate cementation, the marine-derived pore waters of the
Notwithstanding that many aspects and most of them have been considered North Sea and deep-sea chalks were
of pressure-solution are poorly under- recently in that context by Feazel and partly responsible for inhibiting cemen-
stood, still it is useful to try and put Schatzinger (1985). tation and porosity reduction by inhi-
r: together the observations just consid- Burial Depth. Chemical compac- biting pressure-solution. The inhibiting
ered, in a way that may suggest some tion probably starts in marine sediments effect is apparently due to the high
dynamics for the initiation and propa- within the first few hundred metres of hydration energy of Mg2+, which
gation of pressure-solution features. burial. There and until the sediments decreases with rising temperature
As shown diagrammatically in Figure are firmly cemented , particle-to- (Bjorlykke, 1983). The converseof these
20, stylolites and microstylolites may particle pressure-solution and point- ideas is that pressure-solutionshould be
begin either as sutures along contacts contact cementation (the " s p ot- favoured in burial settings characterized
between rigid grains, nodules and the welding" of Mapstone, 1975) seems to by input of meteoric water.
like, or as non-sutured seams in clay- be the dominant style of pressure- Metastable Mineralogy. Wherever
o rich zones and clay partings. Once initi-
ated, the sutures propagate at apparent
solution . Non -sutured and sutured
seam pressure-solution features may
aragonite and high-Mg calcite persist
into the burial environment they should
rates and in patterns that appear to vary begin to form toward the lower end of favor pressure-solution,giving their host
in space and time. It was once thought this depth range and certainly become limestones a high "diagenetic potential"
that stylolite geometr ies are governed obvious after about a kilometre of for alteration (Schlanger and Douglas,
in part by solubility contrasts between burial. 1974). Deep-sea nannofossil-foramini-
r: grains and other rigid entities (Stock- In carbonates being buried in dilute feral oozes have low diagenetic poten-
dale , 1922, 1943; Coogan and Manus , pore waters, the minimum burial depth tials because their calcium carbonate is
1975;Chilingaretal., 1979). Dunnington needed to initiate chemical compaction all low-Mg calcite. This is a factor in
r: (1954) showed, however,that this factor is likely to be more variable and may accounting for their slow rates of
alone cannot be enough because it fails often be less . Pressure-solution in pressure-solution, cementation, and
to explain the variations in geometry shallow-marine grainstone and pack- porosity reduction.
found among stylolites. A more plausi- stone of Mississippian age in south- Clay Minerals. On balance, as dis-
ble kinematic control on the develop- eastern New Mexico apparently began cussed earlier, clays appear to foster
ment and form of stylolites has been after only tens to hundreds of metres of pressure-solution. Marshak and Engel-
proposed by Guzzetta (1984) . This kine- burial (Meyers and Hill , 1983), resulting der (1985) concluded from petrographic
matic model of migrating dissolution in fitted fabrics of microstylolites. Stylo- and X-ray diffraction evidence that in
domains is based on the hypothesis lites are well developed in Mississippian order for spaced, pressure-solution
,-. that dissolution can only take place on lime mudstones in the Illinois Basin sub- cleavage of tectonic origin to develop in
one side at a time of a pressure-solution surface, about 150 m below the uncon- limestones, clays must be present
contact surface, and will shift from one formity separating the Mississippian between grains or along crystal bound-
side to the other through time. Where and Pennsylvanian systems there, and aries to provide "interconnectivity" of
c
88 Diagenesis Geoscience Canada Reprint Series 4 c
c
dissolution sites at grain boundaries until there is no longer an ion-activity Schlanger and Douglas (1974) for a
c
with the larger-scale, free-fluid system. gradient away from the stressed-solid thoughtful review of chalk diagenesis in c
Bathurst has concluded (pers. comm. ,
1986) that the amount of clay and asso-
contact (along the solution film toward
the pore-water system). This can only
DSDP cores, and Coniglio (1985) for an
in-depth study of the petrology of c
ciated fines has an influence on the
style of pressure-solution: Sutured-
obtain where the pore-fluid pressure
equals or exceeds Iithostatic (or other
ancient deep-marine limestones).
Much of the cement in ancient shallow-
c
seam stylolites of the sort illustrated in
Figures 15 and 16 are favoured where
directed-stress) pressure, in which case
the porosity and permeability must
marine, peritidal, and platform-margin
limestones is of burial-diagenetic origin
c
clay/silt content is significant but less effectively be zero. If, as now seems (Talbot, 1971; Meyers, 1974, 1978;
than about 10%, whereas non-sutured
seams like those in Figures 17 and 18
likely, the porosities of sedimentary car-
bonates approach zero asymptotically
Grover and Read, 1983; Mattes and
Mountjoy, 1980; Moore and Druckman,
c
tend to develop if clay/silt content ex- with increasing burial depth, pressure- 1981; Elliott , 1982; Frank et al., 1982; c
ceeds about 10% and/or there is a sig-
nificant amount (more than a few per-
solution may in fact continue, though at
rates approaching the infinitesimal, to
James and Klappa , 1983; Burruss et al.,
1983; Walkden and Berry, 1984; Cho- c
cent) of organic matter. Where there is depths well below 6 km in the litho- quette and Steinen, 1985; Druckman c
neither clay nor organic matter, stylo-
lites are unlikely to develop. Stylolites
sphere. All that is required to sustain
some pressure-SOlution, given aqueous
and Moore, 1985; Mruk, 1985; Brinton,
1986). The importance of burial-diage- c
common ly seem to start developing
along clay-shale partings. The observa-
pore fluids, is enough stress to exceed
the pore-fluid pressure.
netic cementation has also been
forcefully argued on grounds of stable- c
tions of Marshak and Engelder (1985) isotope compositions by Hudson (1975, c
are relevant in this connection. They
found that pure lime grainstones deform
Burial Cements
It is now clear that much of the carbon-
1977)and on this and other evidence by
Bathurst (e.g., 1971, 1984) and Scholle c
primarily by twinning, with only isolated
tectonic stylolites, and rarely develop
ate cement in many well-lithified lime-
stones was emplaced during burial dia-
and Halley (1985).
Shallow Burial "Marine" Cements.
c
tectonic (pressure-solution) cleavage. genesis. Essentially all cementation in Cements of early, shallow burial origin c
They also observed that sutured, stylo-
litic seams develop in relatively clay-
deep-basinal sediments that were
never uplifted into the meteoric, chalks
(first few metres to tens of metres) in
deeper marine settings include displac- c
poor limestones and non-sutured
seams in the more clay-rich limestones.
included, must be of burial origin (see ive fibrous calcite (also called "beef"
c
Early Dolomitization. Early, pre- c
burial or very shallow-burial dolomitiza-
tion can inhibit or preclude stylolites c
from forming . For example , lime mud-
stones in the Ste. Genevieve Formation BURIAL c
(Miss issippian) of the Illinois Basin CALCITE c
have superbly developed bedding-
parallel stylolites, but closely associ- CEMENTS c
ated microcrystalline dolomites that
formed by local alteration of similar
c
precursor lime muds have no style- C
lites (Choquette and Steinen, 1980).
The dolomites acquired a "grain- NON-LUMI NESCENT
E
supported" crystal framework that
resisted stylolitic pressure-solution.
BLADED PRISMATIC
I BRIGHT C
Liquid Hydrocarbons. Early intro- C
duction of oil into the pore systems of
limestones still undergoing chemical
C
compaction tends to inhibit or shut off C
the process, and can entirely prevent
the formation of stylolites (Dunnington, c
1967) as well as other pressure-solution
effects including "autocementation ".
e
Under what conditions, then, apart 1.._
from the factors just considered, can
pressure-solution no longer take place? COARSE MOSAIC DULL
C
If the solution-film model is in fact the CALC SPAR (
mechanism for pressure-solution in
limestones, and diffusion due to stress PLANE LIGHT CATHODOLUMI NESCENCE
at this film is the rate-controlling step
(Brown, 1987), pressure-solution
(
Figure 21 Sketches of burial-diagenetic cements as they appear in plane light and
should continue at diminishing rates cathodoluminescence. C
(

C
cr:
Limestones - The Burial Diagenetic Environment 89

and " cone-in-cone"; see Figure 4), a 40-50°C to perhaps 200°C or higher, moderately reduc ing pore waters
variety peculiar to highly argillaceous burial depths from a few hundred (Oglesby, 1976; Pierson, 1978; Frank et
mudstones; and low-Mg calcite metres or less (Meyers, 1980) to kilo- al., 1982). Near-surfacemeteoricground
cements of micrite, microspar and metres; formation water compositions water is normally well oxygenated
slightly coarser crystal sizes (ca. ranging from brackish to highly saline, (Evamy, 1969), but the distal parts of in-
1-200 m) found in fine-grained sedi- from acidic to strongly alkaline pH termediate and deep carbonate aqui-
ments including chalks. Coniglio (1985) values, and from moderately to strongly fers remote from recharge areas can be
c has recently documented in detail the
sedimentology, petrography and geo-
negative Eh values; water flow rates
that probably range from almost stag-
anoxic (e.g., Grover and Read, 1983).
Cathodoluminescence (Cl) is favour-
chemistry of all these shallow-burial nant to moderately rapid for ground ed by the presence of Mn2 + but inhibited
cements in Cambro-Ordovician slope water (order of less than 10° to 101 by Fe2 + . The ratio of these two cations
and basinal limestones of western rn-yr-i): and time intervals of anywhere seems to be more important than their
o Newfoundland.
Deeper-Burial Cements.
from a few thousand(?) to tens of mil-
lions of years.
absolute concentrations in determining
Cl (Pierson, 1978; Frank et al., 1982;
o In chalks the burial cements are micro- The general characteristics of coarse Grover and Read, 1983;Fairchild, 1983;

o to-nannocrystalline, from around 1to 10


micrometres except in internal cavities
burial cements (Figure 21)are now well
established. The cements are common-
ten Have and Heijnen, 1985). Other
cations such as Pb2+ and Ce2+ may
of some skeletal grains, and so have ly ferroan (more than 500 ppm ferrous serve as activator ions and Ni2+ and
been studied best with the scanning- iron) and enriched in Mn2+ (more than C02+ as inhibitor ions (Machel, 1985),
o electron microscope (e.g., Matter, 1974; 100ppm) but impoverished in Sr2+ com- though they are clearly subordinate to

o Scholle, 1977;Feazelet al., 1985). Chalk


cements have not yet been investigated
pared with associated earlier diage-
netic cements , and have oxygen-iso-
Mn 2+ and Fe2 + and iti s unclearwhether
they affect primarily Cl or photolumin-
o in terms of cement zonation and geo-
chemistry because of their ultra-small
tope compositions depleted in 180 .
Their cathodoluminescence is charac-
escence.
Bladed-prismatic calcite. This
crystal sizes. teristicallydull and mayor may not show cement consists of elongate scaleno-
The principal types of burial cements compositional zonation. Aqueous fluid hedral crystals , generally found grow-
found in shallow-marine/peritidal lime- inclusions (generally containing both ing directly on grain surfaces or atop
stones include: clear coarse calcite gas and liquid phases) and hydrocarbon earlier, marine cements. Crystals are a
(calcspar or coarse equant spar); clear- inclusions are common. few tens of micrometres across and up
to-turbid coarse dolomite or dolospar The significance of iron and manga- to a few hundred micrometres long, and
("saddle" dolomite of Radke and nese in the 2 + valence state is that they have prismatic terminations . Cl is typ-
Mathis , 1980; " baroque" dolomite of require reducing conditions to exist. ically dark with one or more bright lines
o Folk and Aseretto , 1974); the xenotopic
dolomite of Gregg and Sibley (1984);
Although in theory the waters may have
positive Eh values (Carpenter in Frank
(Figure 22). Generally where more than
one burial-cement type occurs, bladed-
and coarse anhydrite. Various lines of et al., 1982), in actuality those deep prismatic calcite is the oldest. In fact,
evidence including aqueous fluid inclu- formation waters for which analyses although bladed and prismatic calcite
sions, oxygen-isotope compositions have been made (e.g., White, 1975;Col- cements have been observed to con-
o and cement zonation demonstrate that lins, 1975; Drever, 1982) have at least tain two-phase fluid inclusions which

o these burial cements can form over a


substantial range of conditions. These
moderately negative Eh. Consequently,
ferroan and manganoan carbonate ce-
suggest precipitation from hot brines
(O'Hearn, 1985),some workers believe
o include temperatures from around ments must precipitate from at least that these cements are "pre-burial" in

o
r:
~
(

Figure 22 Multiple generations of burial calcite cement in a small reef limestone cavity rimmed by Renalcis and early marine cements :
(left) plane light, illustrating bladed prismatic (arrows)and coarse mosaic calcspar.
(right) cathodoluminescence, illustrating black, non-luminescent prismatic crystals (arrows) with brightly luminescent tips and dUll, but zoned,
luminescent coarse mosaic calcspar. Bar scale is 1 mm. Lower Cambrian, Labrador.
c
90 Diagenesis Geoscience Canada Reprint Series 4 c
c
origin and form in the sub-Ienticularmix- 1980; Mattes and Mountjoy, 1980; Cho- cements actually postdate other burial- c
ing zone (e.g., Moore and Druckman, quette and Steinen, 1985; Moore and
Druckman, 1981; Grover and Read,
diagenetic features, such as physical
compaction features, stylolites and
c
1981; James and Klappa, 1983; Grover
and Read, 1983;Saller, 1985;Druckman 1983; James and Klappa, 1983; Druck- microstylolites, and hydrocarbons or c
and Moore, 1985).
Coarse mosaic calcspar. This ce-
man and Moore, 1985; Prezbindowski,
1985). Commonly the dolomite is
their alteration products (Figure 24).
Generally speaking, cements can be
c
ment typically consists of plane-sided, closely associated with burial calcspar safely dated as "late" if they are
equant crystals ranging from tens to
hundreds of micrometres in size, which
cement which it either pre- or post-
dates. Saddle dolomite partly of
involved in one or more of the following
kinds of time-space relationships: c
mayor may not be noticeably ferroan replacement origin has been dis- (1) Cement crystals crosscut stylolites, (
and generally have dull, zoned or covered recently in grainstones of the or microstylolites or pressure-solution
unzoned CL (Figure 22). Jurassic Smackover Formation in the seams end at cement crystals. C
Poikilitic calcite. These crystals Louisiana Gulf Coast (D.H. Mruk, pers. (2) Cements heal fractured grains or
can be several millimetres in size and cornm., 1986).The precipitation of sad- spalled ooid cortices. C
large enough to enclose several deposi-
tional grains, and otherwise have dull
dle dolomite in preference to calcspar
seems to be favoured by the presence
(3) Cement crystals postdate the physi-
calor chemical compaction of grains
C
CL like the coarse mosaic calcspar. of dolomite-crystal substrates, and at (filling "compacted pores"), or enclose C
Coarse dolomite cement. Saddle the relatively high temperatures of the or replace compacted grains.
or baroque dolomite and xenotopic burial diagenetic realm can take place (4)Cement crystals enclose or postdate C
dolomite are other varieties of burial
cement which often areferroan. Saddle
in waters with relatively low Mg2+ICa 2 +
ratios (Rosenberg and Holland, 1964).
. hydrocarbon alteration products such
as asphalt or pyrobitumen.
C
dolomite (Radke and Mathis, 1980) is Coarse anhydrite cement. Large (5) Cements fill tectonic fractures or fill C
typified by curved cleavage traces and crystals of anhydrite, in some instances dissolution pore spaces which them-
crystal faces, a peculiar and distinctive poikilitic forms, can be seen in many selves formed by removal of both grains C
sweeping extinction in cross-polarized buried limestones associated with and early burial cements. ~
light caused by a distorted crystal lat- units of anhydrite, often in carbonate- Conditions of Cement Precipitation.
tice, and often zonation in terms of Fe2+ evaporite cycles (Brinton, 1986). Para- Most burial cements, as outlined earlier, C
and Mn2+ concentrations as well as CL genetically, anhydrite cement may pre- formed over a wide range of conditions.
(Figure 23). Xenotopic dolomite (Gregg date or postdate the burial carbonate Temperature. Burial calcite and
C
and Sibley, 1984) is typically of mosaic cements (Figure 23). Its presence sug- saddle dolomite cements evidently pre- C
style and consists of anhedral crystals gests formation, or conversion from cipitate over a range of temperature
with irregularorcurved boundaries, fine gypsum, at depths of something over from -40°C to 200°C or somewhat C
higher but most commonly between
to coarse crystal sizes (ca. 0.1-1 mm),
and as a rule undulatory extinction.
300 m since above that approximate
depth gypsum is the more stable form of - 50°C and 150°C, and at burial depths
C
From experimental and geochemical calcium sulphate (Murray, 1964). between a few hundred metres and sev- C
considerations it appears to form at tem- Criteria tor Recognition of eral kilometres. Precipitation tempera-
peratures of about 50°C and higher. Burial Cements. tures have been estimated by three C
Late-stage burial dolomite cements
have been reported in limestone and
Although the characteristics just out-
lined are generally reliable indicators of
indirect methods, from (1) the tempera-
tures at which primary two-phase fluid
C
dolomite sequences in many regions deep-burial origin, the surest criteria inclusions homogenize to a single, C
(Choquette, 1971; Radke and Mathis, are those based on determining that vapor phase when heated, (2) stable-
C
C
C
C
(
c
e
c
c
c
Figure 23 Burial cements in a phylloid-algal mold in skeletal grainstone. (left) plane light, illustrating mosaic calcspar (e), saddle dolomite (D)
with inclusion-rich centres, and anhydrite (A) partly replacing a zoned dolomite rhomb. Dark areas in central part of photo are pore spaces. C
(right) cathodoluminescence, illustrating unfilled pore space (black) and outer zones in saddle dolomite cross-cut by non-luminescent anhydrite.
Bar scale is 1 mm. Paradox Formation (Pennsylvanian), southeastern Utah (Brinton, 1986). Photo courtesy of L. Brinton. (

C
C
c
c Limestones - The Burial Diagenetic Environment 91

c
c oxygen isotope compositions, and
t: (3) inferred geothermal gradients (see
EQUANT -MOSAIC CALCSPAR
Figure 2)and burial depths at the time of
(i POST-DATES MICROSTYLOLITES cement precipitation.
( SYNTAXIAL OVERGROWTH Salinity. The solutions from which
burial calc ite and dolomite cements
o precipitate, judging from a large number
of determinations of freezing and initial
(. melting temperatures of fluid inclusions,
are generally brines of varying salin-
ities. Most of these brines seem to be of
Na-Ca-CItype, and the common salinity

o range is about 10 to 100 parts per thou-


sand (seawater = 35 ppt), Some of the
o high salinities reported are from inclu-
sions in cements from sequences asso-
o ciated with evaporites, such as the

o Jurassic Smackover Formation in the


US Gulf Coast (e.g., Klosterman, 1981;
O'Hearn, 1985), where the ambient
CEMENT HEALS pore waters probably reflect dissolution
o SPALLED
0010 of evaporites (Collins , 1975; Carpenter,

o CEMENT
1978; Moore, 1985). Furthermore, not
all cements judged to have formed in
o POST-DATES FRACTURE burial settings have two-phase aqueous
fluid inclusions. Nor does it follow that
c CEMENT HEALS MICRITE ENVELOPE
brines were responsible for al/ burial
cements. Furthermore, Read and his
associates (e.g., Grover and Read,
1983; Dorobek, 1987; Mussman et al.,
1988) have suggested from cathodo-
Figure 24 Criteria for interpreting cements as "late" burial features. luminescence and isotopic evidence
c that shallow-burial cements may be
precipitated from meteoric waters in
regions of especially active recharge
4
c 0
v.
and deep circulation . Despite these
important exceptions, however, the
o III
Q
a.
data acquired thus far point toward

o 0
...
CO)
2 brines as probably the main sources of
burial cements.
Isotopic compositions of cements
l Z
00
and waters. Burial cements typically
o 0
III
0 show a progression, from older to youn-
ger cement generations and also within
o a:
C
0
generations, toward lighter and lighter
stable-isotope compositions: their 013C
( values decline only slightly, whereas
c -12 -10 -8 -6 -4 -2 0 2 their 018 0 compositions decrease
sharply, by as much as 10-15per mil (%0)
OXYGEN, &180pDB'%o (Figure 25). This same progression was
observed by Dickson and his co-
l workers (Dickson and Coleman, 1980;
Figure 25 A graph showing the hypothetical trend of systematic changes in isotopic composi-
C tion which accompany the diagenesis of a marine carbonate sediment (A), first in the meteoric
see also Moore, 1985) in a series of com-
positional zones painstakingly sampled
realm (B), then in possibly a mixing zone with precipitation ofprismatic cement (e), and finally in
within single crystals of burial cement.
three successively deeper domains of the burialrealm with precipitation of coarse calcspar (D.E)
andcoarse saddle dolomite spar(F). Thesequence ofcements from B through E was precipitated Moreover, burial cements are virtually
from progressively hotter waters. This general trend, although hypothetical, has been observed without exception isotopically "lighter"
in carbonates - both limestones anddolomites, with both calcite anddolomite cements - from a (depleted in the heavier isotopes of C
great many areas and stratigraphic units. It may well be the " normal " trend of cement and 0) than earlier marine and meteoric
stratigraphies in the deep-burial domain. cements as well as marine depositional
constituents in the same carbonates.

r
'-
c
92 Diagenesis Geoscience Canada Reprint Series 4 c
c
These relationships have been ob- cement from an imported aqueous been identified? To discern them in c
served in a large number of studies both solution with reasonable CaC0 3 con-
tent, something on the order of 10,000
more finely crystalline cements would
require very critical observations and
c
for calcite-dominated cement systems
(e.g., Tanand Hudson, 1974; Walls etal., to 100,000 unit volumes of solution is some measure of luck. Buxton and Sib- c
1979;Meyers and Lohmann, 1980; Prez-
bindowski, 1985; Moore, 1985; Brinton,
required. Is water flux likely to be large
enough to meet these needs? In rela-
ley (1981) argued that flow rates in lime-
stone aquifers are too high to favour the
c
1986),and for systems of multiple dolo- tively shallow aquifers with flow rates of transport of ions released by pressure- c
mite cements in early-diagenetic dolo-
mite and limestone (e.g., Choquette,
- 5-20metres per year such as the south
Florida Tertiary aquifer (Back and Han-
solution solely by diffusion along solu-
tion films to nearby precipitation sites. c:
1971; Fritz and Jackson, 1972; Mattes
and Mountjoy, 1980; Choquette and
shaw, 1971) and the Madison Limestone
aquifer of Wyoming, Montana and the
Wherever solution films are connected
to water-filled pore systems in which
c
Steinen, 1980; Brinton, 1986). However, Dakotas (Hanshaw et al., 1978),cemen- flow is significant, the films should dis- c
Halley has cautioned that some burial
cements may have relatively heavy
tation appears to be an active present-
day process. But in strata that are bur-
charge their load of ions into the flow
system. c
018 0 values and go unrecognized sim-
ply because we expect strongly nega-
ied at depths of several kilometres such
as the Smackover in much of the US
Factors that promote burial ce-
mentation. It is generally accepted
c
tive values; for example, reservoir water Gulf Coast, and are unconnected with that supersaturation with respect to c
in the Sunniland Field, south Florida has
018 0 of + 10%0 and at present reservoir
active aquifers, formation water flow
rates are likely to be very small. In the
both calcite and dolomite prevails in
most subsurface pore waters. Excep- c
temperature would make calcite cement opinion of some workers (e.g., Wood and tions are the shallow "upstream" (up- c
with only -2 to -3%0. Land and Prezbin-
dowski (1981) report values of + 12 to
Hewett, 1984) no formation waters are
likely to be completely static even if over-
gradient) parts of aquifers that are being
actively recharged, like the Mississip- c
+ 29%0 for waters from deeply buried
Cretaceous carbonates of south Texas
pressured, and some circulation with
flow rates of at least 1 metre per year
pian Madison Formation in the northern
c
(R.B. Halley, pers. comm., 1986). must take place by convection alone. c
The progressive decreases in oxy-
gen-isotope composition primarily
Autocementation. An increasing-
ly convincing body of evidence points c
reflect increasing temperatures of the
precipitating waters. These can be esti-
toward the view that in partly closed
systems pressure-solution may be the
c
mated by using assumed or determined main agent for cementation in lime- c
values for the oxygen-isotopic composi-
tions of the waters. Graphic charts of
stones undergoing burial diagenesis
(Hudson, 1975, 1977; Scholle and Hai- c
the sort published by Prezbindowski
(1985) for calcite-water systems based
ley, 1985). Most studies that have
attempted to find cause-effect relation-
c
on equilibrium relationships worked out ships between stylolites and burial c
by O'Neil et al. (1969), and by Land
(1985) for dolomite-water systems can
cements, however, have not clearly
established such relationships. A few c
be consulted for this purpose. Using the
chart by Prezbindowski (1985) one can
authors have noticed that stylolites
commonly occur in intervals of anoma-
c
get a sense of the temperature ranges lously low porosity (Harms and Cho- C
involved in individual suites of burial quette, 1965;Dunnington, 1967;Nelson,
cements. For example, cements with 1981), but have not established that the E
018 0 values8%0 apart wouldhaveprecipi-
tated at temperatures about 70°C apart,
cement occluding the porosity was
genetically related to the stylolites. The
C
assuming a water of constant isotopic only investigation known to us which C
composition. Since progressivelyyoung- demonstrated a direct link unequiv-
er burial cements commonly have preci- ocally was by Wong and Oldershaw
C
pitated from progressively more saline (1981). Those authors showed not only a (
and presumably more 180-enriched
waters, temperature ranges like the
spatial relationship between stylolites
and intervals of low porosity (Figure 26), c
one just cited must be minimum values.
Origin of Burial Cements.
but a time relationship as well, in which
cement zones were found to be genet- Figure 26 A core-slab surface illustrating
e
Passive cementation. As in any ically related to stages in stylolite growth the common association of anomalously low (
«
other carbonate-water system, CaC0 3
dissolved in one place can be trans-
(Figure 27). The cements are very
coarse and the zones, revealed by stain-
porosity 6%) with stylolites. Porosities
above and below the thin stylolite-related
interval are 15-20%. The arrows indicate
c
ported over large distances before con- ing with KFeCN SOlution, are so spec- l
positions of pores that were used to define
ditions are right for precipitation. It has tacular that they can be seen with the the boundaries of the "tight" horizon.
been shown (e.g., Pray, 1966; Dun- unaided eye. Devonian Kaybob reef, Swan Hills Forma- l
ham, 1969; Bathurst, 1971, p. 440-441; Is it possible that similar time-space
Scholle and Halley, 1985)that in order relationships exist in other stylolitic and
tion, Alberta (Wong and Oldershaw, 1981).
Photo courtesy of P.K. Wong, published by C
to precipitate one volume unit of calcite once-porous limestones but have not permission.
l
C
C
c
c Limestones - The Burial Diagenetic Environment 93

c
c: US Rocky Mountain and high plains cements in situations where fracturing in the subsurface is strongly suggested
( region (Hanshaw et al., 1978) and the and fault ing sharply alter the hydrology by the fact that dilation fractures and
confined Biscayne aquifer(Cenozoic) of and pore-fluid pressure of a sequence breccias in carbonate rocks, whetherof
o south Florida (Kohout, 1970; Back and or basin is CO2 outgassing. Hanshaw at tectonic or other origins, commonly are

c Hanshaw, 1971);there, undersaturation


and dissolution are common. The gen-
al. (1978)suggested this mechanism as
a means of precipitating carbonates
filled by coarse calcite or dolomite
cement for which oxygen-isotope com-
c eral condition, however, is one of super-
saturation. It is likely to be achieved
from meteoric ground water subjected positions indicate precipitation from hot

c primarily by dissolution of CaC0 3


to reduced pressure at the Earth's sur-
face. The same process may operate in
format ion waters; furthermore, these
fracture-filling cements often have the

c increasing the activities of Ca2 + and


CO~ - in ambient pore waters. Super-
special situations in the deep subsur-
face. There, where pore-fluid pressures
same isotopic composition as cements
in the "wall rock" around them (e.g.,
( saturation is likely to be maintained as are likely to be one to two orders of Murata et al., 1969; Choquette, 1971).
long as significant precip itation of car- magnitude larger than any in the near- Baroque dolomite fillings are common
c bonate cement or significant dilution of surface meteoric, PC0 2 also is likely to and well known in breccias, fractures

o system pore waters by meteoric water


do not occur.
be much higher. Any fault or fracture
system that suddenly, in terms of geo-
and "zebra structures" found in Missis-
sippi Valley-type sulphide-ore gangues
o Increasing temperature should also logic time, connects the aqueous pore- and in numerous epigenetic dolomite

o work to enable the precipitation of cal-


cite , which is retrograde (Helgeson,
fluid column in the deep-burial domain
with that in the shallower subsurface
reservoirs of petroleum, Perhaps CO2
outgass ing through fracture systems

o 1969). Although increasing pressure


partially counters the effects of temper-
will abruptly reduce the pore-fluid pres-
sure of the system connected with the
was instrumental in their origin.
Factors that inhibit cementation.
o ature , experimental work by Sippel and opened fractures, dropping the PC0 2 The most clearly identifiable of these

o Glover (1964) and Sharp and Kennedy


(1965) indicates that over the tempera-
and causing carbonates to precipitate
both in the fractures and in the adjoin ing
(Table 3) have been outlined earlier and
are discussedby Feazeland Schatzinger
o ture range from about 25°C to 200°C
the solubility of calcite in water de-
water-filled pore systems,
Rates of outgassing are highly tem-
(1985). Entryof hydrocarbonsisoneofthe
more important inhibiting factorsand has
creases by about two orders of mag- perature dependent; a warm bottle of been documentedin manylimestones, as

o nitude. As much as half ofthis decrease


may be counteracted by increasing
carbonated beverage, for example,
loses its CO2 much more quickly than a
illustrated in Figure 28.

( pressure, but the change may be signifi- cold one. The mechan ism is operative Dissolution in Burial Diagenesis
cant nevertheless. where travertine deposits form at the The discovery of solution porosity in
Another mechanism that may pro- surface vents of hot springs in carbon- sandstones, attributed by some to CO2

o mote the precipitation of carbonate ate terranes. That it may indeed operate and/or H2S generated during burial dia-
genesis (Schmidt and MacDonald,1979;
o Hayes, 1979), led shortly to a successful
search for solution porosity of likely
deep-burial origin in limestones. Pore

o ' POROUS'
space believed to be of this origin
was reported by Moore and Druckman
o HORIZON
(1981; also Druckman and Moore,

o 1985; Moore, 1985) in deeply buried


(> 2-3 km) oolitic and pisolitic lime-

o 'POROUS'
HORIZON TIGH T
stones of the Upper Jurassic Smack-
over Formation in the US Gulf Coast.
o HORIZON
Around that time, solution porosity of
burial-diagenetic origin was reported
and carefully documented by Elliott
o 'POROUS'
HORIZON
(1982) in limestones of the Mississip-
pian Mission Canyon Formation in the
Williston Basin.
The solution pores may be fabric
L selective or not (Choquette and Pray,
(, 1970) and include molds, vugs, and
(
solution-enlarged interparticle voids.
Fabric-selective pores may be relatedto
A c D
previous diagenetic history. A suite of
Figure 27 Diagrams showing the development of a stylolite andthe concurrentprecipitation metastable carbonate sediments which
r Is -altered and lithified in the meteoric
'-, of coarse, zoned cements with CaC03 produced by pressure solution. In its later stages, the
r·· stylolite grew at the expense of some of the earlier cement. Fe-rich cement is black, Fe-poor environment may be entirely calcite, but
1.... cement is white, and pore spar:e is stippled. Devonian Kaybob reef, Swan Hills Formation, not all its components are the same.
Alberta (Wong and Oldershaw, 1981). Diagram courtesy of P. K. Wong, published by permission. Calcite cement is a pure precipitate;

(
C
c
94 Diagenesis Geoscience Canada Reprint Series 4 c
c
calcitized aragonite and Mg-calcite The burial origin of microporosity is of pre-compaction cements; (3) close
c
allochems are precipitated calcite with
minor embedded organic and mineral
often difficult to tie down, but a number
of criteria suggested for occurrences
association of microporosity with sty-
lolites and microstylolites; (4) earlier or
c
relics and high trace element content; in the Jurassic Haynesville Formation closely associated burial cements, in c
original calcite fossils are biogenic cal-
cite containing organic templates . Inthe
of east Texas (Dravis, 1987) are more
widely applicable. These criteria in-
some cases containing hydrocarbons;
and (5) identical microporosity in biotic
c
new burial environment, because of dif-
ferences in crystal size and composi-
clude: (1) lack of early, meteoric pore
space or cements; (2) evidence of per-
materials such as oyster shells made up
of ordinarily stable low-Mg calcite .
c
tion , microporosity, and amount and vasive pressure-solution and absence Microporosity of deep-burial origin is C
kinds of original organic matter, the
relative solubilities of these compo-
c
nents will be subtly different: biogenic C
calcite > calcitized aragonite or Mg-
calcite > calcite cement. Fabric- C
selective dissolution of biogenic calcite
allochems and possibly of calcitized
C
allochems may subsequently take C
place during burial (Donath et al., 1980;
James and Klappa, 1983). This is also C
manifested by silicification of biogenic
calcite and Mg-calcite allochems
C
(bryozoans , brachiopods, echino- C
derms) in the subsurface, while original
aragonite allochems (molluscs, sclerae-
C
tinian corals) are preserved as calcite. G
Non-fabric-selective voids may begin
as interparticle pores or molds and C
quickly enlarge. Features that point
toward a burial-diagenetic origin of
C
these pore spaces are illustrated in Fig- C
ure 24, and examples of these types of
voids are shown in Figure 29 and 30. c:
Pores commonly cross-cut both car-
bonate grains and cements, in situa-
C
tions where the cements are clearly of C
post-compaction, burial origin. In other
cases, solution pores occur along and C
locally cut across stylolites, which they
therefore postdate (Figure 30).
C
Some micro porosity (Choquette and C
Pray, 1970), typified by apparent pore
..diameters" that are generally less than E
0.03 mm and as a class of multiple ori-
gins, almost certainly forms in burial-
C
diagenetic settings. Much chalk that C
has never "seen" pore waters other
than marine has micropore systems
C
(mainly intercrystal and primary inter- C
and intraparticle) which probably are
the result of incomplete pressure-solu- c
tion compaction and associated ce-
mentation that were arrested sometime
e
early in the burial process (Moshier, N~w"C;;'
,"~ " (
POROSITY: MEASURED 0.3\>, PREDICTED, 22\>
1987). Other microporosity includes
both primary types and solution-en- c
hanced micropores which seem to have
originated or been enhanced late
Figure 28 Scanning-electron micrographs of chalk from a well in the Ekofisk area of the North c
Sea, illustrating the retarding effects of hydrocarbons on burial cementation. Samples A,S are
enough in the burial process to have from high in, C,D from the middle of, and E,F from below the hydrocarbon zone. Pore·fluid
postdated, entirely or in part , the
development of stylolites and fitted-
pressures are believed to be approximately equal in the three intervals. Cementation by calcite
was extensive in the lowest, water-saturated zone, but was slight in the two zones above,
c
fabric microstylolites (Dravis, 1986, suggesting that it was impeded by hydrocarbons. From Feazel et al. (1985b). Photo courtesy of (
1987; Moshier, 1987). C.l Feazel, published by permission.
C
C
c
( Limestones - The Burial Diagenetic Environment 95
('
C' especially interesting in petroleum geol- were supplied by the thermal decar- into the Wilcox sandstones from com-
( ogy because its presencehas made eco- boxylation of organic matter(kerogen). pacting shales downdip. A third mecha-
nomic reservoirs of gas out of some car- According to Lundegard (1985), how- nism, the production of strongly acidic
bonates that have low porosities and ever, a more likely source of CO2 to
c permeabilities and might otherwise be account for dissolution of carbonate
waters by sulphate reduction (in reac-
tion with methane, for example) to pro-
c "tight", such as some extensively com-
pacted and/or cemented oolitic lime-
cement in sandstones of the Wilcox
Formation (Tertiary) of the Texas Gulf
duce CO2 and H2S, seems possible in

c stones in the US Gulf Coast Jurassic.


Solution porosity of burial-diagenetic
Coast is a series of hydrous pyrolysis
reactions between organic carbon and
format ion waters reducing enough to
produce cements, and may have found
c or ig in has been ascribed by most oxygen in water to yield CO2 or organic support in the discovery of abundant

c workers to formation waters with anom-


alously high concentrations of CO2 that
acids . These reactions would have
occurred in connate waters expelled
iron sulphides in some Smackover lime-
stones (L.M. Walter, oral comm., 1985).
o
o
o
o
o
o
o
o
o
o
o Figure 29 Solution porosity interpreted as burial diagenetic in origin (Elliott, 1982).
(left) Solution vug that cross-cuts both grains and dolomite-lined microstylolites. Most grains are flattened pisolites.
(right) Smallvug formedby dissolution of micrite matrix in apisolitepackstone. Calcite crystals interpreted as warm -waterprecipitatespartlyline the

o vug. Bar scales are 1 mm. Miss issipp ian Mission Canyon Formation, Williston Basin, North Dakota . Photos courtesy of T.L. Elliott, published by
permission.
o
o
o
o
o Table 3 Factors that influence cementation in the deep-burial environment.
Based in part on Feazel and Schatzinger (1985).

o Inhibiting Enabling
o •

Stable CaC0 3 mineralogy
Dilute pore waters
• Metastable CaC0 3 mineralogy

C • Hydrocarbons displace pore waters


• Pressure solution
• Low-flux hydrology • High-flux hydrology
l • Increase in Pco, • Highly oversaturated pore waters
(higher pore pressure) (if high flux)

c • Decrease in temperature
• Reduced porosity and permeability
• Increase in temperature
• Decrease in Pco,

Figure 30 Solution pores (P) and calcspar


, (C) interpreted as burialdiagenetic, formed by
dissolution along a stylolite. Bar scale is
'-.,'
1 mm . Mississippian Mission Canyon For-
,.---
'-..
mation , Williston Basin, North Dakota
(Elliott, 1982). Photo courtesy of T.L. Elliott,
1".... published by permission.

L
c
96 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
Recently the suggestion has been
made that meteoric-water systems,
published to date, and shows a number
of importantfeatures. The DSDP curve ,
down toabout 1.1 km sub-bottom, and on
chalks in a North Sea well from about 1.6 c
perhaps aided by mixing-corrosion
(see James and Choquette, this vol-
when comb ined with data for North Sea
chalks (1 well, Scholle, 1977), has an
to 2.5 km sub-bottom. Building on inter-
pretations by Schlanger and Douglas c
ume) have more potential on mass-bal-
ance considerations for producing sig-
exponential shape: rates of porosity
reduction are highest at shallow depths
(1974), the chalk curve has been extrap-
olated to about 6 km; there it probably
c
nificant volumes of dissolution porosity and decrease exponentially with burial converges with a somewhat differently
in the deep subsurface (Giles and Mar- depth. The same is true for South Flor- drawn curve for the South Florida lime- (
shall, 1986). It is clear that in active ida basin limestones, even though they stones. Most Phanerozoic limestones
aquifers meteoric water can penetrate appear to be much more var ied Iitho- buried to comparable depths lose all but C
to great depths (2000 m in the Great logicallythan the chalks and likely spent about 5% or less of their porosity
Artesian Basin of Australia, Haberheh, part oftheir burial history in the meteoric (Schlanger and Douglas, 1974; Scholle C
1980) and can travel long distances (up
to 120 km off the east coast of Florida,
environment. The exponential aspect
was what led Pray (1960) and Schmoker
and Halley, 1985). Limestones with that
little porosity generally have so little
C
Manheim, 1967). But the saturation and Halley (1983), respectively, to sug- permeability ( < 0.05 md is typical) that C
states of meteoric water in such distal gestthe concept of a porosity " half-life" further throughput or expulsion of pore
settings are little known, and the or "half-depth". waters is unlikely and compaction and C
amount of dissolved CO 2 carried by
them is likely to be small unless aug-
There is a general porosity versus
depth relationship for oceanic chalks in
cementation should be arrested.
This general curve for chalks in a
C
mented by CO 2 from decarboxylation, marine pore-water systems. The right- marine pore-water system also traces, C
sulphate reduction, hydrous pyrolysis
reactions, orother reactions. The mech-
hand curve in Figure 32 is based on
porosity data from a dozen DSDP sites
albeit in very generalized form , the pro-
gressive lithification of pelagic, nanno- c:
anisms involved in producing large vol-
umes of deep-burial dissolution poros-
C
ity - and indeed the very existence of (;
POROSITY, %
large volumes - remain elusive.
Whatever the mechanism(s) may be,
o 40 80
O,.......---r--.---rr--.~:7r~;rr--r:::;;oo--,
C
there is little doubt that (1) solution NORFOLK
CHA LK, U.K .
.'
C
porosity can be generated in the deep
subsurface and may in places be signifi- NIOBRARA L~l
U.S. GR. PLAIN
C
cant, and (2) organic compounds, possi-
bly including liquid hydrocarbons and!
AUSTIN
CHALK, .:
.... C
or organic acids, are implicated. It is U.S . GUll;"
5
C
unclear as yet whether solution porosity
of this origin is to be found generally in C
limestones and sandstones situated
C
--
.: NORTH SEA IL1611l
updip in the flow paths of connate
E
1,.,-..,. NORMAL CURVE
waters being expelled from compacting ~

o
C
shales, and the prediction of such late
porosity is a difficult challenge.
J:
~
3 11l
10 (:)
C
Changes in Porosity with Depth.
0-
W
o
7\:';::;';::''"u"" , N '" o
o E
The sum of all these processes and
products should be reflected in changes
[
SHALLOW - M A RI NE LS. S FLA. ]
AVG & DATA ENVELOPE
C
in porosity with depth.
General trends. Most reliable infor-
C
mation comes from Cretaceous and Ter-
tiary chalks in oceanic settings as a
15 C
result of the Deep-Sea Drilling Project
POROSITY-DEPTH CURVES
C
(DSDP), synthesized by Garrison
(1981).Data for chalks in the North Sea,
CHALKS c
adjoining areas in Great Britain, and the e
US High Plains and Gulf Coast has been
developed or synthesized by Scholle
6 c.
(1974, 1977), Lockridge and Scholle
c
(1978), Scholle and Halley (1985). All of
the porosity-depth information for the
South Florida basin comes from studies
Figure 31 A plot of percentporosity versus depth for various limestone sequences. All but the
deepest curve (to 6 km) are for Cretaceous and Tertiary chalks. (From Scholle, 1977; Lockridge
c
andSCholle, 1978; SchlangerandDouglas, 1974). Chalk curves other than for DSDP carbonates
by Schmoker and Halley (1983) and and chalks from the SCotian Shelf and North Sea well L 16/1 probably reflect some diagenesis in
Schmoker (1985). the meteoric . Thedeep curve is forshaJlow-marine andperitidal limestones from the south Florida (
Figure 31 gives most of the porosity shelf; the shaded band indicates the spread of data for this curve. (After Schmoker and Halley,
versus depth curves that have been 1982). C
C
C
('
c Limestones - The Burial Diagenetic Environment 97

c
foss il-foraminiferal ooze (unconsoli- If we add average values of initial (Figure 31; Halley and Schmoker, 1982;
c dated) through chalk (poorly consoli-
dated) into Iith ified limestone . Most
porosity for modern shallow-marine car-
bonate sediments (Table 4) at the zero-
Schmoker and Halley, 1983).
From published information about the
C deep-sea oo zes, and also sh allow-
marine lime muds (Ginsburg , 1957),
depth level in Figure 32, we can define
an envelope which should allow us to
stratigrap hic age relationships of the
oceanic chalks (Schlanger and Douglas,
CJ lose some poros ity in the fi rst metre or predict in very appro ximate fashion the 1974) and the south Florida shallow-
so of burial. Afte r this initial reduction porosity -depth characte ristics of vir- marine limestones(Schmoker and Halley,
C' from 80% to 75% , physical compaction tually any CaC0 3 sedimen t buried in a 1983) one can get a crude picture of the
C remains dominant down to around 200- marine pore -water system. This envel- rates at which porosity is reduced in
250 m, where porosities are reduced to ope, which assumes convergence at th ese Cretaceous to Pleistocene sedi-
60% and ooze changes into chalk. From around 5% porosity or less, is in acco rd ments . For chalk (Schlanger and Doug-
r: 200-250 m to around 1000 m chemica l with data from compaction experiments las, 1974), reduct ion from 80 % to 75%
compaction becomes more and more that show rates of porosity reduction poros ity in the top metre or so is accom-
(' dominant as the smaller nann ofossil (compacti on) to be lowest for clean car- plished in around 50 ,000 years; reduc-

o remains dissolve under load and low-Mg


calcite micrite cement precipitates, ini-
bonate sand (grainstones) and highest
for mudstones.
tion from 75% to 60 % by physical com-
paction to depths of 200-250 m takes on
o tially cementing grains at the ir contac ts.
From around a kilometre downward,
It is interesti ng that the south Florida
curve falls within thi s envelope. The
the order of 10 m.y.; and reduction from
60 % to 40% at around 1000 m depth
o pressure-solution and " autocemen- similarit y in trends can be interpreted in takes as long as 120 m.y. For south
tation" clearly must continue to domi- more tha n one way, particular ly since Flo rida lim estones the age relat ion-
nate, until diminishing pe rmeab ilities the data for south Florida limestones ships are less well constrained but point
c end pore-water circulation. show a considerable amount of scatte r to roughly comparable or slower rates of

c POROSITY, %
40 80
POROSITY'"

OOZE - 1- 2 5 0 m
'PH YS. CO MPAC TI O N 00 "1.
' SOM E PO- CEMENTATION
'75 -60 % POR OSITY

CH A LK 250 -1000 m
' C HEM. CO MPACTIO N &
PO CE M ENTATIO N OO M.
, 60 - 40 % PO RO SITY
E
o .x.

o J:
~
a...
3 LI M ESTONE - 1- 6+ krn
' CHEM . CO MPA CTI O N & DISSO LUTION
w
G o
PO C EME NTATION
, 4 0 -5 % OR LESS POR O SITY

. NORMA L' BURIA L CURVE

o OOZE-TO-CHALK-TO -
HYPOTHETICAL
D LIMESTONE CURVE
POROSITY vs DEPTH POROSITY-DEPTH
l MARINE PORE WATERS CURVES
r

6 LL.........L._--L-_.........._ : L - _ L . - . . . - - L _..........- - - - '


(

Figure 32 Generalized porosity versus depth curves . The chalk curve Is Figure 33 Hypothetical cur ves of porosity versus depth for
for DSDP cores of unllthlfied nannofossil-foraminiferal ooze, partly Iithitied five known situa tions:
ch alk, and indurated limestone and rep resents a general lithificatio n 1. " normal" burial of fine-gralned sediments in marine pore
sequence for lime-mud sediments saturated only with marine-derived po re waters;
,,' waters. The lithification stages are from Schlanger and Douglas (1974). The 2. cementation In the meteono (horizontal segments) alternat-
'-....'
south Florida curve is from Schmo ker and Halley (1982). The grainstone ing with burial In marine pore waters;
curve is hypothetical and is extrapolated from an average value at " zero 3. reversalo fnormaltrend by dissolution Inthedeep subsurface
depth " for modern sediments (Enos and Sawats ky, 198 1). fo/lowed by resumption of normal burial;
'-.. 4. poros ity reduction arrested by build-up of abnorma/ly high
pore-fluid press ures.

'-..
r
c('
98 Diagenesis Geoscience Canada Reprint Series 4

c
porosity decrease with depth; the first c
porosity "half-life" (50%-25%) or "half-
depth" would be approximately 50 m.y.
Table 4 General porosity ranges of common textural types of modern
carbonate sediments. Compiled from Enos and Sawatsky c
(1.5 km) and the second and third (25%- (1981), Schlanger and Douglas (1974), and GRAPE porosity
profiles by Harms and Choquette (1965) and by Pray and
c
6%) would be around 150 m.y. (4-6 km).
Rates of porosity reduction appear to
Choquette (unpublished). c
be substantially greater in limestone
sequences that now reside or in the past
Chalks
Lime muds (mudstone texture)
70-80%
60-70%
c
resided in the meteoric realm, as Muddy lime sands (wackestone and packstone) 50-60% (
pointed out by others (e.g., Bathurst,
1985). Unfortunately, there is very little
Clean lime sands (grainstone) 40-50% c
information about porosity variations c
over depth intervals of more than a few
tens or hundreds of metres through c
meteoric zones. The porosity-depth
curves in Figure 33, which are qualita-
c
c
I
tive, portray the shapes one might
expect for different burial-d iagenetic
histories: (1) a "normal" curve of the
PV o
50% to
c
kind shown in Figure 32; (2) a curve for
chalk or lime mud that was subjected
to 80%
38% PV o 35% l c
19% PV o
c
(
j
very early on to meteoric-zone or con- 60%
43%
ceivably marine cementation by im-
ported CaC0 3 ; (3) a curve of the sort 40% 57% c
expected if solution porosity were cre- ~
ated after burial to considerable depth; CASE 1. PHYSICAL COMPACTION ONLY.
and (4) a curve caused by early build-up
75% PV o
c
of high pore-fluid pressure. It seems
possible that the south Florida data,
50% PV o
c
given its rather wide scatter, could 40% c
include thin meteoric zone profiles.
Volumetric considerations. At 80%
60%
c
this point it may be helpful to summarize
the principal ways, and some of their
c
implications, that initially high pore vol- c
umes may be reduced. The simple dia-
grams in Figure 34 illustrate these
20% 20% 20 % 20 %
c
points. Initial porespacecan bereduced,
in principle at least, entirely by physical
CASE 2. CEMENTATION ONLY. ALL CEMENT IMPORTED.
OPEN SYSTEM.
c
compaction (case 1), entirely by precipi- C
tated cement (case 2), or by combina-
tions of compaction and cementation as E
suggested in case 3. It is important to
distinguish between changes in pore 50 % 10
C
volume and changes in porosity, which 80% 38% PV" 35% 10 C
isthe percent of bulk volumeoccupied by
pore volume. Porosity is the property 60%
16% PV "
C
40 %
that is measured whether using wireline
logs, standard core-analysis methods,
l
20%
the GRAPE porosity-profiling device (:
(Harmsand Choquette, 1965), orvarious
other means.
CASE 3. PHYSICAL AND CHEMICAL COMPACTION.
ALL CEMENT INTERNAL, FROM PRESSURE SOLUTION.
i:
In case 1 the original thickness (to) is PARTLY CLOSED SYSTEM, WATERS EXPORTED ONLY. (
reduced to 35% and the original pore
volume (PV0) to 16%, but the measured c
porosity is reduced from 80% to 40%. (' -
The distinctions here are important for
what they imply about the real pore Figure 34 Diagrams showing the changes in pore volume , percentporosity, and thickness for \... ..
space now available for filling by
cement, in th is example only 16 percent
three hypothetical cases of compaction and/or cementation. For purposes of these diagrams, all
solid constituents are shown by the shaded/stipple pattern, the cement portion of the solid
(
fraction is indicated by the hachured pattern, and pore space is white .
C
(
C
c
c Limestones - The Burial Diagenetic Environment 99

c
of the original pore space. A quite dif- pressure-solution work to reduce initial Burial-Diagenetic Models
ferent picture emerges from this way of porosity, is probably closerto reality than In spite of obvious deficiencies in our
look ing at volume changes than that im- the two preceding, extreme situations . data and understanding, it is neverthe-
or plied in the idea of a " porosity half-life"
suggested by Pray (1960) and later re-
The first three stages shown there pro-
bably model closely what happens in
less important to try and summarize
what we know or can surmise about
worded to "porosity half-depth " by chalks and other fine-grained ocean- burial diagenesis. For this purpose it is
c Scholle and Halley (1985), for those con-
cepts are based on measured porosities
basin sediments that undergo marine-
only burial diagenesis (Schlanger and
useful to envision two general end-
memberdomains(Figure 1and Table 5):
( - the only measures of pore-space vol- Douglas, 1974; Garrison, 1981), as dis- (1) a basinal burial domain involving rel-
r ume that are normalized and so can be cussed in the next section. The fourth atively deep-marine sediments which
compared between different data sets. stage, with 5% porosity, is assumed are being buried in undiluted, marine
c Case 1, based as it is on the work of
Shinn and Robbin (1983), should be
from extrapolated porosity versus
depth curves shown in Figures 31 and
pore waters ; and (2) a shelf/platform
burial domain involving shallow-marine
o considered to apply to fine-grained 32. Cement, which at the end stage and peritidal/coastal sediments which
C) sediments that are subjected to in-
creasing load while saturated with
occupies about half of the "rock vol-
ume", is internally generated by pres-
are being buried in varied pore waters
ranging from meteor ic to marine to
o marine pore waters only. It seems likely sure-solution ; the sediment is both occasionally evaporitic, in response to
episodes of emergence and exposure
o that if the same sediments had been
saturated with meteoric water when
donor and receptor, and in the sense
that pore waters are expelled both from that interrupt their ongoing subsidence

o subjected to such extreme stress , some


cementation would have occurred.
the sediment and through it from under-
lying sediments, the system is partly
and burial. Burial loading may be more
or less uninterrupted , as in the deeper
o The other extreme example is shown closed with respect to ambient pore marine parts of many sedimentary
basins (1 above), or repeatedly inter-
c in case 2 of Figure 34. Here the same
initial pore volume is assumed, but it
water.
Another way of analyzing the effects rupted as appears to be the case in
o is reduced entirely by precipitated
cement unaccompanied by compac -
of early meteoric cementation, pres-
sure-solution, and compaction on the
many shallow-marine carbonate shelfl
platform provinces bordering basins (2
o tion, with no significant change in thick - evolution of porosity with depth has
been developed in an extensive thin-
above); or initially uninterrupted as a
sequence is progressively buried, then
o ness. As in case 1, the measured poros-
ity at one stage in pore-volume reduc- section point-count analysis of oolitic arrested or reversed by basin-margin or
o tion is 40 percent. In this case also, a
true "porosity half-life" is represented,
grainstones in the Smackover Forma-
tion of the US Gulf Coast (Grabowski et
intrabasin uplift.
Although the general course of burial
because the real reduction in pore vol- al., 1987). The total intergranular pore diagenesis seems generally similar in

o ume is exactly the same as the reduc-


tion in measured porosity. The impor-
volume (IGV) of these rocks, that is,
open plus cement-occluded intergranu-
many respects, there are important dif-
ferences between the two domains
o tant difference is that the real pore
volume filled and remaining to be filled
lar volume, appears to become "set"
partway through the bur ial process.
which we attempt to summarize in the
discussion that follows (Table 5).
c by cement is far greater here than in Grainstones with porosity inversion and Basinal Burial Domain.

o
(
case 1.
Furthermore, in case 2 all of the
freshwater cements, analyzed from well
depths of 600 to 2800 rn, have IGV =
General characteristics. Sedi-
ments that accumulate in basinal en-
cement required is assumed to have 40% (equal to the assumed average vironments, apart from sand-sized and
been imported from cement donors initial porosity); grainstones with minor coarser allochthonous debr is flows,
o somewhere else; none is supplied by marine and freshwater cements from are dominantly fine-grained. They carry

o the sediment or receptor itself. Case 2


may be a fair representation of those
1800 to 5000 m have IGV = 30% ; and
more extensively compacted grain-
marine pore waters into the subsurface,
which are modified only by reactions
C) shallow-marine, peritidal (e.g., beach- stones without early cements from 1800 between pore fluids and the organic and
rock) and perhaps eolian carbonate to 7300 m have IGV = 20%. During the inorganic constituents of the sedi-
o sediments that "set up" and/or become compaction process , grain inter- ments. Meteoric ground water may im-
o
r ,
partly cemented at the sediment-water
or sediment-air/water interface, then
penetration stopped before 1800 m but
pressure-solution continued to the
pinge on sediments of the outer shelf. or
on sediments short distances down-
during meteoric diagenesis acquire maximum depth of the core samples , slope from exposed shelf/platform and
r, cement quickly enough to withstand a 7300 m. In each of the three diagenetic ramp margins, but should not interact
..... significant (though not predictable) groups of grainstones, reduction of with basinal sediments even during low
amount of load stress and compaction . porosity was by cementation, and while sea-level stands. The diagenet ic sys-
Cementation may be mineral-controlled the porosity decreased exponentially tem is partly closed hydrochemically, in
or water-controlled as discussed earlier with depth, the total of occluded and the sense that pore waters are being
in this series (James and Choquette, unfilled pore space remains essentially expelled only upward and toward the
1984). The sediment is, however, en- constant, indicating that porosity reduc- basin margins (Bonham, 1980) during
tirely a receptor of cement. tion by compaction alone is in these the phases of majo r thickness and
Case 3, in which both physical com- rocks essentially " frozen" at relatively porosity reduction. There should be no
paction and cementation produced by shallow burial depths. significant transport in countercurrent
c
100 Diagenesis Geoscience Canada Reprint Series 4

c
directions, unless by hydrologic con- Cementation will start somewhere The cathodoluminescence of ce-
c
vection (Wood and Hewett, 1984). below 200-250 metres and become ments produced in sub-basin burial dia- c
Sedimentation and burial rates are
slow,in the range of 2-15 metres per m.y.
dominant below 1000 metres, will be
directly due to pressure-solution (auto-
genesis is speculative. Early-burial
displacive fibrous calcite may be dully c
Build-up of abnormal pore-fluid pres-
sure may occur nevertheless, for exam-
cementation), and should be volu-
metrically proportional to the amount of
to rather brightly luminescent (Coniglio,
1985) . Later burial calcite micro-
c
ple beneath hardgrounds or zones of pressure-solution unless flow rates of cements should have dull CL with little C
\_-
intense stylolite development or physi-
cal compaction or beneath zones of
expelled pore fluids are high enough to
move solute ions quickly away from
or no zonation, reflecting the general
monotony of basinal pore-water sys- c:
abundant carbonate concretions and
layers. Geothermal gradients should be
sites of pressure-solution. Because
Mg2+ concentrations and Mg/Ca ratios
tems. Some burial dolomite may form,
especially if the sediments are argilla-
C
low, in the range of -15-20°C ' km-1• are relat ively high in marine pore ceous, and should be ferroan, with dull, C
Nature of sediments entering the waters, stylolites may begin to form possibly zoned CL.
burial realm. Most of these will be at greater depths than they would in Shelf/Platform Burial Domain. C
unlithified, exceptforthin hardgrounds.
The boundary between shallow (few
shelf/platform burial domains involving
more dilute waters. However, pressure-
General characteristics. The sedi-
ments are far more varied and may
C
metres to a few tens of metres?) and solution "bedding" (Figure 18) due to include, in various combinations, lime- C
deep is somewhat arbitrary and is per- intervals of closely spaced stylolites stones of mudstone to grainstone tex-
haps the lower limit at which sulphate and non-sutured seams should be com- ture , reef carbonates, peritidal lime- C
reduction takes place, biogenic meth-
ane is produced, early-burial carbonate
mon, sequences with clay- and/or
organic-rich strata.
stone and dolomite, coastal plain
evaporites, and coastal plain to shallow
C
concretions and layers form, and chert C
nodules originate. Some workers place
the boundary in the transition from bac-
Table 5 Similarities and differences between basinal (B) and shelf/platform
(S/P) burial domains.
C
terially mediated reactions to thermally
mediated reactions, at approximately SIMILARITIES
c
60-80°C (L.S. Land,pers. comm., 1986).
GENERAL TRENDS with increasing burial include:
C
Carbonate fractions of pelagic sedi-
ments will be composed of low-Mg cal- • TEMPERATURE and PRESSURE INCREASE
C
cite, without aragonite or Mg-calcite, • POROSITY REDUCTION, to less than 5-6% after 5-6 km burial. (Many
thin , exposed shelf/platform carbonates are cemented tight before enter-
C
and thus stable, with little or no "diage-
netic potential" (Schlangerand Douglas, ing the shelf/platform burial domain.) (
• EXPULSION OF PORE WATERS
1974). Aragonite and Mg-calcitein alloch-
thonous carbonates should survive
• HYDROUS TO LESS HYDROUS OR ANHYDROUS MINERALS C
• MORE SALINE PORE WATERS
well past the shallow-burial domain . • PHYSICAL COMPACTION FOLLOWED BY CHEMICAL COMPACTION C
Displacive- and replacive-fibrous calcite
cements such as cone-in-cone may also CEMENTS: mostly dull CL and terroan in shelf/platform domain ; less well known C
but finer-crystalline in basinal domain
have formed (see Coniglio (1985) for
detailed information about shallow-burial
C
features in fine-grained limestones).
DIFFERENCES
C
Trends in diagenesis. These will
be dominated in the basinal domain by
BURIAL RATES: slow in basinal (B), high in shelf/platform (SIP) with interludes
of exposure
E
the expulsion of pore waters (dewater-
ing), physical compaction initially and
STARTING PORE WATERS: B: marine C
SIP: meteoric to brackish, marine and hypersaline
later pressure-solution compaction, the
STARTINGSEDIMENTS: B: mostly stable fine-grained CaC03 with low diagenetic
C
consequent long-term reductionof thick-
nessand pore volume, the production of
potential and high physical compactibility; some metastable CaC0 3 in C
shelf-derived debris flows ; thin lith ified intervals; often argillaceous/
carbonate cement by pressure-solution, organic rich
(
and the thermochemical conversion of
organic matter to hydrocarbons.
SIP: metastable to stable CaC0 3 and dolomite, fine- to coarse-grained, com-
monly lithified, with variable diagenetic potential; subt idal muds, evapo- C
Burial-dlagenetic features. Poros-
ity generally decreases sharply in the
rites and shales compactible
C
ACCESS BY METEORIC WATER: B: nil unless uplifted
upper 200-250 metres as outlined in SIP : usual due to eustatic and/or tecton ic uplift
(
Figure 32, mainly due to physical com-
paction. Through the first 800-1000 CARBONATE FOR CEMENTS: B: pressure solution dominant source L
metres(?) of burial the sediments will SIP: meteorically derived water at shallow/proximal depths, pressure solution
more important with burial; sulphate cement from dissolution of evaporites
show decreasing Sr2+, Mg2+ and bulk
018 0 as some of the finer-grained con- POROSITY REDUCTION: B: follows exponential curvets) of type in Figure 32 (
stituents dissolve initially under grain- unless arrested or reversed
contact linear pressure (pressure-solu- SIP: can follow similar curvets) but also can go more swiftly in high-flux (:
settings; rates more variable; reduction by physical compaction variable
tion) and low-Mg, low-Sr finely crystal-
with facies and access of meteoric water
(
line calcite cements begin to precipitate.
C
C
c
c Limestones - The Burial Diagenetic Environment 101

c
c' marine sandstones and shales. Be- form of low-Mg calcite cements or of Burial cements precipitated either
c cause these shallow marine to coastal
sediments are commonly exposed in-
selective dissolution of allochems .
It is unclear in any detail what the
below the reach of fresh meteoric
ground water, or in deep aquifers at long
(' termittently during accretion , they are mineralogies and cements in the car- distances down-gradient from recharge
periodically filled with meteoric ground bonates may be when they exit the len- areas (see Back and Hanshaw, 1971;
C water. Consequently, before they exit ticular mixing zone and enter the sub- Hanshaw et al. , 1978; Grover and Read,
r the meteoric environment they may lenticular, shallow burial realm. The 1983), will by and large have dull cath-
have seen multiple generations of fresh limestones may have acquired non- odoluminescence which mayor maynot
( to brackish to marine or even hyper- luminescent , bladed and prismatic be zoned. These cements will include
( saline waters related to low and high calcite cements with brightly lumines - both coarse calcite spar and saddle or
stands of sea level. cent sub-zones (Figure 22). Early-dia- baroque dolomite, and many of them
c. Sedimentation and burial rates will genetic finely crystalline dolomite will will be ferroan. Older to younger burial

c vary from low to very high in the case of


reef carbonates. The pre-burial diage-
probably have formed in some meteoric
(mixed-water?) settings, and both the
cements will vary systematically in oxy-
gen-isotope composition toward lighter
o,ao values, and in trace-element com-
() netic system will in general be open,
since during times of exposure parts of
dolomite and some limestone may have
acquired some pore-lining limpid dolo- positions toward lowerconcentrationsof
o the shelf/platform sequence will be mite cement. Sr2+ and higher Fe2+ and Mn2+ . Fluid

o recharge areas and others will be con-


fined or unconfined surface aquifers
Trends in diagenesis. The domi-
nant trends will include the evolution of
inclusions will generally record pro-
gressively higher temperatures of pre-
c linked to recharge areas. With burial,
diagenetic systems may become partly
pore waters from a varied suite to mostly
saline to hypersaline brines; greatly
cipitation from aqueous pore fluids that
become more saline with depth and are
( closed as fluid flow directions become varying amounts of physical compac- dominantly of Ca-Na-CI type.
o dominantly upward and laterally toward
the updip margins of these shelf basins.
tion during relatively shallow burial and
of chemical compaction during shal- Cement Sequences and Burial
o Build-up of abnormal pore-fluid pressure
may occur locally beneath evaporites
low(?) to deeper burial; cementation
with both locally sourced CaC0 3 from
History
Many different burial-history scenarios
() and compacted shales, early-cemented pressure-solution and more remotely of course apply in sedimentary basins,
o permeability barriers of various kinds,
and zones of intense stylolite develop-
sourced CaC0 3 produced by dissolu-
tion beneath exposure surfaces; dehy-
and often can be discerned in the intri-
cate "cement stratigraphies" (Meyers,
( ment. Geothermal gradients may range dration of certain minerals such as gyp- 1974) that result. Many authors (e.g. ,
from low to quite high. sum and smectite; and long-term re- Meyers, 1974, 1978 ; Walls et al., 1979;
Nature of sediments entering the duction of porosity. Mattes and Mountjoy, 1980; Dickson
o burial realm. The limestones will vary
in CaC0 3 mineralogies from metastable
Burial-diagenetic features. Poros-
ity should vary considerably in the shal-
and Coleman, 1980; Moore and Druck-
man, 1981; Grover and Read, 1983;
l to completely stabilized (see James and low reaches of the burial domain, but James and Klappa, 1983; Moore, 1985;

o Choquette, 1984). Because some car-


bonates will be Iithified and others not,
generally should decrease overall, at
rates that will vary, if controlled by
Walls and Burrowes, 1985 ; Burruss et
al., 1985; Mruk, 1985; Brinton, 1986)
o their resistance to physical compaction
and/or chemical compaction will range
cementation, according to the amount
of alteration accomplished earlier in the
have used various aspects of cement
stratigraphy and geochemistry to re-
G from low in marine lime muds and unce- meteoric realm. Theduration and extent construct burial histories.

o mented marine lime sands, for example,


to very high for such carbonates as cal-
of physical compaction must vary con-
siderably too, but cannot be predicted
Figure 35 is an attempt to portray
the sequences of carbonate cement
o crete, beachrock, shallow-marine hard-
grounds, Iithified reef carbonates, and
in any but very general terms . Unce-
mented marine sediments will suffer
types, with CL characteristics, that
might be precipitated in various dia-
c dolomites of peritidal/supratidal or mix- substantial compaction. Pressure-solu- genetic realms starting with the sea-
o ing-zone origin. Porosities also will vary
widely. Porewaters will range from fresh
tion features are widespread in shallow-
marine limestones, and include grain-
floor and meteoric settings and pro-
gressing into the basinal and shelf/plat-
c to marine, or in evaporitic sequences to
hypersaline. Limestones associated
to-grain microstylolites and non-su-
tured seams, swarms of non-sutured
form burial domains , during three com-
monly encountered stages: (1) wide-
C with karst terranes will have acquired seams in nodular arrays, and bedding spread marine transgression (high sea
stable mineralogies and a wide variety parallel stylol ites and non-sutured level), (2) lowered sea level with conse-
L~ of water-controlled alteration features seams. Pressure-solution features in quent exposure, and (3) continued sub-
C (James and Choquette, 1984) including
vugs, caves and solution-enlarged
limestones may begin developing at
shallower depths than in sub-basin dia-
sidence and burial, all without tectonic
uplift.
fractures, internal sediment, and a vari- genesis - perhaps after was little as a Where sedimentary basins, contain-
ety of speleothems. Limestones that few tens of metres in some cases - ing a spectrum of facies from shallow-
still retain their metastable miner- because of the more dilute waters with marine/peritidal or continental to shelf
alogies, or retained them while in the lower Mg/Ca ratios and lower Mg2+ basin or basinal, are deformed and their

c meteoric or shallow-marine setting,


may already have undergone mineral-
controlled alteration, perhaps in the
concentrations.
Cementation should continue from
the lenticular mixing zone downward.
margins exhumed and exposed to re-
charge by meteoric waters into aqui-
fers, a whole array of major changes
~

C.
(
c
102 Diagenesis Geoscience Canada Reprint Series 4 c
c
(
must then take place: the hydrology of
the system commonly becomes domi- MARINE-FLOODED SHELF c
nated by meteoric waters which are
modified with transport into the subsur- _1 __L _ _____ J ____ l_l"•• c
face; geothermal gradients may be
altered, becoming lower in the recharge
SHALLOW AOUIF~

~~ Prism-NL e Bolry-MOD
c
areas and changing laterally to steeper
gradients across the subsurface parts
SEA WATER,
e Mosa ic-DU
c
of the deformed basin - changes that
EVOLVING WITH DEPTH eM icrile-DU? (
c

may influence the course of carbonate
cement precipitation; and the recharge
portions of limestone aquifers may then
become major donors of cement be-
cause of large-scale dissolution.
c
All of these modifications to the basin
LOWERED SEA LEVEL
c
dynamics will inevitably be recorded in ----..:;----\:.---1----:;-----'-.::-------'= -----7 - . "..:.lr------~--~ c
! L
~
l 6~sR~~~~ON
the burial-diagenetic record. Investiga-
tions ofthe present-day and past hydrol-
ogy and the geochemistry of many
e

~QUIFER
t h
-: c
basins and deep aquifers, notably the
DEEP ACTIVE
\ \
'--- "-.---
"---
, - - - - e Mosaic-DU (Fe)
Biaded-NLIDU ~ eMlcrlte-DU c
Western Canada or Alberta basin (e.g., BRACKISH DEWATERING
Micrile-DU
c

Hitchon, 1963a-d, 1969a,b; Garven and
Freeze, 1984a,b), provided the basis for
a model sketched in Figure 36. As in
c
many other basins, the general paleo- (
hydrology, hydrochemistry, and burial-
diagenetic history of this particular
PROLONGED SUBSIDENCE & BURIAL
c
basin have also been intimately bound c
up in the generation and migration of
hydrocarbons in the basin and the origin
of lead-zinc sulphide ore deposits and
their associated epigenetic dolomite
host rocks in the Pine Point and other e Prism-NL
CORROSION
SLUGGISH
CIRCULATION
eBolry-MOD
' \ Prlsm-NL
-- ---
-~-----1

Spar-DU (Fe)
c
c
c
districts. Spar-DU (Fe)
e Mosaic-DU
"o:::::::-~~~
eMicrite-D
c
Conclusion
Much of what we see when we look
Bladed-NLIDU
Spar-DU (Fe)
" Mlcrile-DU
Spar-DU c
ata limestoneis the resultof its residence c
inthe burialdiagenetic environment. The
most dramatic changes are brought Figure 35 A diagram showing the cement stratigraphies that might develop in different c
about through compaction. Physical
compaction, occurring first, may trans-
settings with lowered sea level followed by prolonged subsidence and burial of a carbonate
sequence. The basinal burial domain is at right and the shelf/platform domain at left. c
form depositional texture from wacke-
Abbreviations: DU, dull cathodoluminescence; NL, non-luminescent; MOD, moderately
luminescent. Prism, prismatic; Bofry, botryoidal; Spar, coarse calcspar. c
stone to packstone, compress unlithi-
fied sediment, squash and obscure crit- c
ical depositional features, and through
plastic and brittle deformation rotate,
c
fracture and crush sedimentary parti-
~---~.....
c
cles. Chemical compaction or pressure-
solution, taking place deeper, results in
W
I-
W
c
stylolites or non-sutured seams, which
can create a new style of diagenetic
::;;
LL
o
c
bedding/stratification, pressure-solu- ~ (,
o
o
tion pseudo-bedding. Dissolved car-
bonate is precipitated locally (autoce-
o CEMENTATION LIKELY c..
mentation) and probably accounts for
much burial cementation. The bladed,
~ LOW T GRAD
MAY BE UNDERSATURATED
HIGH T GRAD
c
coarsely crystalline, poikilotopic, com-
o
o ...........- - - - - 10's-100 's KILOMETERS
• (
monly ferroan burial cements have dis- (
tinctive isotopic, cathodoluminescence Figure 36 A schematic cross-section of an asymmetricalforelandbasin, the Alberta Basin,
and fluid-inclusion signatures which showing hydrologic flow lines and temperature gradients . (After Hitchon, 1969). (
C
C
(
( Limestones - The Burial Diagenetic Environment 103

(
'- point to precipitat ion from brines , pro- Acknowledgements Bathurst, R.G.C., 1980a, Lith ification of car-
moted by gene ral carbonate super- This art icle has benefited from the ideas bonate sediments : Blackwell Scientific
saturation and elevated temperature. and suggestions of many colleagues . Publications, Oxford, Science Progress,
( The dominant, prevailing trend in We are grateful to Robin G.C. Bathurst, p.451-471.
bur ial diagenesis, as pointed out many Robert B. Halley, and Lynton S. Land, A review of research on cementation in
C1 years ago (e.g., Pray and Choquette, and to our colleagues Mario Coniglio ,
carbonates.
Bathurst, R.G.C., 1980b, Deep crustal dia-
C 1966; Choquette and Pray, 1970), is
toward complete or nearly complete
Dexter H. Craig and Neil F. Hurley for
critical reviews of the manuscript.
genes is in limestones : Revista del
Instituto de Investigac iones Geologicas
C occlusion of porosity. Some porosity Photographs were graciously lent us by Diputacion Provincial , Universidad de
may be retained, however, for a variety Robin Bathurst, David K. Beach, Lise Barcelona, v. 34, p. 89-100.
, of reasons: if the sediments were
already low-Mg calcite or dolomite prior
Brinton, Nancy Chow, Mario Coniglio,
Charles T. Feazel, Eugene A. Shinn ,
Probably the first recent review specif-
ically on burial diagenesis .
to burial; or formation-water flux was and P.K. Wong. We owe much to the Bathurst , R.G.C ., 1985, Carbonate dia-
( sluggish over much of the sediment's thoughtful treatises on aspects of burial genesis and reservoir development -
conservation, destruction and creation
burial history, and/or residence time in diagenesis by three distinguished
of pores : Notes for a short course: Colo-
the burial setting and depth of burial friends , Robin Bathurst, Robert Halley
o were insufficient for pressure-solution and Peter A. Scholle . Finally, we thank
rado School of Mines , Golden, Colo-
rado, April 8-10, 1985, 63 p.
o cementation to proceed to completion;
or perhaps the geothermal gradient
our wives, Jean and Judith, for assis-
tance in the preparat ion of this review
A useful review on carbonate diagenesis
and porosity. Soon to be published, with
was low and the temperature effect on and the two that preceded it (James and other short-course notes from the same
carbonate solubility was suppressed; Choquette, 1983,1984).N.P.Jo acknowl- series , in the Colorado School of Mines
r
or again, perhaps most desireable and edges the Natural Sciences and Engi- Quarterly.

o serendipitous of all, if the occlusion of


porosity was shut off by the influx of
neering Research Council of Canada
for ongoing support. PoW.C. acknowl-
Bricker, O.P., 1971, ed ., Carbonate Ce-
ments : Johns Hopkins Press, Baltimore,

o hydrocarbons. Dissolution may also


take place, though perhaps on a limited
edges the management of Marathon Oil
Company, particularly S.G. Andrew and
MD, 376 p.
The last third of this book contains arti-
( scale, through reactions between for- F.G.Knight, for support and permission
cles on burial cements and cementation .
Other parts have examples of marine and
o mation waters and maturing organic
matter.
to publish. meteoric carbonate cementation.
Chanda , S.D., Bhatlacharyya , A. and
Although the processes and general REFERENCES Sarkan , S., 1983, Compact ion in lime-
products of burial diagenesis give us an stones - a reappraisal: Journal of the
idea of the features and the kinds of General References and Reviews Geolog ical Society of India, v.24,
limestones to expect in deep-burial set- p.73-92.
ADREF- , 1984, Stylolites and associated
tings, the actual fabrics and structures An extensive review that forcefully
phenomena - relevance to hydrocarbon argues the case for commonly extensive
that develop in limestones are largely reservoirs: - Abu Dhab i National Reser- compaction in fine-grained limestones.
dependent on differences in the original voir Research Foundation, Special Pub-
Choquette, P.W. and Pray, L.C., 1970, Geo-
composition and early diagenetic his- lication, P.O. Box 6838, Abu Dhabi,
logic nomenclature and classification of
r tory of the sediments. Two prelim inary U.AoE., 304 p.
porosity in sedimentary carbonates:
diagenetic models representing burial A compendium of recent papers on the
American Association of Petroleum
of basinal versus shelf/platform sedi- burial diagenesis of sediments in general
Geologists, Bulletin, v. 54, p. 207-250.
and on stylolites in particular.
ments, respectively removed from or An outline of the basic concepts of poros-
Barnes , M.A., Barnes, W.C. and Bustin ,
associated with early " exposure" to ity evolution in carbonate rocks. Con-
R.M., 1984, Diagenesis and chemistry
waters of meteoric origin, are proposed tains a comprehensive descriptive clas-
and evolution of organic matter: Geo-
to highlight these differences. sification that has been widely accepted.
science Canada, v. 11, p. 103-114.
Only with hindsight are we likely to Enos, P. and Sawatsky, L.H., 1981, Pore net-
An overview of the alteration of sedimen-
works in Holocene carbonate sedi-
know whether or not in the 1980s we tary organic matter.
ments : Journal of Sedimentary Petrol-
have been on a plateau or a steep climb Bathurst, R.G.C ., 1975, Carbonate sed i-
ogy, v. 51, p. 961-985.
(, in the search for unifying principles in ments and their diagenesis: Elsev ier
The best single reference to the porosity
the burial diagenesis of sedimentary Scientific Publishing Co., Amsterdam,
r. carbonates. It does seem clear that our Developments in Sedimentology 12,
Second Edition, 658 p.
of modern carbonate sediments, with
abundant data.

e understanding of the dynamics and our


. ability to forecast or even adequately
The most comprehensive synthesis ever
written on diagenes is in carbonates, and
Feazel , C.T. and Schatzinger, A.A., 1985,
Prevention of carbonate cementat ion in
petroleum reservoirs , in Schneider-
chart the different courses of diagene- like its predecessor first edition (Bath·
sis in this largely occult realm are still mann N. and Harris , P.M., eds., Carbon-
urst, 1971), the standard reference on the
quite primitive. There is much to learn ate Cements : Society of Economic
subject. The bibliography, although now
Paleontologists and Mineralogists, Spe-
but we have come a long way; the next in need of updating, is extensive and
cial Publication 36, p. 97-106.
steps in the search are sure to be unusually valuable.
A conc ise overview on factors respon-
excit ing. sible for preserving carbonate poros ity is
preserved in the geologic record.
.....
c
104 Diagenesis Geoscience Canada Reprint Series 4 C
r
Friedman , G .M ., 1975 , The mak ing or The first paper to outline succinctly the Coogan , A.H., 1970, Measurements of com-
(
unmak ing of limestones or the ups and
downs of porosity: Journal of Sedimen-
diagenesis ofpelagic carbonates and pro-
pose the concept of diagenetic potential.
paction in oolite grainstone : Journal of
Sedimentary Petrology, v. 40, p. 921-929.
C
tary Petrology, v. 45, p. 379-398.
A general review on both cementation
Scholle, PA and Halley, R.B., 1985, Burial
diagenesis - out of sight, out of mind!, in
Ebhardt, G., 1968, Experimental compaction
of carbonate sediments, in Muller, G. and
C
and porosity. Schneidermann, N. and Harris, P.M., Friedman, G.M., eds., Recent Develop- C
Garrison , R.E , 1981, Diagenesis of oceanic eds. , Carbonate Cements: Society of ments in Carbonate Sedimentology in
carbonate sed iments - a review of the Economic Paleontolog ists and Minera l- Central Europe : Springer-Verlag, Berlin,
(
DSDP perspective, in Warme , J.E .,
Douglas , R.G . and Winte rer, E.L., eds .,
ogists , Special Publication 36,
p.309-334.
p.58-.65.
Fruth, L.S., Jr., Orme, G.R. and Donath, FA ,
(
The Deep Sea Drilling Project -a decade
of progress: Society of Economic Pale-
An outstanding review of burial diagene-
sis of carbonate sediments. Argues per-
1966, Experimental compaction effects
in carbonate sediments: Journal of Sedi-
C
ontologists and Mineralogists, Spec ial suasively the case for extensive cemen- mentary Petrology, v. 36, p. 747-754. (
Publication 32, p. 181-207. tation of pressure-solution, burial-diage- Gaillard, C. and Jautee, E., 1987, The use of
A synthes is of results from the DSDP
project concerning diagenesis of chalk
netic origin. Has an excellent bibliography.
Shinn, E.A . and Robbin, D.M., 1983,
burrows to detect compact ion and sliding
in fine-grained sediments : an example
C
and other deep-marine carbonate sedi- Mechanical and chemical compaction in from the Cretaceous of SE France: Sedi- C
ments in the marine burial environment. fine-grained shallow-water limestones: mentology, v. 34, p. 585-593.
Halley, A.B., 1984, Post-depositional dia- Journal of Sedimentary Petrology, v. 53, Ginsburg, R.N., 1957, Early diagenesis of C
genesis of metastable carbonates - an
overview: Palaeontographia Amer i-
p.595-618.
Thefirst detailed experimentalstudy using
lithification of shallow-water carbonate
sediments in south Florida, in LeBlanc,
C
cana, no . 54, p. 245-253 .
A brief review emphasizing characteris-
cores of modern carbonate sediments
with their original in situ pore fluids. A well-
R.J. and Breeding , J.G., eds., Regional
Aspects of Carbonate Deposition:
C
tics of starting carbonate skeletalconstit- illustrated work that helps explain many Society of Economic Paleontologists C
uents and sediments. features seen in fine-grained limestones. and Mineralogists, Special Publication 5,
Halley, A.B. , 1985, Burial diagenes is of car- Tissot, B.P.and Welte, D.H., 1978, Petroleum p.80-98. C
bonate rocks : Notes for a short course Formation and Ocurrence - a new Hallam, A., 1964, Origin of the limestone-
(unpublished): Colorado School of Mines , approach to oil and gas exploration: shale rhythms in the Blue Lias of England: C
Golden, Colorado, April 1985, 44 p.
An excellent review covering many of the
Springer-Verlag, Berlin, 538 p.
Probably the standard reference on the
a composite theory: Journal of Geology,
v. 72, p. 157-168.
(
same topics discussed in this article, but
from a different perspective. Soon to be
geochemistry, maturation, and genera -
tion of organic matterandhydrocarbons in
Hathaway, J.C. and Robertson , E.C., 1961,
Micro-texture of artificially consolidated
C
published in the Colorado School ofMines
Quarterly.
sedimentary rocks , emphasizing shales
more than carbonates.
aragonite mud : United States Geological C
Survey, Professional Paper 424-G ,
Meyers, w.J ., 1974, Carbonate cement stra- p.301-304. C
tigraphy of the Lake Valley Formation Physical Compaction Meyers, W.J., 1980,Compaction in Mississip-
(Mississippian), Sacramento Mountains, pian skeletal limestones , southwestern C
New Mexico: Journal of Sedimentary
Petrology, v. 44. p. 837-861.
Baldwin, B. and Butler, C.O., 1985, Com-
paction curves: American Association of
New Mex ico : Journal of Sedimentary
Petrology, v. 50, p. 457-474.
C
Thefirst paper to use cement stratigraphy
based on cathodoluminescence to un-
Petroleum Geologists, Bulletin, v. 69,
p.622-626.
Meyers, w.J . and Hill, B.E, 1983, Quantita-
tive studies of compaction in Mississip-
C
ravel the burial diagenetic history of a
group of shallow-water carbonates. This
Beach, D.K . and Schumacher, A., 1982,
Stanley Field, North Dakota - a new
pian skeletal limestones, New Mexico:
Journal of Sedimentary Petrology, v. 53,
C
paper stimulated a new generation of model for a new exploration play,in Chris- p.231-242. C
studies and discoveries in diagenesis. topher, J.E. and Kaldi, J., eds., 4th Inter- Oertel , G. and Curtis, C.D. , 1972, Clay iron-
Roehl, P.O. and Choquette, P.W., 1985, eds ., national W illiston Basin Symposium, stone concretion preserving fabrics due E
Carbonate Petroleum Reservoirs :
Springer-Verlag , Heidelberg, 622 p.
Saskatchewan Geological Society, Spe-
cial Publication 6, p. 235-243.
to progressive compaction: Geological
Society of America Bulletin, v.83,
C
Numerous papers in this volume contain
excellent illustrations of diagenesis in the
Bhattacharyya, A. and Friedman, G.M.,
1979, Experimental compaction of ooids
p. 2597-2606.
Pray, L.C., 1960, Compaction in calcilulites
C
burial realm.
Schneidermann, N. and Harris, P.M., 1985,
and lime mud and its implication for lithi-
fication during burial: Journal of Sedi-
(abstr.): Geolog ical Society of America
Bulletin, v. 71, p. 1946.
C
eds., Carbonate Cements: Society of mentary Petrology, v.49, p. 1279-1286. Rieken, w., 1987, The carbonate compaction C
Economic Paleontologists and Mineral- Brown, P.A., 1969, Compaction of fine- law: a new tool: Sedimentology, v. 34,
ogists, Special Publication 36, 379 p. grained terrigenous and carbonate sedi- p.571·584. (
Many papers in this votume specifically ments - a review: Bulletin of Canadian Robertson, E.C., 1967, Laboratoryconsolida-
address burial diagenesis and cementa- Petroleum Geology, v. 17, p. 486-495 . tion of carbonate sediment, in Richards, i:
tion. An important collection of works on Byers, C.w. and Stasko , L.E., 1978, Trace A.F., ed., Marine Geotechnique: lnterna- (
the subject. fossils and sedimentologic interpretation tional Research Conference on Marine
Schlanger, S.O. and Douglas , R.G., 1974,
The pelagic ooze-chalk-Iimestone transi-
- McGregor Member of Platteville For-
mation (Ordovician) of Wisconsin: Jour-
Geotechnique, Urbana, Illinois, Univer-
sity of Illinois Press, p. 118-127.
c
tion and its implications for marine stratig- nal of Sed imentary Petrology, v. 48, Shinn, EA., Halley, R.B., Hudson , J.H. and c
raphy, in Hsii, K.J. and Jenkyns, H.C.,
eds., Pelag ic Sediments on Land and
Under the Sea: International Association
p. 1303-1310. Lidz, B.H., 1977, Limestone compaction -
an enigma : Geology, v. 5, p. 21-14. c
of Sedimentologists, Special Publication
(
1, p. 117-148.
c.
c
(
Limestones - The Burial Diagenetic Environment 105

Shinn, E.A. and Robbin, D.M ., 1983 , Choquette, P.W. and Steinen, R.P. , 1980, Groshong, R;H., Jr., 1974, "Slip" cleavage
Mechanical and chemical compaction in Mississippian non-supratidal dolom ite, caused by pressure solution in a buckle
fine-grained shallow-wate r limestones: Ste . Genevieve Limestone , Ill inois fold: Geology, v. 3, p. 411-413.
(1 Groshong , R.H., Jr., 1975, Strain , fracture
Journal of Sedimentary Petrology, v. 53, Basin: evidence for mixed-water dolo -
1....
p.595-618. mitization, in Zenger, D.H., Dunham , and pressure solution in natural single-
Q Terzaghi, R.D., 1940, Compact ion of lime J.B. and Ethington, R.L., eds., Concepts layer folds: Geological Society of Amer-
mud as a cause of seconda ry structure: and Models of Dolomit izat ion - a sym- ica Bullet in, v. 86, p. 1363-1376.
( Journal of Sedimentary Petrology,v. 49, posium: Society of Economic Paleon- Guzzetta, G., 1984, Kinematics of stylolite
p.437-462. tologists and Mineralogists, Special formation and physics of the pressure-
( Weller, J.M., 1959, Compaction of sedi- Publication 28, p. 163-196. solution process : Tectonophysics,
ments: American Associat ion of Petro- DeBoer, R.B ., 1977a , On the thermo- v. 101, p. 383-394.
leum Geolog ists, Bullet in , v.43, dynamics of pressure solution: inter- Harms, J.C. and Choquette, P.W., 1965,
c p.273-319.
Zankl , H., 1969, Structural and textura l evi-
action between chemical and mechan-
ical forces : Geochimica et Cosmo-
Geologic evaluation of a gamma-ray
porosity device: Society of Professional
dence of early lithification in fine- chimica Acta, v. 41, p. 249-256. Well Log Analysts, 6th Annual Sympo-
gra ined carbonate rocks : Sedimen- DeBoer, R.B., 1977b, Pressuresoluton ,the- sium, Transactions, v. 2, p. C1-C37.
tology, v. 12, p. 241-256. ory and experiments: Tectonophysics, Hurley, N.F., 1986, Geology of the Oscar

o Chemical Compaction, Stylolites and


v. 39, p. 287-30t
Dunnington , H.V., 1954, Stylolite develop-
Range Devonian reef complex, Canning
Basin, Western Austral ia, unpublished
o Cementation ment post-dates rock induration: Jour-
nal of Sed imentary Petrology, v. 24,
Ph.D. Thesis, University of Michigan,
Ann Arbor, Michigan, 269 p.
Alvarez , W, Engelder, T. and Lowrie , W , p.27-49. Koepnick, R.B., 1984, Distribution andverti-
1976, Formation of spaced cleavage and Dunn ington, H.V., 1967, Aspects of dia- cal permeability of stylolites within a
folds in brittle limestone by dissolution : genesis and shape change in stylol ite Lower Cretaceous carbonate reservoir,
Geology, v. 4, p. 698-701. limestone reservoirs: 7th World Petro- Abu Dhabi, U.A.E. , in Stylolites and
o Baker, P.A., Gieskes, J.M. and Elderfield, leum Congress, Proceed ings, Mexico Associated Phenomena - relevance to

o H., 1982, Diagenesis of carbonates in


deep-sea sediments - evidence from SrI
City, v. 20, p. 339-352 .
Droxler, A. and Schaer, J.P., 1979, Deforma -
hydrocarbon reservoirs : Abu Dhabi
National Reservoir Research Founda-
() Ca ratios and interstitial dissolved Sr
data: Journal of Sedimentary Petrology,
tion cataclastique plastique lors du
plissement, sous faible couverture, de
tion , Special Publication, Abu Dhabi ,
UAE. , p. 261-278.
v. 52, p. 71-82. strates calcaires: Eclogae Geologicae Lloyd, A.M ., 1977, Porosity reduct ion by
Baker, P.A., Kastner, M., Byerlee, J.D. and Helveticae, v. 72(2), p. 551-570. chemical compaction - stable isotope
Lockner, D.A., 1980, Pressure solution Durney, D.W., 1972, Solution-transfer, an model (abstr.): American Association of
and hydrothermal recrystallization of car- i mpo r t ant geological deformation Petroleum Geologists, Bulletin , v. 61,
bonate sediments - an experimental mechanism : Nature, v. 235, p. 315-317. p.809.
study: Marine Geology,v. 38, p. 185-203. Durney, D.W., 1976, Pressure-solution and Logan , B.W. and Semeniuk, V.• 1976,
Barrett, P.J., 1964, Residual seams and crystallizat ion deformation : Royal Dynamic metamorph ism : processes
cementation in Oligocene shell calc- Society of London, Philosophical Trans- and products in Devonian carbonate
arenites, TeKuiti Group :Journal of Sedi- actions , v. 283A, p. 229-240. rocks , Canning Basin, Western Aus-
mentary Petrology, v. 34, p. 524-531. Eder, W, 1982, Diagenetic redistribution of tralia : Geological Society of Australia,
Bathurst, R.G.C., 1984, The integration of carbonate, a process in forming lime- Special Publication 16, 138 p.
pressure-solution and mechanical com- stone-marl alterations (Devonian and Manus, A.W. and Coogan, A.H., 1974, Bulk
r paction and cementation , in Stylolites Carboniferous, Rheinisches Schiefer- volume reduction and pressure solution
and Associated Phenomena - relevance gebirge , West Germany) , in Einsele, G. derived cements: Journal of Sedimen-
to hydrocarbon reservoirs: Abu Dhabi and Seilacher, A., eds., Cyclic and Event tary Petrology, v. 44, p. 466-471-
National Reservoir Research Founda- Stratification: Springer-Verlag , New Marshak, S. and Engelder, T., 1985 ,
tion , Special Publication, Abu Dhab i, York, p. 98-112. Development of cleavage in limestones
U.A.E., p. 41-56. Engelder, T., Geiser, P.A. and Alvarez, W , of a fold-thrust belt in eastern New
Bathurst, R.G.C ., 1987, Diagenetically 1981, Role of pressure solution and dis- York: Journal of Structural Geology, v. 7,
enhanced bedding in argillaceous plat- solution in geology: Geology, v.9, p.345-359.
form limestones : stratified cementation p.44-45. Merino, E., Ortoleva, P. and Strickholm, P.,
and selective compaction : Sedimentol- Fletcher, R.C. and Pollard, D.D., 1981, Anti - 1983. Generation of evenly-spaced
ogy, v. 34, in press. crack model for pressure solution sur- pressure-solution seams during (late)
r Bochon , P. , 1976, L'importance des joints faces: Geology, v. 9, p. 419-424. diagenesis - a kinetic theory : Contribu-
stylolithiques dans la compaction des Garrison, R.E. and Kennedy, WJ ., 1977, tions to Mineralogy and Petrology, v. 82,
r carbonates: Centre des Recherches de Origin of solution seams and flaser p.360-370.
Pau, Bulletin , v. 10, p. 627-644. structure in Upper Cretaceous chalks of Meyers, W.J. and Hill, B.E., 1983, Quantita-
Brown, A.A., 1987, Mechanisms of porosity southern England: Sedimentary Geol- tive studies of compaction in Mississip-
loss in limestones: applications to ogy, v. 19, p. 107-137. pian skeletal limestones, New Mexico:
numerical models of porosity loss : Geiser, P.A., 1974, Cleavage in some sedi- Journal of Sedimentary Petrology, v. 53.
Society of Economic Paleontologists mentary rocks of the Valley and Ridge p.231-242.
and Mineralog ists, Abstracts v. IV, 1987 province, Maryland: Geological Society
Midyear Meeting , p. 10. of America Bulletin, v. 85, p. 1399-1412.
Buxton , T.M. and Sibley, D.F., 1981, Pres- Geiser, P.A. and Sansone , S., 1981, Joints ,
sure solution features in a shallow bur- microfractu res and the format ion of
ied limestone: Journal of Sedimentary solution cleavage in limestone: Geology,
Petrology, v. 51, p. 19-26. v. 9, p. 280-285.
c
106 Diagenesis Geoscience Canada Reprint Series 4 c
c
Morse, J.W., 1983, The kinetics of calc ium Sprunt , E.A. and Nur, A., 1977a, Experimen- Burial Cements - Petrography
c
carbonate dissolution and precipitation,
in Reeder, R.J., ed., Carbonates: Miner-
tal study of the effects of stress on solu-
tion rate : Journal of Geophysical Burruss , R.C., Cercone, K.R. and Harris,
c
alogy and Chem istry: Mineralogical Research, v. 82, p, 3013-3022. P.M., 1983, Fluid inclusion petrography c
Society of America, Reviews in Mineral-
ogy, v. 11, p, 227-264.
Mossop, G.D., 1972,Origin olthe peripheral
Sprunt, E.A. and Nur, A., 1977b, Destruc-
tion of poros ity through pressure solu-
tion: Geophysics, v. 42, p. 726-741.
and tectonic burial history of the AI Ali
No. 2 well: evidence for the timing and
diagenesis and oil migration, northern
c
rim, Redwater Reef, Alberta: Bulletin of Stockdale, P.B., 1922, Stylolites - the ir Oman foredeep : Geology, v.11 ,
(
Canadian Petroleum Geology, v.20,
p.238-280.
nature and origin: Indiana Univers ity p.567-570. (
Studies, v. 9, p. 1-97. Cayeux, L., 1935, Carbonate rocks - lime-
Nelson, R.A., 1981, Significance offracture
sets associated with stylolite zones:
Stockdale, P.B.,1926,The stratigraphic sig-
nificanceofsolutions in rocks: Journal of
stones and dolomites, [1970 translation
by A.V. Carozzi [: Habner Publ ishing
C
American Associat ion of Petroleum Geology, v. 34, p. 1-97. Company, Connecticut, 506 p. C
Geologists, Bulletin , v. 65, p. 2417-2425. Stockdale, P.B., 1943, Stylolites: primary or Cercone, K.R. and Lohmann, K.C., 1987, Late
Park, W.C. and Schot, E.W., 1968, Styloliti- secondary?: Journal of Sed imentary burial diagenesisof Niagaran(MiddleSilu- C
zation in carbonate rocks, in Muller, G. Petrology, v. 13, p. 3-12. rian) pinnacle reefs in Michigan Basin:
and Friedman, G.M., eds., Recent Thompson, J., 1862, On crystallization and American Associationof Petroleum Geolo-
(
Developments in Carbonate Sedimen-
tology in Central Europe: Springer-Ver-
liquefaction , as influenced by stresses
tending to change of form in crystals :
gists, Bulletin, v. 71, p. 156-166.
Choquette, P.W. and Steinen, R.P., 1985,
C
lag, Berlin , p. 66-74.
Playford, P.E., 1980, Devonian " Great Bar-
Royal Society of London, Proceedings ,
v. 11, p. 473-480.
Mississ ippian oolite and non-supratidal
dolomite reservoirs in the Ste. Gen-
C
rier Reef" of Canning Basin, Western Trurnit, P., 1968, Analysis of pressure-solu- evieve Formation, North Bridgeport C
Australia: American Association of tion contacts and classification of pres- Field, Illinois Basin, in Roehl, P.O. and
Petroleum Gecloqists, Bulletin, v. 64, sure-solution phenomena, in Muller, G. Choquette, P.w., eds., Carbonate Petro- C
p.814-840. and Friedman, G.M . , eds ., Recent leum Reservoirs: Springer-Verlag, New
Pratt, B.R., 1982, Limestone response to Developments in Carbonate Sedimen- York, p. 207-227. C
stress: pressure solution and dolomiti-
zation - Discussion and examples of
tology in Central Europe: Springer-Ver-
lag, Berlin, p. 75-84 .
Coniglio, M., 1985,Origin and diagenesis of
fine-gra ined slope sed iments, Cow
C
compaction in carbonate sediments:
Journal of Sedimentary Petrology, v. 52,
Wanless, H.R., 1979, Limestone response
to stress - pressure solution and dolomi-
Head Group (Cambro-Ordovician),
western Newfoundland, unpublished
C
p.323-328. tizat ion: Journal of Sed imentary Petrol- Ph.D. dissertation, Memorial University C
Rheinhardt, J . and Hardie, L., 1976, ogy, v. 49, p. 437-462. of Newfoundland, v. 1 and 2, 684 p.
Selected examples of carbonate sedi- Wanless, H.R., 1982, Limestone response Dorobek, S.L., 1987, Petrography, geo- C
mentation, Lower Paleozoic of Mary- to stress - pressure solution and dolomi- chemistry and origin of burial diage-
land : Maryland Geological Survey, tization - reply: Journal of Sedimentary netic facies, Siluro-Devonian Hulderberg
(
Guidebook 5, 53 p.
Robin, P.F., 1978,Pressure solution at grain-
Petrology, v. 52, p. 328-332.
Wanless, H.R., 1983, Burial diagenesis in
Group (carbonate rocks), central Appa-
lachians: American Association of Pe-
C
to-grain contacts: Geochimica et Cosmo-
chimica Acta, v. 42, p. 1383-1389.
limestones , in Parker, A. and Sellwood,
B.W., eds ., Sediment Diagenesis : J.
troleum Geologists, Bulletin , v.71 ,
p.492-514.
C
Roehl, P.O., 1967, Stony Mountain (Ordovi -
cian) and Interlake (Silurian) facies ana-
Reidel and Company, Lancaster,
p.379-417.
Druckman, Y. and Moore, C.H., 1985, Late
subsurface secondary porosity in a
C
logs of Recent low-energy marine and Weyl, P.K., 1958, The solution kinetics of Jurassic grainstone reservoir, Smack- C
subaerial carbonates, Bahamas: Ameri- calcite: Journal of Geology, v.66 , over Formation , Mt. Vernon field , south-
can Assoc iation of Petroleum Geolo- p.163-176. ern Arkansas, in Roehl, P.O. and Cho- C
gists, Bulletin, v. 51, p. 1979-2032.
Rutter, E.H. , 1976, The kinetics of rock
Weyl, P.K., 1959, Pressure solution and the
force of crystallization - a phenomeno-
quette, P.w.,eds. , Carbonate Petroleum
Reservo irs: Springer-Verlag, New York,
E:
deformation by pressure solution: Royal
Society of London, Philosophical Trans-
logical theory: Journal of Geophysical
Research, v. 64, p. 2001-2025.
p.369-384.
Elliott, T.L., 1982,Carbonate facies, deposi-
C
actions, v. 283A, p. 203-219.
Rutter, E.H., 1983, Pressure solution in
Wolfe, M.J., 1968, Lithification of a carbon-
ate mud: Senonian Chalk in northern
tional cycles, and the development of C
secondary porosity duringburial diagene-
nature, theory and experiment: Journal Ireland: Sed imentary Geology, v. 2, sis, in Christopher,J.E. andKaldi,J., eds., C
of the Geological Society of London, p.263-290. 4th International Willisto n Basin Sym-
v. 140, p. 725-740. Wong, P.K., 1984, Origin of low-per- posium : Saskatchewan Geological C
Sorby, H.C., 1879, On the structure and meability zones in the Upper Devonian Society, Special Publication 6, p. 131-151. (
origin of limestones : Quarterly Journal Kaybob reef, Alberta, Canada , in Sty- Folk, R.L. and Assereto, R., 1974, Great
of the Geological Society of London ,
v. 35, p. 56-95.
lolites and Associated Phenomena - rel-
evance to hydrocarbon reservo irs: Abu
aragon ite rays and baroque white dolo-
mite in tepee fillings, Triassic of Lom-
C
Sorby, H.C., 1908, On the application of Dhabi National Reservoir Research bardy, Italy : American Association of (.>--
quantitative methods to the study of the Foundation , Special Publication, Abu Petroleum Geologists, Abstracts with
structure and history of rocks: Quarterly Dhabi, U.A.E., p. 247-260. Programs, Annual Meeting, San C
Journal of the Geological Society of Wong, P.K. and Oldershaw, A., 1981, Burial Antonio, Texas, p, 34-39.
London, v. 64, p. 171-233. cementation in the Kaybob reef com- Frank, J.R., Carpenter, A.B. and Oglesby, C
Simpson, J., 1985, Stylolite-controlled plex, Alberta, Canada: Journal of Sedi- T.W., 1982, Cathodoluminescence and
layering in an homogeneous limestone: mentary Petrology, v. 51, p. 507-520. composition of calcite cement in the
(
pseudo-bedding produced by burial Taum Sauk Limestone(UpperCambrian), (
diagenesis: Sedimentology, v. 32, southeast Missouri: Journal of Sedimen-
p.495-505. tary Petrology, v. 52, p. 631-638. (

c
Limestones - The Burial Diagenetic Environment 107

Franks , P.C., 1969, Nature , orig in and signi- Meyers, w.J ., 1974, Carbonate cement stra- facies and diagenetic history : American
r: ficance of cone-in-cone structures in the tigraphy of the Lake Valley Formation Association of Petroleum Geologists ,
Kiowa Forma tion (Ear ly Cretaceous), (Mississipp ian) , Sac ramento Moun - Bulletin, v. 68, p. 542.
c north-central Kansas: Journal of Sedi- tains, New Mexico : Journal of Sedimen-

c. mentary Petrology, v. 39, p. 1438-1454.


Grover, G., Jr. and Read, J.F., 1983, Paleo-
aquifer and deep-burial-related ce-
tary Petrology, v. 44, p. 837-861.
Meyers, W.J., 1978, Carbonate cements -
their regional distr ibution and interpre-
Burial Cements -
Hydrology
Water Chemistry and

( ments defined by regiona l cathodolumi- tation in Mississ ippian limestones of Back, W. and Hanshaw, B.B., 1970, Com-

C
r
nescent patterns , Middle Ordovician
carbonates, Virginia: American Assoc i-
southwestern New Mexico : Sed imen-
tology, v. 25, p. 371-400.
parison of chemical hydrogeology of the
carbonate peninsulas of Florida and
ation of Petroleum Geologists, Bulletin , Moore, C.H., 1985, Upper Jurassic subsur- Yucatan peninsulas : Journal of Hydrol-
'-
, v. 67, p. 1275-1303.
Hallam, A., 1960, A sedimentary and faunal
face cements - a case history, in
Schneidermann , N. and Harris, P.M.,
ogy, v. 10, p. 330-368.
Back, W. and Hanshaw, B.B., 1971, Ratesof
r study of the Blue Lias of Dorset and Gla- eds., Carbonate Cements: Society of physical and chemical processes in a
morgan: Royal Society of London , Philo- Economic Paleontologists and Mineral - carbonate aquifer : American Chemical
sophical Transactions , v. 243B, p. 1-44. ogists, Special Publication 36, Society, Advances in Chemistry, v. 106,
Hallam, A., 1964, Origin of the limestone- p.291-308. p.77-93.
shale rhythm in the Blue Lias of England Mruk, D.H., 1985, Cementat ion and dolo- Baker, P.A., Gieskes ,J.M.and Elderfeld, H.,
• a composite theory: Journal of Geol- mitization of the Capitan Limestone, 1982, Diagenesis of carbonates in deep-
ogy, v. 72, p. 137-169. McKittrick Canyon, west Texas: M.S. sea sediments - evidence from Sr/Ca
Harris , D.C., 1982, Carbonate cement stra- Thesis, University of Colorado/Boulder, ratios and interst iti al dissolved Sr 2 ..
tigraphy and diagenesis of the Bur- Boulder, CO, 153 p. data: Journal of Sedimentary Petrology,
lington Limestone (Mississippian), Oldershaw, A.E. and Scoffin, T.P.,1967, The v. 52, p. 71-82.
southeastern Iowa and western Illinois : source of ferroan and non-ferroan cal- Berner, R.A., 1975, Diagenetic models of
M.S. Thesis , State University of New cite cements in the Halkin and Wenlock dissolved species in the interstiti al
York, Stony Brook, 220 p. limestones: Geological Journal , v. 5, waters of compacting sediments : Ameri-
Heckel, P.H., 1983, Diagenetic model for car- part 2, p. 309·320 . can Journal of Science, v. 275, p. 88-96.
bonate rocks in midcontinent Pennsyl- Prezbindowski, D.R., 1985, Burial cemen- Bonham, L.C., 1980, Migration of hydro-
vanian eustatic cyclothems: Journal of tation - is it important? A case study, carbons in compacting basins, in
Sedimentary Petrology, v. 53, p. 733- Stuart City trend , south-central Texas, Roberts, W.H., III and Cordell , R.J., eds.,
759. in Schneidermann , N. and Harris, P.M., Problemsof PetroleumMigration: Ameri-
Irwin , H., 1980, Early diagenetic carbonate eds., Carbonate Cements: Society of can Assoc iat ion of Petroleum Geolo-
precipitation and pore-fluid migration Econom ic Paleontologists and Min- gists, Studies in Geology,v. 10, p. 69-88.
in the Kimmeridge Clay of Dorset, Eng- eralog ists, Special Publication 36 , Bredehoeft , J.D. and Papadopulous, I.S.,
land: Sedimentology, v. 27, p. 577-591. p.241-264. 1965, Rates of vertical groundwater
James, N.P. and Klappa, C.F., 1983, Petro- Saller, A.H., 1984, Diagenesis of Cenozoic movement estimated from the earth 's
genesis of early Cambrian reef lime- limestones on Enewetak Atoll : Ph.D. thermal profile : Water Resources
r .. stones, Labrador, Canada: Journal of Thesis, Louisiana State University, Research, v. 1, p. 325-328.
J
Sedimentary Petrology, v. 53, p. 1051- Baton Rouge, LA, 363 p. Carpenter, A.B. , 1978, Origin and chemical
( 1096. Saller, A.H., 1986, Radiaxial calcite in Lower evolut ion of brines i n sed imentary
Loucks, R.E. and Budd, D.A., 1985, Diagen- Miocene strata , subsurface Enewetak basins: Oklahoma Geological Survey,
o esis and reservoir potent ial of the upper
Jurassic Smackover Formation of south
Atoll: Journal of Sedimentary Petrology,
v. 56, p. 743-762.
Circular 79, p. 60-77.
Champ, D.R., Gulens,J . and Jackson, R.E.,
(
Texas: Gulf Coast Association of Geo- Talbot, M.R., 1971, Calcite cements in the 1979, Oxidat ion-reduction sequences in

o logical Societies, Transactions , v. 31,


p.339-346.
Corallian Beds (Upper Oxfordian) of
southern England : Journal of Sedimen-
ground-water flow systems: Canadian
Journal of Earth Sc iences , v.16,
C) Marshall , J.D., 1982, Isotopic composition tary Petrology, v. 41, p. 261-273. p. 12-23.
of displacive fibrous calcite veins , rever- Walkden, G.M. and Berry, J.R., 1984, Syn- Clayton, R.N. , Friedman, I., Graf, D.L.,
L sals in pore-water composition during
burial diagenes is: Journal of Sedimen-
taxial overgrow1hs in muddy crinoidal
limestones; cathodoluminescence
Mayeda, T.K., Meents, WF. and Shimp,
N.F.,1966,Theoriginofsalineformation
tary Petrology, v. 52, p. 615-630. sheds new light on an old problem : Sedi- waters. I. Isotopic composition: Journal

c(, Matter, A., 1974, Burial diagenesis of pelitic


and carbonate deep-sea sediments
from the Arabian sea: Deep Sea Drilling
mentology, v. 31, p. 251-268.
Walls, R.A. and Burrowes, G., 1985, The
role of cementation in the diagenetic
of Geophysical Research, v. 71, p. 3869-
3882.
Collins , A.G., 1975, The Geochemistry of
Project Initial Reports , v. XXIII. history of Devonian reefs, in Schneider- Oil Field Waters: New York, Elsevier
(, Mattes, B.Wand Mountjoy, EW., 1980,Bur- mann , N.and Harris , P.M., eds., Carbon- Scientific Publishing Company, 496 p.
ial dolomitization of the Upper Devonian ate Cements: Society of Economic Cook, P.J., 1974, Geochemistry and diagen-
Miette buildup, Jasper National Park, Paleontologists and Mineralogists, Spe- esis of interst itial fluids and associated
Alberta, in Zenger, D.H., Dunham, J.B. cial Publication 36, p. 185-220. oozes, Deep Sea Drilling Project, Leg27,
and Ethington, R.L., eds., Concepts and Woodland, B.G., 1964, The nature and ori- Site 262, Timor Trough,in Veevers, J.J.,
Models of Dolomitization: Society of gin of "cone-in-cone" structure: Field- Heirtzler, J.R., et a/., Initial Reports of
Economic Paleontolog ists and Mineral- iana, Geology (Field Museum of Natural the Deep Sea Drilling Project, v. XXVII,
ogists , Spec ial Publication 28, History, Chicago), v. 13, p. 185-305. p.463·480 .
p.259·297. Yurewicz, D.A. and Dravis, J .J., 1984, Drever,J.I., 1982,The Geochemistry of Nat-
Improved recogn ition of sedimentary ural Waters: Prentice-Hall, Englewood
fabrics using fluorescence microscopy- Cliffs, J, 388 p.
implications for interpreting carbonate

r
c
108 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
Dunham, R.J., 1969, Early vadose silt in
Townsend mound (reef), New Mexico, in
Hitchon, B., Bill ings, G.K. and Klovan, J.E.,
1971, Geochemistry and origin of forma-
Roehl, P.O., 1981, Dilation brecciation - a
proposed mechanism of fracturing, c
Friedman , G .M ., ed., Depositional
Env ironments in Carbonate Rocks : a
symposium: Society of Economic Pale-
tion waters in the western Canada sedi-
mentary basin . 3. Factors controlling
chemical compos ition : Geochimica et
petroleum expulsion and dolomitization
in the Monterey Formation, California, in
Garrison RE ., Douglas, R.G., Pisciotto,
c
onto logists and Mineralogists, Special Cosmochimica Acta , v. 35, p. 567-598. K.E., Isaacs, C.M. and Ingle, J.C., eds.,
C
Publication 14, p. 139-181.
Galloway, W.E. , 1985, Hydrogeologic
Hitchon, B. and Friedman , I., 1975, Geo-
chemistry and origin offormation waters
The Monterey Formation and Related
Siliceous Rocks of California: Society of
c
regimes of sandstone diagenesis, in in the western Canada sedimentary Econom ic Paleontologists and Mineral- (
McDonald, D.A. and Surdam, RC., eds., basin. 1. Stable isotopes of hydrogen ogists, Pacific Section, Symposium ,
Clastic Diagenesis: American Assoc i- and oxygen: Geochim ica et Cosmo- p.285-315. C
ation of Petroleum Geologists, Memoir chimica Acta, v. 33, p. 1321-1349. Rosenberg, P.E. and Holland, H.D., 1964,
37, p. 3-13. Holland, H.D. and Malinin, S.D., 1979, The Calcite-dolomite-magnesite stabil ity C
relations in solutions at elevated temper-
Garven, G., 1985, The role of regional fluid
flow in the genesis of the Pine Point
solubility and occurrence of non-ore
deposits, in Barnes, H.L. , ed., Geo- atures: Science, v. 145, p. 700-701. C
depos it, Western Canada sedimentary
basin : Econom ic Geology, v.80,
chemistry of Hydrothermal Ore Depos-
its, Second Edition: Wiley, New York,
Sayles, E.L. and Manheim, F.G., 1975,Inter-
stitial solutions and diagenesis in buried
C
p.307-324. p.461-508. marine sediments : results from the C
Garven, G. and Freeze, RA. , 1984a, Theo-
retical analysis of the role of ground-
Kharaka, Y.K., Hull, R.W. and Carothers,
W.W., 1985, Water-rock interactions in
Deep Sea Drilling Project: Geochim ica
et Cosmochimica Acta , v. 39, p. 103-127. r
'-
water flow in the genesis of stratabound sedimentary basins, in Gautier, D. L., Secor, D.T., Jr., 1965, Role of fluid pressure
ore deposits. 1. Mathematical and Kharaka, Y.K. and Surdam, RC., eds., in jointing: American Journal of Science,
.[
numerical models : American Journal of Relationship of Organic Matter and v. 263, p. 633-646.
Science, v. 284, p. 1085-1124. Mineral Diagenesis: Society of Eco- Sharp , W.E. and Kennedy, G.C., 1965, The C
Garven , G. and Freeze, RA. , 1984b, Theo-
retical analysis of the role of ground-
nomic Paleontologists and Mineralo-
gists, Notes for Short Course No. 17,
system CaO-C0 2-H 20 in the two-phase
region calc ite + aqueous solution: Jour-
C
water flow in the genesis of stratabound
ore deposits. 2. Quantitative results:
p.79-176.
Klosterman , M.J., 1981, Application of fluid
nal of Geology, v. 73, p. 391-403.
Sippel , R.F. and Glover, E.D., 1964, The
c
Amer ican Journal of Science, v. 284 , inclusion techniques to burial diagene- solution alteration of carbonate rocks,
the effects of temperature and pressure :
C
p. 1125-1174. sis in carbonate rock sequences: M.S.
Graf, D.L. and Anderson, D.E., 1981, Geo- Thesis, Louisiana State University, Geochimica et Cosmochimica Acta , C
chem ical inputs for hydrologic models Baton Rouge, LA , 102 p. v. 28, p. 1401-1417.
of deep-lying sedimentary units - loss Kohout, EA ., 1965, A hypothesis concern- White, D.E., 1975, Saline waters of sedi- C
of mineral hydrat ion water: Journal of
Hydrology, v. 54, p. 297-314.
ing cyclic flow of salt water related to
geothermal heating in the Floridian
mentary rocks, in Young, A. and Galley,
G .E . , eds ., Fluids in Subsurface
C
Hanor, J.S., 1979, Sedimentary genesis of
hydrothermal fluids, in Barnes, H.L., ed.,
aquifer: New YorkAcademy of Sciences,
Transactions, Series II, v. 28, p. 249-271.
Environments: American Association of
Petroleum Geologists, Memoir 4,
C
Geochemistry of Hydrothermal Ore Kohout, EA ., 1967, Groundwater flow and p.342-366. C
Deposits , Second Edition: Wiley, New the geothermal regime of the Floridian Wood, J.R and Hewett, T.A., 1984, Reser-
York, p. 137-168. plateau : Gulf Coast Association of Geo- voir diagenesis and convective flu id C
Hanshaw, B.B., Busby, J. and Lee, R., 1978, logical Societies, Transactions, v. 17, flow, in McDonald, D.A. and Surdam,
Geochemical aspects of the Madison p.339-354. RC., eds., Clastic Diagenesis : Amer i- C
aquifer system, in Rehrig, D., ed., The
Economic Geology of the Williston
Land, L.S. and Prezbindowski, D.R, 1981,
The origin and evolution of saline forma -
can Assoc iation of Petroleum Geolo-
gists , Memoir 37, p. 99-110.
C
Basin : Montana, North Dakota, Sas-
katchewan, Manitoba: Montana Geo-
tion water, Lower Cretaceous carbon-
ates, south-central Texas: Journal of Burial Cements - Trace Elements and
C
logical Society, 24th Annual Confer- Hydrology, v. 54, p. 51-74. Cathodoluminescence C
ence, 1978 Williston Basin Symposium, O'Hearn, T.C., 1985, A fluid inclusion study
p.385-389. of diagenetic mineral phases, Upper Carpenter, A.B. and Oglesby, TW., 1976, A C
Helgeson, H.C., 1969, Thermodynamics of Jurassic Smackover Formation, south model for the formation of luminescently
hydrothermal systems at elevated tem- west Arkansas and northeast Texas: zoned calcite cements and its implica- C
peratures and pressures: American Applied Carbonate Research Program, tions: Geological Society of America, (
Journal of Science , v. 269, p. 729-804 . Lous iana State University, Technical Abstracts with Programs, v.8,
Helgeson , H.C.,1979 , Masstransferamong
mine rals and hydrothermal solutions, in
Series, Contribution No. 24, 189 p.
Plummer, L.N . and Back, W., 1980, The
p.469-470.
Fairchild, I.J., 1983, Chemical controls of
C
Barnes, H.L., ed., Geochemistry of mass balance approach - application to cathodoluminescence of natural dolo- -:t
Hydrothermal Ore Deposits, Second interpreting the chemical evolution of mites and calcites - new data and review:
Edition : Wiley, New York, p.568-610. hydrologic systems : American Journal Sedimentology, v. 30, p. 579-583. C
Hitchon , B., 1969a, Fluid flow in the western of Science, v. 280, p. 130-142. Frank, J.R, Carpenter, A.B. and Oglesby,
Canada sedimentary basin - 1. Effect Pray,L.C., 1966, Informal comments on cal- T.W., 1982, Cathodolum inescence and C
of topography: Water Resources cium carbonate cementation: Society of composition of calcite cement in the
G
Research, v. 5, p. 166-185.
Hitchon, B., 1969b, Fluid flow in the western
Canada sedimentary basin - 2. Effect of
Economic Paleontologists and Miner-
alogists, Technical session on lithifica-
tion and Diagenesis, St. Louis meetings ,
Taum Sauk limestone (Upper Cambrian),
Southeast Missouri: Journal of Sedi-
mentary Petrology, v. 52, p. 631-638.
..
geology: Water Resources Research,
v. 5, p. 460-469.
April 1966 (unpublished). Machel , H.G., 1985, Cathodoluminescence
in calcite and dolomite and its chemical
C
interpretation: Geoscience Canada, C
v. 12, p. 139-148.

c
(~
c Limestones - The Burial Diagenetic Environment 109

c
( Oglesby, T.W., 1976, A model for the dis- Irwin, H., Curtis, C.D . and Coleman , M., Prezbindowski , D.A ., 1985, Burialcementa-
tribution of manganese, iron and mag- 1977, Isotopic evidence for source of dia- tion - is it important? A case study,
( nesium in authigen ic calcite and dolo- genetic carbonates formed during burial Stuart City trend , south central Texas,in
c mite cements in the upper Smackover
Formation in eastern Mississippi : M.S.
of organic-rich sed iments: Nature,
v. 269, p. 209-213.
Schneidermann, N. and Harris, P.M.,
eds., Carbonate Cements : Society of
( Thesis, University of Missouri/Colum- Land, L.S., 1980, The isotopic and trace- Economic Paleontologists and Miner-
bia, Columbia, MO, 122 p. element geochemistry of dolomite - the alogists, Special Publication 36,
Pierson , B.J., 1981, The control of cath - state of the art, in Zenger, D.H., Dun- p.241-264.

c odoluminescence in dolomite by iron


and manganese : Sedimentology, v. 28,
p.601-610 .
ham, J.B. and Eth ington , A.L., eds.,
Concepts and Models of Dolomitization:
Society of Economic Paleontologists
Sofer,Z., 1978, Isotope compositionof hydra-
tion water in gypsum: GeochimicaetCos-
mochimica Acta, v. 42, p. 1141-1149.
( ten Have, T. and Heijen, w., 1985, Cath- and Mineralogists, Special Publication Stueber, A .M. and Pushkar, P., 1983,
(~ odoluminescence activation and zona- No. 28, p. 87-110 . Application of stront ium isotopes to ori-
tion in carbonate rocks: an exper imental Land , L.S., 1985, Environments of lime- gin of Smackover brines and diagenetic
o approach: Geologie en Mijnbouw, v. 64,
p.297-310.
stone and dolomite diagenesis - some
geochemical considerations: Notes for a
phases, southern Arkansas (abstr.):
American Associat ion of Petroleum
o Burial Cements - Stable Isotopes
short course on carbonate diagenes is,
Colorado School of Mines, Golden, CO,
Geologists, Bulletin , v. 67, p. 553-554.
Tan, F.C. and Hudson , J.D., 1974, Isotopic
April 8-10, 1985. studies of the paleoecology and diagen-

o Brinton, L., 1986, Deposition and diagene-


sis of phylloid algal banks, Ismay Field
Lohmann, K.C., 1983, Unravelling the dia-
genetic history of carbonate reservo irs -
esis of the Great Estuarine Series
(Jurassic) of Scotland : Scottish Journal

o and San Juan Aiver Canyon, Paradox


Basin, Utah: M.S. Thesis, Colorado
integration of petrographic and geo-
chemical techniques, in Wilson, J.L., et
of Geology, v. 10, p. 91-108.
Veizer,J. and Compston, W., 1974, 87Sr/ 86Sr
( School of Mines, Golden , CO, 316 p. et., Notes for a short course, American composition of seawater during the
Burke , W.H., Denison, A.E., Hetherington, Association of Petroleum Geologists Phanerozoic: Geochimica et Cosmo-
o A.B., Koepnick, A.B ., Nelson, H.F. and Annual Meeting , Dallas, Texas, April chimica Acta, v. 38, p. 1461-1484.

o Otto, J.B., 1982, Variation of seawater


87Sr/ 86Sr throughout Phanerozoic time:
1983.
Matter, A ., Douglas, A .G. and Perch-
Veizer,J. and Hoefs, J., 1976, The nature of
'80/'60 and '3C/'2C secular trends in

o Geology, v. 10, p. 516-519.


Choquette, P.W., 1971, Late ferroan dolo-
Nielsen, K., 1975, Fossil preservation,
geochemistry, and diagenesis of pelagic
sedimentary carbonate rocks: Geo-
chimica et Cosmochimica Acta, v. 49,

o mite cement, Mississippian carbonates,


Illinois Basin, U.S.A., in Bricker, O.P.,
carbonates from Shatsky Aise, north-
west Pacific, in Larson, A.L., Moberly,
p. 1387-1395.
Walls, A.A., Mountjoy, E.W. and Fritz, P.,
ed., Carbonate Cements: The Johns A., et aI., Initial Aeports of the Deep Sea 1979, Isotopic composit ion and dia-
Hopkins Press, Baltimore, MD, Drilling Project, v. XXXII, p. 891-921. genetic history of carbonate cements in
p.339-346. McKenzie , J.A., Bernoulli , D. and Garr ison, Devonian Golden Spike reef, Alberta,

o Choquette, P.w. and Steinen, A.P., 1980,


Mississippian non-supratidal dolomite,
A.G., 1978, Studies on lithification and
diagenesis - lithification of pelagic-
Canada: Geological Society of America
Bulletin, v. 90, p. 963-98.

o Ste. Genevieve Limestone , Illinois


Basin : evidence for mixed-water dolo-
mitization, in Zenger, D.H., Dunham ,
hemipelagic sediments at DSDP Site
372, oxygen-isotope alteration with dia-
genesis, in HsO, K.J., Montadert, L., et
Organ ic Geochemistry and Organic-
Inorganic Interactions
)
J.B. and Ethington , A.L., eds., Concepts al., Initial Aeports of the Deep Sea Drill-
o and Models of Dolomitization - a sym-
posium: Society of Economic Paleon-
ing Project, v. XLII, p. 473-478.
Meyers, W.J.and Lohmann, K.C., 1985, Iso-
Barnes, M.A., Barnes, W.C. and Bustin ,
A.M., 1984, Diagenes is and chemistry
tologists and Mineralogists, Special tope geochemistry of regionally exten- and evolution of organic matter: Geo-
science Canada, v. 11, p. 103-114.
o Publication 28, p. 163-196.
Czerniakowski, L.A., Lohmann , K.C. and
sive calcite cement zones and marine
components in Miss issippian lime- Berner, A.A., 1975, Diagenetic models of .

o Wilson, J.L., 1984, Closed-system


marine burial diagenesis - isotopic data
from the Austin chalk and its compo-
stones, New Mex ico , in Schneider-
mann , N.andHarris, P.M., eds., Carbon-
ate Cements: Society of Economic
dissolved species i n the interstitial
waters of compacting sediments: Ameri-
can Journal of Science , v. 275, p. 88·96.
l nents: Sedimentology, v. 31, p. 863-877. Paleontologists and Mineralogists, Spe- Bjorlykke , K., 1984, Formation of secondary
Dickson, J.A .D. and Coleman, M.L., 1980, cial Publication 36, p. 223-240. poros ity: how important is it? , in
l Changes in carbon and oxygen isotope Moldovanyi, E.P. and Lohmann, K.C., 1984, McDonald, D.A. and Surdam, A.C., eds.,
o composition during limestone diagene-
sis: Sedimentology, v. 27, p. 107-118.
Isotopic and petrographic record of phre-
atic diagenesis - LowerCretaceous Sligo
Clastic Diagenesis: American Associa-
tion of Petroleum Geologists, Memoir37,
C Fritz, P. and Jackson, S.A., 1972,Geochem-
ical and isotopic characteristics of Mid-
and Cupido Formations: Journal of Sedi-
mentary Petrology, v. 54, p. 972-985.
p. 127-151.
Curtis, C.D., 1977, Sedimentary geochem-
(~ dle Devonian dolomites from Pine Point, Murata , K.J., Friedman, I. and Madsen , istry - environments and processes
northern Canada: 24th International B.M., 1969, Isotopic composition of dia- dom inated by involvement of an
C' Geological Congress, Montreal, Pro- genetic carbonates in marine Miocene aqueous phase : Aoyal Society of
( ceedings, Section 6, p. 230-242. formations of California and Oregon : London , Philosophical Transactions ,
Hudson, J.D., 1975, Carbon isotopes and United States Geological Survey, Pro- v. 286A, p. 353-372.
:'r .
limestone cement: Geology, v.3 , fessional Paper 614-B. Curtis , C.D., 1978, Possible links between
'-. p.19-22. O'Neil, J.A., Clayton , A.N. and Mayeda, sandstone diagenesis and depth-
c
f"
Hudson, J.D., 1977, Stable isotopes and
limestone lithification: Journal of the
T.K., 1969,Oxygen isotope fractionation
in divalent metal carbonates: Journal of
related geochemical react ions occur-
ring in enclosing mudstones: Journal of
\. Geological Society of London, v. 133, Chemistry and Physics, v. 51, p. 5547- the Geological Society of London,
p.637-660. 5558. v. 135, p. 107-117.
c
110 Diagenesis Geoscience Canada Reprint Series 4 c
c
Deroo , G . , Power, T.G ., Tissot, B., Mackenzie, A.S., Patience, R.L. and Max- Hancock, J.M., 1976, The petrology of the
c
McCrossan , R.G. and Hacquebard, P.A., well , J.R ., 1981, Molecular changes and Chalk : Geological Soc iety of London, c
1977, The origin and migration of petro-
leum in the western Canadian Sedimen-
tary basin - a geochemical and thermal
the maturation of sedimentary organ ic
matter, in Atkinson, G. and Zuckerman,
J., eds., Origin and Chemistry of Petro-
Proceedings, v. 86, p. 499-535.
Mapstone , N.B., 1975,Diagenet ic history of
a North Sea chalk: Sedimentology, v. 22,
c-
maturation study : Geological Survey of leum: Pergamon Press, Oxford , p. 1-31, p.601·613. C
Canada, Bulletin 262.
Dow, w., 1977, Kerogen studies and geo-
McBr ide, E.E , 1977, Secondary porosity -
importance in sandstone reservoirs in
Matter, A ., Douglas, R.G . and Perch-
Nielsen, K., 1975, Fossil preservation,
r:
logical interpretations: Journal of Geo-
chemical Exploration, v. 7, p. 79-99 .
Texas: Gulf Coast Association of Geo-
logical Societies, Transactions, v. 27,
geOChemistry, and diagenesis of pelagic
carbonates from Shatsky Rise, north -
(~
Espitalie, J., Laporte, J .L., Madec , M.,
Marquis , E , Leplat , P., Paulet , J. and
p. 121-122.
Mitterer, R.M ., 1968, Amino acid composi -
west Pacific, in Larson , R.L., Moberly,
R., et ei., Initial Reports of the Deep Sea
C
Boutefen, A., 1977, Methode rapide de tion of organic matrix in calcareous Drilling Project, v. XXXII, p. 891-921, C
characterisation des roches-meres, de
leur potentiel petrolier et de leur degre
oolites: Science, v. 162, p. 1498-1499.
Powell, T.G., Foscolos, A.E ., Cunther, P.R.
McKenzie , J.A., Bernoulli, D. and Garrison,
R.E., 1978, Studies on lithification and r
d'evolution: Revue de l'lnstitut Francais and Snowdon, L.R., 1978, Diagenesis of diagenesis - lithification of pelagic-
du Petrote, v. 32, p. 23-42 . organic matter and fine clay minerals - a hemipelagic sediments at DSDP Site C
Foscolos, A.E. and Powell, T.G., 1980, Min-
eralogical and geochemical transforma-
comparative study: Geochimica et Cos-
mochim ica Acta, v. 42, p. 1181-1198.
372, oxygen- isotope alteration with dia-
genesis, in HsG, K.J., Montadert, L., et
C
tions of clays during catagenesis and
the ir relation to oil generation, in Miall,
Schmidt, V. and McDonald, D.A., 1979, The
role of secondary porosity in the course
aI., Initial Reports of the Deep Sea Drill-
ing Project, v. XLII, p. 473-478.
C
A.D., ed., Facts and Principles of World
Petroleum Occurrence: Canadian Soci-
of sandstone diagenesis, in Scholle, P.A.
and Schluger, P.R. , eds., AspectsofDia-
Mimran, Y., 1977, Chalk deformation and
large-scale migration of calcium carbon-
·C
ety of Petroleum Geologists, Memoir 6, genesis: Society of Economic Paleon- ate: Sedimentology, v. 24, p. 333-360. C
p. 153-172. tologists and Mineralogists, Spec ial Neugebauer, J., 1973, The diagenetic pro-
Froelich, P.N., Klinkhammer, G.P., Bender, Publication 26, p. 175-207. blem of chalk - the role of pressure solu- C
M.L., Luedtke, N.A ., Heath, G.R .,
Cullen, D., Dauphin, P., Hammond, D.,
Snowden , L.R . and Powell , T.G., 1982,
Immature oil and condensate - modi-
tion and pore fluid: Neues Jahrbuch fUr
Geologie und Palaontoloqie, Abhand-
c
Hartmann, B. and Maynard, V.,1979,
Early oxidation of organic matter in
fication of hydrocarbon generation
model for terrestrial organic matter:
lungen, v. 143, p. 223-245.
Neugebauer, J., 1974, Some aspects of
C
pelagic sediments of the eastern equa- American Association of Petroleum cementation in chalk, in HsG, K.J. and c
torial Atlantic: suboxic diagenesis: Geo-
chimica et Cosmochimica Acta, v. 43,
Geologists, Bulletin , v. 66 , p. 775-788.
Suess, E., 1970, Interaction of organic com-
Jenkyns, H.C., eds ., Pelagic Sediments
on Land and Under the Sea: Interna- c
p. 1075-1090.
Hayes, J.B., 1979, Sandstone diagenesis-
pounds with calc ium carbonate. I. Asso-
ciation phenomena and geochemical
tional Association of Sedimentologists,
Special Publication 1, p. 149-176. c
the hole truth, in Scholle, P.A. and
Schluger, P.R., eds ., Aspects of Diagen -
implications: Geoch imica et Cosmo-
chimica Acta, v. 34, p. 157-168.
Scholle , P.A., 1974, Diagenesis of Upper
Cretaceous chalks from England, North-
c
esis: Society of Economic Paleontolo- Suess, E. and FOtterer, D., 1972, Aragonitic ern Ireland and the North Sea, in HsO, ,C
gists and Mineralogists, Special Pub- ooids - experimental precipitation from K.J. and Jenkyns, H.C., eds ., Pelagic
lication 26, p. 127-140.
Hood, A. and Castano, J.R., 1974,Organ ic
seawater in the presence of humic acid :
Sedimentology, v. 19, p. 129-139.
Sediments on Land and Under the
Sea: International Assoc iation of Sedi-
C
metamorphism - its relationship to Surdam , R.C., Boese, S.w. and Crossey, mentologists, Special Publication 1, C
petroleum generation and application to L.J., 1984, The chem istry of secondary p.177·210.
studies of authigenic minerals: United porosity, in McDonald, D.A. and Sur- Scholle, P.A., 1977, Chalk diagenesis and its C
Nations ESCAP, CCOP, Technical Bul- dam , R.C ., eds ., Clastic Diagenesis: relation to petroleum exploration - oil
letin 8, p. 87-118. American Association of Petroleum from chalks, a modern miracle?: Ameri- C
Hue, A.Y. and Durand, B.M., 1977, Occur-
rence and significance of humic acids in
Geologists, Memoir 37, p. 127-149.
Tissot , B.P., Bard, J.F. and Espitalie, J.,
can Association of Petroleum Geolo-
gists, Bulletin, v. 61, p. 982-1009.
C
ancient sediments: Fuel, v. 56, p. 73-80.
Irwin, H., Curtis, C.D. and Coleman, M.,
1980, Principal factors controlling the
timing of petroleum generation, in Miall,
Van den Bark, E. and Thomas, O.D., 1980,
Ekofisk : first of the giant oil fields in
C
1977, Isotopic evidence for source of dia- A.D., ed., Facts and Principles of World western Europe, in Halbouty, M.T., ed., C
genetic carbonates formed during burial Petroleum Occurrence : Canadian Giant Oil and Gas Fields of the Decade
of organic-r ich sediments : Nature, Society of Petroleum Geologists, 1968- 1978: Amer ican Assoc iation of (
v. 269, p. 209-213.
Kharaka, Y.K., Hull , R.w. and Carothers,
Memoir 6, p. 143-152. Petroleum Geologists, Memoir 30,
p.195-224. c
W.W., 1985, Water-rock interactions in
sedimentary basins, in Gaut ier, D.L.,
Burial Diagenesis of Chalks and Other
Fine-Grained Oceanic Carbonates
Wolfe, M.J., 1968, Lith ificat ion of a carbon-
ate mud - Devonian chalk in Northern
c:
Kharaka, Y.K. and Surdam, R.C., eds.,
Relationship of Organic Matter and Min- Beall , A.O. and Fischer, A.G ., 1969, Sedi-
Ireland: Sed imentary Geology, v.2,
p.263-290.
c
erai Diagenesis: Society of Economic mentology, in Ewing , M., et a/., eds. ,
Paleontologists and Mineralogists , Initial Reports of the Deep Sea Drilling Porosity in Burial Diagenesis
Notes for Short Course No. 17, p. 79-176. Project, v. I, p. 521-593. c
Lundegard, P.A., 1985, Carbon dioxide and
organic acids: origin and role in burial
Feazel, C.T., Keany, J. and Peterson , R.M.,
1985, Cretaceous and Tertiary chalk of
Choquette, P.w. and Pray, L.C., 1970, Geo-
logic nomenclature and classification of c
diagenesis, Texas Gulf Coast Tertiary:
Ph.D. Thesis, University of Texas/Aus-
the Ekofisk Field area , central North
Sea, in Roehl, P.O. and Choquette, PW.,
porosity in sedimentary carbonates:
American Association of Petroleum
(
tin , Austin, TX, 145 p. eds. , Carbonate Petroleum Reservoirs :
Springer-Verlag, New York, p. 495-511.
Geologists, Bulletin , v. 54, p. 207·250. c
c
c Limestones - The Burial Diagenetic Environment 111

('
c Donath, EE ., Carozzi, A.V., Fruth, L.S., Jr. Moore, C.H. and Druckman, Y., 1981, Burial Isaacs, C.M., 1981, Porosity distribution dur-
( and Rich, DW., 1980, Oomold ic porosity diagenesis and poros ity evolution, upper ing diagenesis of the Monterey Forma-
experimentally developed in Mississip- Jurassic Smackover, Arkansas and tion , Santa Barbara coastal area, Califor-
c(. pian oolitic limestones : Journal of Sedi-
mentary Petrology, v. 50, p. 1249-1260.
Louisiana: American Assoc iat ion of
Petroleum Geologists, Bulletin , v. 65,
nia, in Garr ison, R.E., Douglas, R.G.,
Pisciotto, K.E., Isaacs, C.M. and Ingle,
Dravis, J.J., 1987, Reservo ir poros ity in Up- p.597-628. J.C., The Monterey Formation and Re-
per Jurassic Haynesville limestones in Moshier, S.O., 1987, Microporosity in micritic lated Siliceous Rocks of California: So-
east Texas: evidence for deep-burial gen- limestones: a review: Society of Eco- ciety of Economic Paleontologists and

cr eration: Society of Economic Paleontolo-


gists and Mineralogists, Abstracts, v. IV,
1987 Midyear Meeting , p. 22.
nom ic Paleontologists and Mineralo-
gists, Abstracts, v. IV, 1987Midyear Meet-
ing, p. 58.
- Mineralogists, Pacific Section, Sym-
posium, p. 257-272.
James, N.P. and Choquette, P.W., 1983,
Elliott , T.L., 1982, Carbonate fac ies, deposi- Schmoker, JW., 1984, Empirical relation be- Limestones - The Sea-floor Diagenetic
c tional cycles and the development of sec-
ondary porosity during burial diagene-
tween carbonate porosity and thermal
maturity - an approach to regional poros-
Environment: Geoscience Canada, v. 10,
p.162-179.
o sis, in Christopher, J.E and Kaldi,J., eds. , ity predict ion: Amer ican Association of James, N.P. and Choquette, PW., 1984,

c 4th International Williston Basin Sym-


posium: Saskatchewan Geological So-
Petroleum Geologists, Bulletin, v. 68,
p. 1697-1703.
Limestones - The Meteoric Diagenetic
Environment: Geoscience Canada, v. 11,

o ciety, Special Publication 6, p. 131-151.


Enos, P.and Sawatsky, L.H., 1981, Pore net-
Schmoker, J.w. and Halley, R.B., 1982, Car-
bonate porosity versus depth - a predict-
p. 161-194.
Kendall, A.C., 1984, Evaporites, in Walker,

o works in Holocene carbonate sediments:


Journal of Sedimentary Petrology, v. 51,
able relation for south Florida: American
Association of Petroleum Geologists,
A.G., ed., Facies Models, Second Edi-
tion: Geological Association of Canada,
o p.961-985.
Feazel, C.T. and Schatzinger, A.A. , 1985,
Bulletin , v. 66, p. 2561-2570.
Scholle , PA and Halley, A.B. , 1985, Burial
Geoscience Canada Reprint Series 1,
p.259-298.
o Prevention of carbonate cementation in
petroleum reservoirs , in Schneider-
diagnesis: out of sight , out of mind! , in
Schneidermann, N. and Harris, P.M.,
Lippman, E, 1973, Sedimentary Carbonate
Minerals: Springer-Verlag, Berlin, 228 p.
( mann , N. and Harris , P.M., eds., Carbon- eds., Carbonate Cements: Society of Murray, A.C., 1964, Origin and diagenesis of

o ate Cements: Society of Economic Pale-


ontologists and Mineralogists, Special
Economic Paleontologists and Mineralo-
gists, Special Publication 36, p. 309-334 .
gypsum and anhydrite : Journal of Sedi-
mentary Petrology, v. 34, p. 512-523.

o Publication 36, p. 97-106.


Giles, M.A. and Marshall, J.D., 1986, Con-
Yanguas, J.E. and Dravis, J.J., 1985, Blue
fluorescent dye technique for recognition
Perry, E.A. and Hower, J., 1970, Burial dia-
genesis in Gulf Coast pelitic sediments:
o straints on the development of secondary
porosity in the subsurface: re-evaluation
of micro porosity in sedimentary rocks:
Journal of Sedimentary Petrology, v. 55,
Clays and Clay Minerals, v. 18, p. 165-177.
Radke, R.M. and Mathis, R.L., 1980, On the
of processes : Marine and Petroleum Ge- p.600-602. formation of saddle dolomite: Journal of
ology, v. 3, no. 3, p. 243-255. Sedimentary Petrology, v. 50, p. 1149-1168.
(' Grabowski, G.J., Jr., Wendte, J.C., Williams, Minerai Transformations, and Other Sando, W.J., 1974, Ancient solution pheno-

o S.C.,Anderson,J.H ., Kick, A.M., Harrison,


W.J., McFarlan, E, Jr., Reeckmann, SA
References mena in the Madison Limestone (Missis-
sippian) of north-central Wyoming :

c and Kaufman,J., 1987, Grain interpenetra-


tion, pressure solution and cementation of
Beach, D.K., 1982, Depositional and diage-
netic history of Pliocene-Ple istocene car-
United States Geological Survey, Jour-
nal of Research, v. 2, no. 2, p. 133-141.
() Upper Smackover lime grainstones, Gulf
of Mexico: Society of Economic Paleon-
bonates of northwestern Great Bahama
Bank: evolution of a carbonate platform :
Sando, w.J ., 1985, Revised Mississippian
time scale, western interior region, con-
o tologists and Mineralogists, Abstracts,
v.I\I, 1987 Midyear Meeting, p. 30-31.
Ph.D. Thesis, University of Miami, Miami,
FL, v. 1, 447 p.
terminous USA: United States Geolo!]i-
cal Survey, Bulletin 160SA, 18 p.
(, Halley, A.B. and Harris, P.M., 1979, Fresh- Boles, J.R. and Franks , G., 1979, Clay dia- Schlee, J.S ., 1974, ed., Interregional Uncon-

o water cementation of a 1000-year-old


oolite: Journal of Sedimentary Geology,
genesis in Wilcox sandstone of southeast
Texas: implications of smectite diagene-
formities and Hydrocarbon Accumula-
tion: American Association of Petroleum

o v. 49, p. 969-988.
Halley, A.B . and Schmoker, J.M., 1982, High
sis on sandstone cementation: Journal of
Sedimentary Petrology, v.49, p.55-70.
Geologists, Memo ir 36, 184 p.
Steinen, R.P., 1974, Phreatic and vadose
poros ity Cenozoic carbonate rocks of Burst, J.E, 1969, Diagenesis of Gulf Coast diagenetic modification of Pleistocene
l South Florida : progressive loss of poros- clay sediments and its possible relation to limestone: petrographic observations
o ity with depth: American Association of
Petroleum Geologists, Bulletin , v. 67,
petroleum migration: Amer ican Assocta-
tion of Petroleum Geologists, Bulletin,
from subsurface of Barbados, West
Indies: American Association of Pe-
o p.191-200.
Harrison, A.S., 1975,Porosity in Pleistocene
v. 53, p. 73-93.
Enos, P. and Perkins, R.D., 1977, Quaternary
troleum Geo logists , Bulletin, v.58,
p. 1008·1024.
c grainstones from Barbados: some prelimi- Sedimentation in South Florida: Geologi- Steinen, R.P. and Matthews, R.K., 1973,

o nary observations: Bulletin of Canadian


Petroleum Geology, v. 23, p. 383-392.
Lockridge, J.P. and Scholle , P.A., 1978,
cal Society of America, Memoir 147,
198 p.
Gregg, J.M. and Sibley, D.E, 1984, Epigene-
Phreatic versus vadose diagenesis :
stratigraphy and mineralogy of a cored
borehole on Barbados, w.1.: Journal
Niobrara gas in eastern Colorado and tic dolomit ization and the origin of xeno- of Sed imentary Petrology, v.43 ,
(
northwestern Kansas: Rocky Mountain topic dolomite texture : Journal of Sedi- p. 1012-1020.
/- ,
Association of Geologists 1978 Sym- mentary Petrology, v. 54, p. 908-931.
posium , p, 35-49. Hower, J., Eslinger, EV., Hower, M.E. and
Moore, C .H., 1985, Upper Jurassic sub- Perry, EA. , 1976, Mechan ism of burial
surface cements: a case history, in metamorphism of argillaceous sed i-
Schneidermann, N. and Harris, P.M., ments - 1. Mineralogical and chemical Originally published in
eds., Carbonate Cements: Society of evidence: Geological Society of America Geoscience Canada v. 14 Number 1
r: , Economic Paleontologists and Mineralo- Bulletin, v. 87, p. 725-737. (March 1987)
'-..' gists, Special Publication 36, p. 291-308. Revised 1987
/-

'-
c
c
112 Diagenesis Geoscience Canada Reprint Series 4 c
C
C
C
c-
C
C
('
C
C
{
C
C
C
C
C
C
~
c
c
c
c
c
c
C
c
C
Photographs of diagenetic dolomite of the Manetoe Facies developed in the Middle Devonian Nahanni Formation in the Kotaneelee Gas
C
Field of Southeastern Yukon Territory. The box outline on the core photograph on the left indicates the area covered by the photomicrograph (.
on the right (image reversed). Coarsely crystalline "saddle" dolomite with curved crystal faces infills pore spaces (P) in a dolomitized pelletal
packstone laminite. Stylolites (S) postdate dolomitization. Photograph courtesy of D. W. Morrow (Geological Survey of Canada). C
C
C
c
e
c
c
c
c.
c
c
c
C
l Dolomites - Chemistry and Precipitation 113

~
(, erable amount of experimental and the- dolomite and, like the emperor who had
( oretical data concerning the chemistry no clothes, it stands before us embar-
of the dolom itization process and the rassingly naked. In this review, I will
G precipitation of the mineral dolomite
from solution, no consensus exists
assemble and stitch together the
experimental, field and theoretical evi-
( regarding the general chemical condi- dence concerning the chemistry of
( tions required for dolomitization. The dolomitization into what I hope will pass
absence of a widely. acc.ep.te_d~th~.or.y as an example of sartorial elegance.
c
(
concernin g the chemistrY.Ql(loJQJIlit.im:.
tion is due Rr imatil¥-toJhe..dif.ficuLt.y..i~ DOLOMITE CRYSTAL STRUCTURE
precipitatin9 dolomite from aePJ:QB.!iate • AND COMPOSITIONAL VARIABILITY
Dolomite - Part 1:
solutions at tem w~tu~e.s..less-than The mineral dolomite has an ideal
C The Chemistry of 1OO° C.• This has prevented direct inter- chemical composition of CaMg(C03)2
Cl Dolomitization and pretation of the physico-chemical con- and a sxmmeJ,!:y..§tructure3 in the trigo-
ditions that prevailed during the pre- nal subsystem of the hexagonal GLY.s!&
( Dolomite Precipitation cipitation of most dolostones in nature ~ste!I! . The unit cell is a rhombohe-

o with the exception of those that were


formed at high temperature. lJJg.in.;,
dron elongate parallel to the "c" crys-
tallographic axis (Figure 3) similar to
o D.W. Morrow
Institute of Sedimentary and
abilityto precip.!t?t~99Jqmite undetcoji-
trolled laboratoryconditions constitutes
that of calcite but more highly ordered,
and has a lower degree of symmetry
( Petroleum Geology the essence of the g!Qtllem 01the Qr)gio because of the substitution of magn~·
3303-33rd Street N. W.
( of dolomite. sium atoms for half of the calcium
Calgary, Alberta T2L 2A7 The interpretation of the origin of a atoms. eiKe calcite, the dolomite crystal
( particular dolostone is therefore de- l'SbliiitU poflayersofcations(Ca2+ ,Mg2+)
INTRODUCTION pendant upon inferences that are alternating with anions (CO~-) perpen-
Dolostones form a large part of the Pro- derived mainly from comparisons with dicular to the c-axis direction with the
terozoic and Phanerozoic successions a variety of dolomitization models, distinction that half of the cation layers
in many areas of Canada, but are par- such as the Evaporative Pumping Mo- are magnesium layers. It is this regular
ticularly abundant in lower Paleozoic del, the Reflu x Model , the Cooron g alternation of calci~Rd-ma9ReSium
c strata (Figure 1). These strata are pre-
dominantly carbonate unlike the overly-
~el, the Solution-Cannibalization
Model, the Mixed-Water or Dorag Mo-
layers with intervening carbonate layers
mat uniquely character rzesthe r nlnerar
o ing Mesozoic and underly ing Protero-
zoic strata that are dominated by
del, the Compaction Model and other,
less commonly encountered ones.
dolomite.
Dolomite crystals in nature and those
o terr igenous sediments. This reflects the These models are discussed in a fol- synthesized experimentally are better
o fact that during early Paleozoic time
Canada was part of the Laurentian land-
lowing paper on dolomite entitled
"Dolomitization Models and Ancient
represented by the formula:
Ca(1 + x) Mg(1-x)(C03)2 and commonly
C) mass that was situated in the tropical Dolostones". Taken together, they pre- depart considerably from an ideal com-
equatorial belt (Ziegler et el., 1979). The position and structure. Three distinct
o economic importance of dolostones
sent a bewildering complexity of choice
and it is commonly not apparent or uni- factors contribute to this departure.
parallels their abundance in the strati- versally agreed upon as to what are the The degree of order of a composi- 5"0 : .
C graphic record (Figure 1). Dolostones essential features of these models that tionally ideal (i.e., stoichiometric) dolo-
C form important reserveif:&.fGr...oil (e.g., renders them agents of dolomitization mite crystal is affected by the degree to
the Leduc Formation or 03) and gas (e.g., high Mg/Ca solution ratios, low which calcium and magnesium are seg-
(e.g., Manetoe Facies, Figure 2) and are salinities, high salinities, high [C0 3 2-1, regated into their respective layers .
the main host rock in Canada foriea(j': large organiccontent,low sulphate con- Firstly, l! calcium atoms from calciLUIl_
ZinC mineral deposits {e.g. , the Pres- tent) or even why such features promote layers are i nter£han~~ an equa). .D-Q
qu'i1e Facies of the Pine Point deposit).
The importance of dolostones in Can-
dolomitization . For example, does a
lowering of salinity favour dolomitiza-
-.number of m ~gnesium atomsfrom mag-
. .-
neslum layers the degree of order of the
~

ada is a true reflection ofthe world-wide tion from a kinetic standpoint (Folk and crystal is lowerea artnough its comlLQ.S.L
importance of dolostones as reservoirs Land, 1975) or largely from a thermo- tion is unaffected. Most natural dolo-
for hydrocarbons and as hosts for lead- dynamic stand oint Badiozamani, mites display some degree of mixing of
zinc deposits (e.g., see Davies, 1979 1 3? It is not sufficient merely to state calcium and magnesium between cat-
r: and Macqueen , 1979). that a drop in salinity promotes dolomiti- ion layers (Goldsmith and Graf, 1958;
Given the major, albeit indirect, role zation, we must know why and under Carpenter, 1980). Secondly, dolomites
that the mineral dolomite has played in what circumstances this is true if we are commonl y depart from a stoichiometric-zfC
contributing to the well being and growth to make full use of this insight in our com position because of an excess Of.~
of the Canadian and world economies, interpretations. In other words, the for- calcium which is accommodated in the
one might assume that the process of midable array of current models for magnesil ,mlayers {Goldsmith and Graf,
dolomitization and the precipitation dolomitization is not clothed by any cer- 1958; Lumsden and Chimahusky, 1980).
of dolomite are well understood. Un- tain or complete understanding of the Finally, a multitude of cations, primarily
fortunately, although there is a consid- precipitational conditions of the mineral Fe, Sr, Na and Mn, substitute for cal-

'-....

c
c
114 Diagenesis Geoscience Canada Reprint Series 4 (

C
C
C
SOUTHEASTERN CANADA C
WESTERN REGION AND OFFSHORE
c
TRIASSIC-JURASSIC
PERMIAN 1-:-"':::';:'=:='-=-=---""
TURNER VALLEY _ _...,
MI SS.-PENN, ""::"~=~~:=-'--
30- 1
(LODGEPOLE) ARCTl C CANADA
c
PRESQU'ILE
20- (
MANETOE
KEG RIVER
WINNIPEGOSIS 10- c
DEVONIAN 31 LEDUC
NISKU
2(DUNDEE AND LUCAS) 3
c
GROSMONT
(SWAN HILLS)
(PINE POINT)
0- T-J P M-P D S 0 € P
c
c
SILURI AN 16
CANADIAN SHIELD
17 GUELPH 2 ALLEN BAY (BLUE FIORD)
c
c
ORDOVICIAN 9 \<ll-iITIAKER 2 9 (TRENTON)
(ST. GEORGE)
2 (THUMB MOUNTAIN)
c
CAMBRIAN
c
11 6 THER£SA 8
C
c
PROTEROZOIC 3+unnamed parts of
4 groups
7+ unnamed parts of 5 groups 1 5 SOCIETY CLIFFS
c
c
c
Figure 1 (top) A chart showing the c
numerical distr ibution of Canadian doto-
stones that have been formally named. Units
c
that are named in the chart have economic
importance both as reservoirs for oil and gas
c
or as hosts for Pb-Zn deposits. Names in C
brackets are partly dolomitized limestone
units in which the dolomite phase has eco- c
nomic importance. Inset graph shows dis-
tribution of Canadian dolostones according c
to geolog ic age.
c
(
c
c
Figure 2 (right) An SEM photomicro-
graph of the gas-bearing dolomite of the c
Manetoe Facies in the Yukonand Northwe st
Territories. Well-formed (Le., idiotopic) crys- c
tals of white dolomite (D) project into a vug
that is lined in part by reniform bitumen (B). c
The surrounding dolomite has very low (
porosity and permeability. Dolomitization
preceded the introduction of hydrocarbons. L

c
(
C
\...
C
Dolomites - Chemistry and Precipitation 115

cium in many dolomites (e.g., Veizer et 1978; Gidman, 1978) to dolomites that other species that have a lower free
al., 1978). Iron in particular may be pre- are not ideal in structure or composition. energy of formation, but the process
sent in concentrations of up to 4 or 5 Such names tend to obscure the sim- may be extremely slow, as, for example
mole% in ferroan dolomites. ilarity of these non-ideal dolomites to in the conversion of diamond to gra-
These departures from the ideal com- ideal dolomite and Land (1980) sug- phite on the earth's surface. Such com-
position also diminish the ordering of gested retaining the name dolomite for pounds are commonly called meta-
( the crystals (Carpenter, 1980). Intra- all such phases that have a composition stable to indicate the fact that they exist
crystal variations in composition and near CaMg(C0 3 b and display evi- for variably long periods of time within
C- degree of order are also common, par-
ticularly in larger crystals (e.g., Fritz and
dence, such as superstructure reflec-
tions in x-ray patterns, of the degree of
the stability field of other compounds of
similar composition. The appropriate-
O Katz, 1972). There is even some evi- order characteristic of dolomite. ness of the terms "metastable" and
r dence that compositional var iations
have influenced the shape of the coarse THE STABILITY OF DOLOMITE IN
"inert" are obviously dependent on the
period of time over which a reaction is
crystals with curved faces that are com- NATURAL ENVIRONMENTS being considered , which in this case, is
mon in some late diagenetic dolostones Minerals that have survived unchanged geolog ic time.
(Radke and Mathis, 1980). The degree for long periods of time in natural The factors (e.g., catalysts , tempera-
of disorder and of departure from environments do so for one of two rea- ture and concentration) that influence
stoichiometry also affects the unit cell sons. The mineral may be stable ther- the speed of a chemical reaction are
r:
dimensions and the solubility of dolo- modynamically, whiph isJ.~L~Y. i! wfllriOt known collectively as reaction kinetic
..!!!!ill (Land, 1980). § affected by small chan ges in the
o Many authors have applied the name environment,..QIjrnuninera.li&J.lo.stable
effects . The dolomite-calcite relation-
ship is one of the more spectacular
protodolomite or even pseudodolomite ~rmod¥oamica1Ly_buUs..itle.r.t Inert natural examples of the influence of
(e.g ., Gaines, 1977, 1978; Deelman , minerals are in the process of change to kinetic factors . Under a wide range of
surface and near-surface conditions
DOLOMITE dolomite is favoured thermodynam-
ically ove r co-existing calcite . The
o CaMg(C03 ) 2

I~
dolomitization reaction, as it is corn-

o SUBSTITUTION
/ <,SUBSTITUTION
monly expressed (e.g., Bathurst, 1975)
2CaC0 3 + Mg2+ ..... CaMg(C03 h + Ca 2+ (1)
is characterized by a free energy
OF Fe,Sr,No OF Co
change of ~Go r = -1.83 kilocallmole for
the transformation of aragonite to dolo-
mite of ideal composition and structure
o (Table 1), which indicates that this reac-
r tion has a thermodynamic drive toward
lAYERED dolomitization under standard condi-
A SUPERSTRUCTURE tions and unit molar concentrations.
5 We may use the relationship ~Gr =
o .4 ~Go r + RTlnQ (where, Q = activity

() ratio of Ca 2+ IMg2+, R = the gas con-


3
stant, andT = absolute temperature), to
2
derive a value of 21.96 for the activity
1 ..... ... ratio Ca2+IMg2+ for reaction (1) at equi-
o o Co
librium. The accuracy of this value
.. C03 depends upon the accuracy of esti-
r:
mates for the free energies of formation
'M9 of the products and reactants in equa-
r tion (1) (see table 2 in Carpenter, 1980).
Solutions with smaller values of Q will
favour the replacement of aragon ite
by ordered dolomite. Seawater is one
such solution with a Q value of only 0.16
(Garrels and Thompson, 1962; Wigley
and Plummer, 1976) indicating a strong
thermodynamic drive toward the re-
placement of aragonite and calcite by
Figure 3 Diagram of four rhombohedral unit cells of dolomite showing its layered super- dolomite in the world 's oceans. What
structure perpendicular to the "c " axis direction composed of regularly alternating sheets of perversity of nature has left the vast
calcium, magnesium, andcarbonate. Commonly Ca and Mg are incompletely segregated into present-day submarine blankets of
their respective layers and there is an excess of calcium. Also many foreign ions substitute for aragonite undolomitized?
calcium. These defects affect the thermodynamic properties of dolomite.

r
c
116 Diagenesis Geoscience Canada Reprint Series 4 c
c
The Mg2+ in equation (1) is neces- tion and lower the thermodynamic drive tions that fall in the region of the immis- c
sarily supplied in solution to the reaction
site from an external source. Lippman
toward dolomitization of reaction (2).
It may be assumed that, like other
ci bility gap between calCite and dOlo-
mite (Figure 4) is evidence of slow reac-
c
(1973) has emphasized that dolomite diagenetic reactions involving carbon- •tion rates. However, recent work has (
precipitates from ions in solution and
that the CaC0 3 must dissolve before
ates, dolomitization is entirely a wet
chemical process (see Lippman, 1973;
shown that there may be some stable
phases of intermediate composition c
dolomite can form if the Ca2+ and CO~­
ions are derived from the CaC0 3 alone .
Bathurst, 1975; Land, 1980). Solid state
reactions between carbonate minerals
between the low temperature calcite
and dolomite stable end members
c
It is also possible that part of the CO~- in in the absence of an aqueous phase (Reeder and Wenk, 1979). (
dolomite may have been supplied by the
solutionfrom anexternalsourceand Lipp-
proceed prohibitively slowly at tempera-
tures lessthan several hundred degrees
Water of various compositions occu-
pies even sub-micron-sized lamellar c
man (1973) has proposed the reaction
CaC0 3 + Mg2+ + CO§- ...... CaMg(C0 3)2 (2)
Celsius (e.g. 1 Fyfe and Bischoff, 1965). spaces between adjacent crystals in
carbonate rocks and participates in
c
in which the CO~' anions as well as Mg2+
are supplied by solution to the reaction
The existence of calcium-rich, non-
stoichoimetric dolomite with com~ their diagenesis (Pingitore, 1976; and c
site as an alternative to the traditional C
"::.
equation of reaction (1). Forthe dolomi-
tization of aragonite, the free energy for
Table 1 Free energies of dolomitization reactions (1), (2) and (3) under
standard thermodynamic conditions.
C
reaction (2) is ~Go r = -13.24, favouring C
the formation of ordered dolomite even ~GO r calcite ~GO r aragonite
more strongly than reaction (1). Reac- (kilocal/mole) (kilocal/mole) C
tion (2) also has the advantage that the Reaction (1) - 1.38- - 1.83 (
calcium liberated by dissolution of Reaction (2) -13.01 -13.24
CaC03is removed entirely from solution Reaction (3) - 4.29 - 3.08 (
by dolomite whereas dolomitization by
reaction (1) poses the problem of Ca 2+ - Calculation of free energies from data of Helgeson et a/. (1978) using fully C
removal from the reaction site. If this ordered dolomite. These numbers vary depending on the degree of order ofthe
dolomite, but ordered dolomite is the mostfavoured phase thermodynamically.
C
evolved calcium is not removed its pre-
sence will raise the Ca/Mg ratio of solu- One calorie is equivalent to 4.184 joules in SI units. C
C
C
1000
M C
(
860 0 0 00
C
C

)(

~
;r;
C
500 z
Q
!;r
0 .8
E
UNMIXING
oU I-AREA OF
w
~ ~ Ca.MAGNESITES
a:
:::>
~ 0 .4 C
~
II: C
iw C
~
SAMPlE 2 ' SEIWATER
C
25 so 75 100
Figure 6 A dolomite structure, showing (
CaMglCO,12 MgC°3 - 0.8
watermolecules preferentiaffy bondedto the
-0.4 -0.2 0 0.2 0.4 0.6 cations of the crystal surface. Calcium ions C
Figure 4 Phase diagram of (water-free) CAlOTE SATURATION INDEX (1) are less strongly hydrated than magne-
CaC03> CaMg(C0:J2(do/omite). andMgC03 sium ions (2) so calcium ions tend to be
(
(Magnesite) at temperatures between 0°
and 1200°C. Only pure dolomite and calcite
Figure 5 Calcite and dolom ite saturation
index changes for mixing of sample 1
incorporated into magnesium layer posi-
tions causing the growth of a disordered Ca-
C
are thermodynamically stable at earth sur- (Peo. = 10-2 atm; broken fine) and sample 2 rich carbonate. Carbonate ions are unhy- (
"--
face temperatures . (After Deelman, 1978; (Peo 2 = 10-3 atm; solid fine) with seawater. drated but must have sufficient energy to
Goldsmith and Graf, 1958; and Goldsmith Shaded region is where Badiozamani (1973) displace the water molecules adjacent to the (.
and Heard, 1961). Recent work by Reeder and others have argued that dolomitization cation layer(e.g ., 3 and 4). Forsimplicity, an
and Wenk (1979) may cause some modifica- is favoured (diagram after Wigley and NaCI type of crystal structure is shown (after (
tion of this simple scenario. Plummer, 1976). Lippman, 1973,fig. 32).
C
C
C
c
c· Dolomites - Chemistry and Precipitation 117

c
(;
Wardlaw, 1976). Most of these natural (3) The low activity or concentration of environments of modern dolomite for-
(J solutions are mixtures of waters of CO~- relative to Ca2+ or Mg2+ in most mation, such as the Persian Gulf

c meteoric and marine origin modified by


bur ial processes and commonly are
natural solutions inhibits the precipita-
tion of magnesium-bearing carbonate
sabkhas or ephemeral lakes associated
with the Coorong Lagoon in Australia

c' supersaturated with respect to dolomite


even when undersaturated with calcite,
minerals in general (Lippman, 1973).
Some have argued that the growth of
(Alderman , 1965; Patterson, 1972), are
accompanied by magnesite precipita-
c except for dilute solutions undersatu-
rated in both phases (Figure 5). In warm
dolomite crystals is predominantly by
the sequential addition of successive
tion (plus assorted hydrous magnesium
carbonates).
c'
(
subsurface environments , the relative
stability of dolomite with respect to cal-
cation-anion layers (e.g . , Deelman ,
1975, but see also Towe, 1975) . ~
Calcium ions, which are less strongly
hydrated than magnesium ions, are
cite is even more pronounced than in ever, in modern environments of dolo- more readily incorporated into a grow-
c surface environments because the
dolomite-calcite equilibrium is shifted
mite formation dolomite isJr.l1J.al:iabl¥-
present in the s~.Q1rneotas...c.b.ombs.tba.l
ing Ca-Mg carbonate and will tend to
occupy sites within magnesium layers
( .
towards higher Ca/Mg ratios at higher range in size from less tban_1JL to. as well (Figure 3). Again, rapid rates
Q temperatures (Rosenberg and Holland,
1964). In other words, the increase of
about 10JLm. No crystals have been
caught in t e act of adding layers as
crystal growth reduces the time avail-
able for magnesium ions in solution to
o temperature attendant on progressive planar sheets perpendicular to the displaceerrant calcium ions beforethese

o burial in sedimentary basins will in-


crease the saturation level of dolomite
c-axis. Instead, dolomite crystals ap-
pear to grow as rhombs at more or less
defects are buried by continued crystal
growth.Thus,morerapidcrystalgrowthor
with respecttothat of calcite in solutions equal rates in all directions in spite of crystallization rates favour the develop-
with constant Ca/Mg ratios . their layered construction (Figure 3). ment of more calcium-rich phases.
.::J, . In summary, we can state that dolo- y The speed of crystallization inf u- Another important kinetic effect
~mite is stable in most natural solutions '(" ences the degree of order because ions related to the strength of the magne-
and that the existence of aragonite ~nd that adhere to incorrect lattice positions sium ion hydration sheath, is the inabil-
calcite in these solutions is a metastable on the surfaces of rapidly growing crys- ity of the relatively_unh drated carbon-

-condition.

THE ROLE OF KINETIC EFFECTS


tals are more likely to be entombed in
these positions than if the crystals grow
slowly. Slower growth permits a longer
ate ion to batter its wa through this
~ dration barrier ~:tG.omejn contac
with the cr stal surfac!i(Figure 6). Only
ON THE CRYSTALLIZATION OF period of exposure to e so u Ion 0 an a part of the total CO~- in solution has
DOLOMITE Incorrectl sited ion. This increases t e sufficient energy of motion (transla-
Several kinetic factors that impede the likelihood that it will be displaced by an tional or vibrational) to break through
precipitation of dolomite from super- ion of proper type for this lattice site. the hydration barrier surrounding mag-
saturated solution have been identi- Calcium and magnesium ions are easily nesium ions on the surface of a growing
fied and studied in the past several interchanged in dolomite's crystal lat- dolomite crystal. This low activity of the
( decades. These factors involve the tice because of the small differences of CO~· ion compared to the activities of
r molecular mechanics of precipitation lattice energy that are involved (Folk the Ca2+ and Mg2+ ions in many neutral
and difficulties associated with the for- and Land, 1975). and acid natural solutions, such as in
mation of the regularly alternating The strength of the electrostatic ion of seawater, is therefore a kinetic hin-
sheets of calcium and magnesium magnesium to water molecular bond is drance to the formation of dolomite
o atoms in growing dolomite crystals. about 20% greater than that of its cal- although the thermodynamic solubility

o Many of these kinetic effects interlock


and it is difficult to separate cause and
cium counterpart and much greater
than that ofthe carbonate ion (Lippman,
product of dolomite is exceeded by a
wide margin(Lippman, 1973, p. 158·161).
o effect. However, there are three major 1973, table 20). The relatively strong ¥ Consequently, three parameters that
underlying kinetic barriers to the pre- attachment of the magnesium ion to will affect the kinetics of the growth of
[I cipitation of dolomite: its water of hydration shell (Figure 6), dolomite al~_tbe Mg2+ICa 2 + r atio, the
(1) Rapid crystallization from super- is even more evident in the data ~y, and the CO~·ICa2+ ratio. The
saturated, concentrated (i.e. , saline) of Samoilov (1965, see Horne, 1969 , block diagram shown in Figure 7 is a
o
r
solutions impedes the segregation of
calcium and magnesium ions into their
p. 106) in which magnesium is cited as
being about 40 times as likely to carry its
plot of these solution parameters and
the dolomite-calcite field boundary is
respective layers so that magnesium water of hydration sheath with it during shown as a plane separating a dolomite
layers are contaminated by calcium migration through the liquid. The multi- field on the near side and a calcite field
8 atoms and vice versa and disordered tude of metastable, naturally occurring on the far side. This plane represents a
Ca-Mg carbonates are formed (Folk, hydrous magnesium carbonates , such generalized kinetic boundary that lies
1979; Folk and Land, 1975; Lippman, as hydromagnesite or nesquehonite, entirely within the region of thermody-
1973, p. 179); that crystallize in the thermodynamic namic stability of dolomite. The lower
(2) Pronounced differences in the stability field of anhydrous magnesite, is surface is the bivariate plot of Folk and
hydration behavior in aqueous solution also evidence of the relative strength of Land (1975).A solution in the calcitefield
of the constituent ions of dolomite pro- the hydration sheath of the magnesium can move into the dolomite field by
mote precipitation of calcium-rich ion. Magnesite, like dolomite, is highly increasing its Mg/Ca ratio, decreasingits
'-' phases (Lippman, 1973); and super-saturated in seawater and many salinity or by increasing its CO~· content.
,.
'-...-.

r.
c
118 Diagenesis (
Geoscience Canada Reprint Series 4
(

An increase in the solution's Mg/Ca It is certainly true that mixing a wide also be an important variable for pro-
C
ratio favours the uptake of magnesium variety of solution compositions can moting dolomitization in that a greater C
into a precipitating Mg-Ca carbonate. induce limestone dissolution. However, number of CO~- ions with sufficient
This is because an increase in the it is less clear why this fact in itself energy to shoulder aside the hydration
(
amount of magnesium in solution pro-
bably increases the number of magne-
should induce dolomitization. The dis-
solution of aragonite and ~Ritgtiorf
shield of magnesium ions would be pre-
sent. A variety of laboratory experi-
C
sium ions relative to calcium ions that of dolomite takes place in So" .tions that ments by Lippman (1968a) and Davies C
are energetic enough to shed their are saturated or su ersaturated with et al. (1977) have indicated the impor-
water of hydration and be incorporated ot phases i ·D.QS-liIJ. as the tance of the CO~- concentration . Lieber-
(
into a growing Ca-Mg carbonate (Figure
8). The laboratory syntheses by Glover
sabkhaenvironment (Kinsman, 1964) or
evaporite lagoons or ponds (Morrow,
mann (1967) also synthesized dolomite
from artificial solutions moresaline than
C
and Sippel (1967) and Erenburg (1961) 1978; Friedman, 1980) because of an seawater and with a Mg/Ca ration C
of magnesium calcites containing pro- appropriate rise in the solution Mg/Ca approximately that of seawater but with
gressively greater mole% MgC03 con- ratio through the precipitation of gyp- a relatively high pH and CO~' concen-
C
tents with increasing Mg/Ca ratios in
solution, constitute agood illustration of
sum. It seems likely therefore, that the
undersaturation of calcite that results
tration.
Sources for naturally occurring alka-
~
the effect of independently varying the from the mixing of saline with dilute line solutions containing high CO~- con- C
Mg/Ca ratio of the solution. The sabkha solutions is not an important factor for centrations include continental ground- (
environment of the Persian Gulf is a dolomitization. The dilution of saline waters that have been involved in the
natural setting where the influence of
the solution MG/Ca ratio on dolomit iza-
solutions favours dolomite precipitation weathering of siliceous rocks or that C
simplyoec.!use oOdnetic. eJie.cLoUb.L have dissolved continental alkalic car-
tion of aragonitic sediments is par- attendant decrease in th e rate of bonate minerals, or marine and conti- C
ticularly well documented (e.g., Kins- precipitation. nental waters that have been involved (
man, 1965; and Patterson, 1972). At An increase in the CO~- ion con- in anaerobic bacterial sulphate reduc-
high temperature (100° C) the rateor-
dolomite preci pitation is increasea by
centration of the SOlution, particularly in tion (Lippman, 1973). The Coorong <:
excess of the Ca2 + concentration, may Lagoon is the bestdocumented modern
higher Mg/Ca ratios up to an optimum C
value (Gaines, 1980). This may apply
aiSO"at lower temperatures.
~----......,:::or-------~ .... 10:1
c
The disordering effect caused by (
rapid precipitation may be overcome by
a reduction in the rate of precipitation by c
dilution of these solutions. This is diffi- 01 -(
cult to verify by laboratory experiments, \ Co Mg(CO,), g,
because of the slowness of crystalliza-
tion from solutions more dilute than sea-
CoCO, 1'1
' u
0
M
c
water, but has been inferred from natu- C
ral examples such as modern dolo-
mitization from brackish waters in the 1:5
c
Floridan Aquifer (Hanshaw et al., 1971; (
Fanning et al., 1981), in the sediments of
Lake Balaton, Hungary (Muller et al.,
~
1972), and from Pleistocene examples C
wherethe geologic history is known with
a high degree of certainty (e.g., Land, (
1973a,b).
Calculations of the thermodynamic
C
stability of various carbonate minerals C
in mixtures of seawater and fresh
goundwater show that there is a large c
region in the mixing continuum in which ".
calcite is undersaturated but dolomite Mg/Ca
e
remains supersaturated (Badiozamani, (
1973; Wigley and Plummer, 1976; and
Figure 7 Block diagram showing the effect of variation in the three parameters, the MgICa
Figure 5). Badiozamani (1973) specu-
solution ratio , the salinity, and the CO:/Ca solution ratio . The plane represents the kinetic
lated that the replacement of c~
dolomite would be considerably easier
boundary between dolomite and calcite or aragonite and it includes the hidden corner of the
Coorong Lagoon waters as a point on the plane. The basalplane is afterFolk and Land(1975).
c
within this mixing region bgcause of the Note that the vertical projection of Coorong Lagoon waters falls largely on the calcite-aragonite C
thermodynamic drive causin calcite to
...99 into SoJU1iOUlD~_
side of the stabifity boundary on the basal plane. A decrease in salinity, an increase in the MgI
Ca rat io or an increase in the CO:/Ca ratio favours the precipitation of dolomite, C
C
C
C
(
( Dolomites - Chemistry and Precipitat ion 119
(
(' occurrence of dolomitization under the ::l<'The relati~ase-of-dissolution_of.thEL­ 1966; Glover and Sippel , 1967). But
c influence of continental groundwater
(Vonder Borch et al., 1975; Vonder Borch,
~P.Qlyrno~pl:1s.0f.CaC03-1s.also.an.
important rate; deter:minmg.step-in.-t he
the degree of disorder introduced by
the faster rate of precipitation from
c 1976; Von der Borch and Lock, 1979). dOIomitimi9J:l_pr.ocess.(Gaines, 1974). more saline solutions overshadowsthe
c The composition of groundwater in
the Coorong Lagoon Area is shown in
Tile dolomitization of aragonitic sedi-
ments proceeds considerably more
effect of the diminution of the hydration
barrier of the magnes ium ion with
( Figure 7. Note that the projection of this rapidly than for calcitic sediments (e.g., increasing salinity so that, although the

c solution composition onto the Folk and


Land (1975) bivariate diagram falls
largely outside the region of dolomite
Schmidt, 1966).The rapid conversion of
aragonite to low-magnesian calcite in
humid climates has been cited as a fac-
Ca/Mg carbonates that are formed
approach a dolomite composition, they
tend to be disordered (Glover and Sip-
(
kinetic stability.This maybe an indication tor in the resistance to dolomitization of pel , 1967;Folk and Land, 1975; Morrow,
c. that the high CO~- concentration in the Pleistocene shelf limestones exposed
during low stands of sea level (Sibley,
1978). More experimental data are

o Coorong ground waters also promotes


the precipitationof dolomite and Figure 7 1980).
needed to separate the effects of pre-
cipitation rate versus the Mg/Ca ratio of
o«: has been constructed on this basis.
Generation of the CO~- by anaero-
The presence of certain cations, such
as lithium and possibly iron, haveacata-
the solution .
The origins of many dolomite occur-
bic sulphate reduction may have lytic effect on the precipitation of dolo- rences are consistent with the model

o occurred in many burial environments


from depths less than a metre to several
mite (Carpenter, 1980; Gaines, 1980).
Carpenter (1976) has also suggested
outlined in Figure 7 part icularly for
those that have formed in near surface
o hundred metres below the sediment-
water interface. This process has been
that because the proportion of strongly
hydrated magnesium ions decreases
settings. However, in subsurface en-
vironments, the increase of tempera-
c suggested as a factor in the dolomitiza-
tion of some Recent burrow fillings
markedly with increasing salinity, dolo-
mitization should be favoured by high
ture with depth is probably of dominant
importance. The increase of tempera-
( (Brown and Farrow, 1978). A supply of salinities and it does appear that dolo- ture that occurs with burial will reduce
SO~- ions in excess of the Ca2 + con- mites that have formed under co.o.d .L the kinetic inhibitions to dolomitization
centration is probably necessary be- tions of higher salinit y and higher..sAlu.:.... (see Gaines, 1974; Mattes and Moun -
( cause the initial rise in alkalinity will tion Mg/C a ra..Jip.s_t.l:!D.cLto_b.e_Le..§.§... joy, 1980) and cause dolomite to
precipitate CaC0 3 before proceeding to calcium-rich and heDce mace stoichjo- become more saturated relative to cal-
C dolomitization (Lippman, 1973). ~(Fuehtbauer and Goldschmidt, cite (Rosenberg and Holland, 1964).
C The amount of dolomiteJ.o..r.me.d will
depend on the rate that magnesium is
ION DEHYDRATION ENERGY
C supp lied and oJ1..the_time _available
( MEAN ENERGY Mg2+ ION- (Hanshaw et al., 1971).

RECENT INITIATIVES IN
DOLOMITIZATION CHEMISTRY
Baker and Kastner (1981) introduced a
( new dimension to the study of dolomiti-
zation with their discovery that sul-
phate ions in solution exert a strong
--80 KCAL/MOLE-
inhibition on the dolomitization of cal-
cite and aragonite. Their laboratory'
experiments , conducted at 200°C,
indicated that dolomitization of calcite
is prevented by the presence of sul-
( phate in solution at concentrations of
only 5% of that of seawater sulphate
concentration (0.028 M). Dolomitiza-
tion of ara . e was somewhat less
influenced b sui hate in solution .
ENERGY OF MOTION OF Mg "AND Ca "IONS Dolomitization in many diverse geo-
(RELATIVE TO DEHYDRATION ENERGY OF Mg2" AND Ca 2"IONS)
. logic settings has been suggested to be
primarily a response to reductions of
sulphate concentrations in these set-
Figure 8 Diagram showing energy (of motion) distribution of Mg2+ and Ca2 + ions in
tings, such as during the dilution of sea-
solution relative to the ion dehydration energy. It is possible to have an equal number of Mg2+
water by fresh groundwater in coastal
ions with energies exceeding the dehydration barrier by increasing the amount of Mg2+
in solution relative to the amount of Ca2 + in solution. A similar argument also applies to the aquifers (Kastner, 1984) or by the
C~- ion in solution . A normal distribution of ion kinetic energies is shown here for simplicity. microbial reduction of sulphate within
The true shape of the distr ibuiton of the kinetic energies of molecules in a liquid is not known organic-rich sea floor sediments (Baker
and is probably unique for each ion in solution but probably lies somewhere between a and Burns, 1985).
normal distribution and the asymmetric Soltzman distribution for the energies of molecules in
a gas.
c
120 Diagenesis Geoscience Canada Reprint Series 4 c
(

However, as discussed by Hardie and CO~- but is not required to remove slightly acid diagenetic environment of
c
(1987), it is difficult to rationalize the
occurrence of Recent dolomites in set-
any reaction products .
Both of these equations involve con-
the sabkha. Patterson suggested that
the average value of x in reaction (4) is
c
tings characterized by high solution sul- siderable volume changes. A loss of close to 0.1 based on the organic content (
phate concentrations, such as in the
much-studied sabkhas of the Persian
volume of 6% to 13% (aragonite or
calcite replacement) accompanies
of sabkha sediments. This value of x
also satisfies the conservation of vol-
c
Gulf(e.g., Patterson, 1972),in terms of a dolomitization according to reaction (1), ume criter ion. c
sulphate inhibition of dolomitization. A
point that has not been discussed overt-
a circumstance commonly cited by
workers in the oil industry. On the other
Reaction (3) implies that the-e.quiUb...
rium constant for dolomitization de- c
Iy is that a kinetic control on a reaction
rate, such as the sulphate inhibition
hand, dolomitization according to reac-
tion (2), if applied literally, involves a
pends on the CO~- concentration aswell
asfne Mg2+ aod-~c:~mcentrations .
c
effect, which has been determined for a tremendous volume gain of about 75% However, Stoessell (1987, see also c
part icular temperature (e.g., 200°C),
should be more pronounced at lower
to 88% (Lippman, 1973, table 28). Machel and Mountjoy, 1987) has dem-
However, most dolomitized rocks do - onstrated that equilibrium between cal- c
temperature because of the tempera- not appear to have undergone volume cite (or aragonite) and dolomite in reac- (;.
ture dependence of reaction rates. We changes during dolomitization indicat- tion (3) is dependent only on the Ca/Mg
may infer that it is not appropriate to
apply the same concentration levels of
ing a volume for volume replacement
ratherthan a mole for mole replacement
activity ratio and independant of the
activity of CO~- . But, because of kinetic
c
sulphate found to inhibit dolomit ization (Friedman and Sanders, 1967).Deposi- factors , the concentrations of Mg2+and C!::
at 200°C (Baker and Kastner, 1981) to
lower temperature (e.g., 20-40°C) set-
tionalfabricssuchasthosedisplayedb
algal laminites (Gebelein and Hoffman,
CO~- in the solution must be higher than
that necessary merely to satisfy the
C
tings for dolomitization (Kastner, 1984). 1973) or by oolitic sediments (Powers, thermodynamic requirements of dolo- C
Instead, much lower sulphate concen- 1962) are not disrupted by dolomitiza- mitization and the dolomitizing solution
trations should suffice to inhibit dolomi- tion. The increase in permeability that must play an active role as a transporter C
tization at lower temperatures. This fac- accompanies total dolomitization may of ions to and from the reaction site.This C
tor lends weight to the observations of be related to the idiomorphic shape and has important implications for carbon
Hardie (1987) concerning the occur- uniformity of size of the dolomite crys- and oxygen stable isotope studies of C
renee of dolomite in Recent sulphate- tals (Wardlaw, 1979). dolostones.
bearing near-surface env ironments. ;it.... The conservation of volume during The release of Ca2+ to solution during
C
Undoubtedly, further laboratory studies -{ 'the dolomitization reaction may be an dolomitization can lead to the local pre- C
concerning sulphate inbibjtion..w.i~ important constraint. For a volume-for- cipitation of gypsum as has been docu-
conducted and ~ ps some research volume reaction the net dolomit ization mented in Persian Gulf sabkhas (Patter- C
will be done on the sul ghate content of
ancieii'i dotcmltes.,
reaction may be written
(2-x)CaC0 3 + Mg2+ + xCO~- +-+
son, 1972). This may be an alternative
explanation also for the minute gypsum
C
Less attention has been focussed CaMg(C0 3 )2 + (1-x)Ca2+ (3) or anhydrite crystal inclusions in the C
recently on the effect of organic material where, x = 0.11 and 0.25 for the dolo- coarsely crystalline white dolostones of
on dolomitization. The precipitation of mitization of aragonite and calcite, res- the Mississippi Valley and Pine Point C
dolomite-similar phases by the action
of transition-metals and organic chelat-
pectively. Any departure from a volume
for volume replacement will result in
Districts which Beales and Hardy (1977,
1980) suggested were remnants of for-
C
ing agents (Mirsal and Zankle, 1985) changes in these numbers which repre- mer evaporites. C
may cause more research in this direc- sent the net exchange of ions between
tion. They found that metal chelates the solution and the solid phases. Reac- "THE DOLOMITIZATION PROCESS - C
mediated the transfer of magnesium car-
bonate to crystal surfaces causing the
tion (3)is characterized by a free energy
charge of dG r = -3.085 for dolomitiza-
CONCLUSIONS
(1) Dolomite is thermodynamically sta-
C
incomplete dolomitization of calcite. tion of aragonite (Table1) which is inter- ble in most natural solut ions at earth C
mediate between the free energies of surface conditions and a thermody-
DOLOMITIZATION AND THE reaction of (1) and (2). Reaction (3) is a namic drive exists for the conversion of C
VOLUME PROBLEM
The chemical reaction for dolomitiza-
composite of reactions (1) and (2)which
may be regarded as end members of a
calcite and aragonite to dolomite.
(2) The precipitation of dolomite is hin-
C
tion is most commonly given in the form series of reactions dependant on the dered by kinetic factors that are a conse- C
shown in reaction (1) lD wbklll a !D..Q@_of degree to which there is a gain or loss of quence of the high degree of order of
dolomite re laces two moles of calcite. rock volume during dolomitization. the dolomite crystal lattice and of the
C
The alternative dolomitization reaction Patterson (1972, p. 325) has pro- differences in hydration behavior of (
given in reaction (2) was proposed by posed the reaction the Ca2+, Mg2+ and CO~- ions.
Lippman (1973, p. 180) largely because (2-x)CaC0 3 + Mg2+ + xHC03 +-+ (3) The extent to which these factors C
of the advantages of a high CO~' con- . CaMg(C0 3)2 + (1-x)Ca2+ + xW (4) inhibit dolomitization appear to be gov-
centration in solution. In reaction (1) the based on chemical mass balance con- erned largely by the interplay of three
C
dolomitizating solution supplies the siderations for dolomitization of sabkha critical parameters: (a) the rate of crys- C
Mg2+ required and removes the Ca 2 + sediments which is similar to reaction (3) tallization governs the degree of order
released to SOlution, whereas in reac- except that carbonate is supplied in the of precipitating Ca-Mg carbonates. Dilu- C
tion (2)the solution supplies both Mg2+ form of bicarbonate because of the tion of supersaturated natural solutions
C
C
C
G
C Dolomites - Chemistry and Precipitation 121
C'
r:
,
is one method of reducing the crystalli- REFERENCES Concepts and Models of Dolomitization:
zation rate; (b) the Mg/Ca ratio of the Society of Economic Paleontologists
solution determines the degree to which Dolomite Crystal Structure and and Mineralogists, Special Publication
Mg2+ is incorporated into precipitating Compositional Variability 28, p. 87-110.
Ca-Mg carbonates. This ratio com- Lippman, F., 1973, Sedimentary Carbonate
monly rises during the precipitation of Carpenter, A.B., 1980, The chemistry of Minerals: Springer-Verlag, New York,
dolomite formation 1: the stability of 228 p.
gypsum and/or anhydrite to a level
dolomite, in Zenger, D.H., Dunham, J.B. Rosenberg, P.E. and Holland, H.D., 1964,
favourable for dolomitization; and (c) a
and Ethington, R.L., eds., Concepts Calcite-dolomite-magnesite stability
C03/Ca ratio greater than one will aid in and Models of Dolomitization: Society relations in solutions at elevated tem-
the precipitation of dolomite. This ratio of Economic Paleontologists and Min- peratures: Science, v. 145, p. 700-701.
may rise in ground water involved in eralogists, Special Publication 28,
weathering of igneous rocks or where p. 111-121. The Role of Kinetic Effects on the
'\ anaerobic bacterial reduction of sulphate Gaines, A.M., 1977, Protodolomite re- Crystallization of Dolomite
J
occurs. The presenceof sulphate in solu- defined: Journal of Sedimentary Petrol-
tion may also inhibit dolomitization. ogy, v. 47, p. 543-546. Badiozamani, K., 1973, The Dorag dolo-
(4) A conservation of volume constraint Goldsmith, J.R. and Graf, D.G., 1958,Struc- mitization model-application to the Mid-
c implies a reaction of the form: tural and compositional variations in
some natural dolomites: Journal ofGeol-
dle Ordovician of Wisconsian: Jour-
nal of Sedimentary Petrology, v. 43,
(2-x)CaC0 3 + Mg2+ + xCO~- ......
ogy, v. 66, p. 678-693. p.965-984.
CaMg(C0 3)2 + (1-x)Ca 2+ Land, L.S., 1980, The isotopic and trace Carpenter, A.B., 1976, Discussion: Dorag
where, x equals 0.11 or 0.25 for dolomiti- element geochemistry of dolomite: the dolomitization model: by K. Badioza-
zation of aragonite or calcite, respec- state of the art, in Zenger, D.H., Dun- mani: Jour. Sed. Petrology, v.43,
tively. All three of the constituent ions of ham, J.B. and Ethington, R.L., eds., p. 965-984: Journal of Sedimentary
dolomite are exchanged between the Concepts and Models of Dolomitization: Petrology, v. 46, p. 258-261.
solution and the solid phases emphasiz- Society of Economic Paleontologists Davies, P.J., Bubela, B. and Ferguson, J.,
ingthe roleoffluid movements and com- and Mineralogists, Special Publication 1977, Simulation of carbonate dia-
positions during dolomitization. 28, p. 87-110. genetic processes: formation of dolo-
Lippman, F., 1973, Sedimentary Carbonate mite, huntite and monohydro-calcite by
It is hoped that this review has suc-
Minerals: Springer-Verlag, New York, the reactions between nesquehonite
ceeded in providing a coherent syn-
228 p. and brine: Chemical Geology, v. 19,
thesis of evidence and theories spe- p. 187-214.
cifically concerning the chemistry of the The Stability of Dolomite in Natural Folk, R.G., 1974, The natural history of crys-
dolomitization process. The main kine- Environments talline calcium carbonate: effect of mag-
tic factors controlling dolomite pre- nesium content and salinity: Journal of
cipitation may have been identified, but Carpenter, A.B., 1980, The chemistry of Sedimentary Petrology, v. 44, p. 40-53.
a more determined effort should be dolomite formation 1: the stability of Folk, R.L. and Land, L.S., 1975, Mg/Ca ratio
madeto precipitate dolomite in the labo- dolomite, in Zenger, D.H., Dunham, J.B. and salinity: two controls over crystalli-
ratory in quantities large enough to ver- and Ethington, R.L., eds., Concepts zation of dolomite: American Associa-
and Models of Dolomitization: Society tion of Petroleum Geologists, Bulletin,
ify the influence of these kinetic effects
of Economic Paleontologists and Min- v. 59, p. 60-68.
and perhaps even to gain a degree of
eralogists, Special Publication 28, Friedman, G.C., 1980, Dolomite is an evap-
quantitative understanding of them. p. 111-121. orite mineral: evidence from therock
Only then will we be in a position to fully Gaines, A.M., 1977, Protodolomite re- record and from sea-marginal ponds of
understand the significance of the iso- defined: Journal of Sedimentary Petrol- the Red Sea, in Zenger, D.H., Dunham,
topic composition and of the trace ele- ogy, v. 47, p. 543-546. J.B. and Ethington, R.L., eds., Concepts
ment contents of dolostones because of Garrels, G.M. and Thompson, M.E., 1962,A and Models of Dolomitization: Society of
r: their dependence on the chemistry of chemical model for sea water at 25°C Economic Paleontologists and Mineral-
the dolomitization process. Knowledge and one atmosphere total pressure: ogists, Special Publication 28, p. 69-80.
r: ofthe chemical environment of dolomiti- American Journal of Science, v. 258, FOchtbauer, H. and Goldschmidt, H., 1965,
V p.402-418. Beziehugen zwishen calcium-gehalt
zation also provides a clearer insight
Goldsmith, J.R. and Heard, H.C., 1961,.Sub- und bild ungsbed ingungen der dolom ite:
into the process of dolomitization in spe-
solidus phase relations in the system Geologische Rundschau, v. 55, p. 29-40.
( cific models for dolomitization. CaC0 3 : Journal of Geology, v.69, Gaines, A.M., 1980, Dolomitization kine-
p.45-74. tics; recent experimental studies, in
ACKNOWLEDGEMENTS Helgeson, H.C., Delany, J.M., Nesbitt, H.W. Zenger, D.H., Dunham, J.B. and Eth-
Douglas Kent of the University of and Bird, D.K., 1978, Summary and cri- ington, R.L., eds., Concepts and Models
Saskatchewan and Alan Kendall of tique of the thermodynamic propert- of Dolomitization: Society of Economic
r: Amoco Canada Ltd. critically read the ies of rock-forming minerals: American Paleontologists and Mineralogists, Spe-
manuscript. I also wish to thank many Journal of Science, v. 278-A, 229 p. cial Publication 28, p. 81-86.
individuals, such as H.G. Machel (Uni- Land, L.S., 1980, The isotopic and trace
element geochemistry of dolomite: the
versity of Alberta), E. Sass (Hebrew Uni-
state of the art, in Zenger, D.H., Dun-
versityof Jerusalem) and R.K. Stoessell
ham, J.B. and Ethington, R.L., eds.,
(University of New Orleans), who con-
tributed to this paper through discus-
sions on dolomitization.
c
122 Diagenesis Geoscience Canada Reprint Series 4 c
(

c
Glover, E.D. and Sippel , R.F., 1967, Syn-
thesis of magnesium calcite: Geo-
Baker, P.A. and Kastner, M., 1981, Con-
straints on the formation of sedimentary
Brown, R.J. and Farrow, G.E., 1978,Recent
dolomitic concretions of crustacean c
chimica et Cosmochimica Acta, v. 33,
p.603-613.
dolomite: Science , v. 213, p. 214-216.
Hardie, L.A., 1987, Dolomitization: a criti-
burrow orig in from Goch Sunart, West
Coast of Scotland : Journal of Sedimen- c
Hanshaw, B.C., Back, W. and Deike, R.G.,
1971, A geochemical hypothesis for
cal view of some current views: Journal
of Sedimentary Petrology, v.57,
tary Petrology, v. 48, p. 825-834 .
Davies, G.R., 1979, Dolom ite rese rvoir c
dolomitization by groundwater: Eco-
nomic Geology, v. 66, p. 710-724.
p. 166-183.
Kastner, M., 1984, Control of dolomite for-
rocks : processes, controls, porosity
developments , in Geology of Carbonate
c
Land, L.S ., 1973a, Contemporaneous dolo- mation: Nature, v. 311, p. 410-411. Porosity: American Association of Pe- c
mitization of Middle Pleistocene reefs by
meteroic water, North Jamaica: Bulletin
Mirsal, I.A. and Zankle , H., 1985, Pheno-
menological aspects of carbonate geo-
troleum Geologists, Continuing Educa-
tion Course Note Series 11, p. C1-C17. c
of Marine Science, v. 23, p. 64-92 .
Land, L.S., 1973b, Holocene meteoric dolo-
chemistry. The control effect of transi-
tion metals: Geologische Aundschau,
Deelman , J.C., 1975, Dolomite synthesis
and crystal growth : Geology, v.3, c
mitization of Pleistocene limestones,
North Jamaica: Sedimentology, v. 20,
v. 74, p. 367-377. p.471-472 .
Deelman , J.C., 1978, Discussion : proto- c
p.411-424.
Liebermann, 0., 1967, Synthesis of dolo-
Dolomitization and the Volume Problem dolomite redefined : Journal of Sedimen-
tary Petrology, v. 48, p. 1004-1067.
c
mite: Nature, v. 213, p. 241-245. Friedman , G.M. and Sanders, J.E., 1967, Erenberg , B.G ., 1961, Artificial mixed c
Lippman, F., 1968, Synthesis of BaMg
(C0 3 b (Norsethite) at 20°C and the for-
Origin and occurrence of dolostones, in
Chlingar, G.V., Bissell, H.J. and Fair-
carbonates in the CaC0 3-MgC0 3
series : Zhurnal Skrukturny Khimiia , v. 2, c
mation of dolomite in sediments, in
Muller, G. and Friedman, G.M., eds.,
bridge, R.W., eds. , Carbonate Rocks:
Elsevier, Amsterdam, Developments in
p. 178-182.
Fanning, K.A., Byrne , R.H., Breland, JA, c
Recent Developments in Carbonate
Sedimentology in Central Europe :
Sedimentology, No. 9A, p. 267-348.
Lippman, F., 1973,Sedimentary Carbonate
Betzer, R.R., Moore, W.S., Eisinger, R.J.
and Pyle, T.E., 1981, Geothermal springs c
Springer-Verlag , New York, p. 33-37.
Lippman, F., 1973, Sedimentary Carbonate
Minerals: Springer-Verlag , New York,
228 p.
of the west of Florida Continental Shelf:
evidence for dolomitization and radio-
c
Minerals: Springer Verlag, New York, Powers, R.W., 1962, Arabian Upper Juras- nuclide enrichment: Earth and Plane- c
228 p.
Morrow, D.W., 1978, The influence of the
sic carbonate reservoir rocks, in Ham,
W.E., ed., Classification of Carbonate
tary Science Letters , v. 52, p. 345-354.
Fritz, P. and Katz, A., 1972, The sodium c
Mg/Ca ratio and salinity on dolomiti-
zation in evaporite basins : Canadian
Rocks -A Symposium: American Asso-
ciation of Petroleum Geologists, Memoir
distribution of dolomite crystals : Chemi-
cal Geology, v. 10, p. 237-244. c
Petroleum Geology Bulletin, v.26,
p.389-392.
1, p. 122-192.
Wardlaw, N.C., 1979, Pore systems in car-
Fyfe, W.S. and Bischoff, J.L., 1965, The
calcite-aragonite problem , in Pray, L.C. c
Muller, G., Irion, G. and Forstner, V., 1972,
Formation and diagenesis of inorganic
bonate rocks and their influence on
hydrocarbon recovery efficiency, in
and Murray, R.C., eds., Dolomitization
and Limestone Diagenesis - A Sym-
c
Ca-Mg carbonates in the lacustrine Geology of carbonate porosity: Ameri- posium: Society of Economic Paleontol- c
environment: Naturwissenschaften,
v. 59, p. 158-164.
can Association of Petroleum Geolo-
gists, Continuing Education Course
gists and Mineralogists, Special Pub-
lication No. 13, p. 3-13. c
Patterson , R.J., 1972, Hydrology and car-
bonate diagenesis of a coastal sabkha in
Note Series 11, p. E1-E24. Gaines, A.M., 1978, Reply - protodolomite
redef ined : Journal of Sedimentary c
the Pers ian Gulf, Ph.D. Dissertation,
Princeton Univ., Princeton , New Jersey,
Other References Cited in the Text Petrology, v. 48, p. 1009-1011.
Gebelein, C.D. and Hoffman, P., 1973, Algal c
498 p.
Sibley, D.F., 1980, Climatic control of dolo-
Alderman, A.R., 1965, Dolomitic sediments
and their environment in the south-east
origin of dolomite laminations in stro-
matolitic limestone: Journal of Sedi-
C
mitization, Seroe Domi Formation (Plio-
cene), Bonaire, N.A ., in Zenger, D.H.,
of South Australia: Geochimica et Cos-
mochimica Acta, v. 29, p. 1353-1365.
mentary Petrology, v. 43, p. 603-613.
Gidman , J., 1978, Discussion - proto-
E
Dunham, J.B. and Ethington, R.L., eds.,
Concepts and Models of DolomitizatIon:
Bathurst, R.G.C., 1975, Carbonate Sedi-
ments and Their Diagenesis: Elsevier,
dolomite redefined :Journal of Sedimen-
tary Petrology, v. 48, p. 1007-1008.
C
Society of Economic Paleontologists Amsterdam , Developments in Sedimen- Horne, A.A ., 1969 , Marine Chemistry: C
and Mineralogists, Special Publication tology No. 12, 658 p. Wiley-Interscience, New York, 568 p.
28, p. p. 247-258. Beales, F.W.and Hardy, J.L., 1977, The pro- Kinsman, D.D .J., 1965, Gypsum and C
Von der Borch, C.C., 1976, Stratigraphy blem of recognition of occult evaporites anhydrite of recent age, Trucial Coast,
and formation of Holocene dolomitic with special reference to southeast Persian Gulf, in Aau, J.L., ed., Second
C
carbonate deposits of the Coorong area,
South Australia:Journal of Sedimentary
Missouri: Econom ic Geology, v. 72,
p.487-490.
Sympos ium on Salt, v. 1: Northern Ohio
Geological Society, Cleveland, Ohio,
c
Petrology, v. 46, p. 952-966. Beales, F.W. and Hardy, J.L., 1980, Criteria p.302-236. e
Recent Initiatives In Dolomlrlzation
for the recognition of diverse dolomite
types with an emphasis on studies on
Lumsden , D.N. and Chimahusky, J.S.,
1980, Relationship between dolomite c
Chemistry host rocks for Mississippi Valley type ore
deposits, in Zenger, D.H., Dunham, J.B.
nonstoichiometry and carbonate facies
parameters, in Zenger, D.H., Dunham, c
Baker, P.A. and Burns, S.J., 1985, Occur-
rence and formation of dolomite in
and Ethington, R.L., eds., Concepts and
Models of Dolomitization : Society of
J.B. and Ethington, R.L., eds., Concepts
and Models of Dolomitization: Society c
organic-rich continental margin sedi- Economic Paleontologists and Min- of Economic Paleontolog ists and Min-
ments : American Association of Petro- eralogists, Special Publication 28 , eralogists, Special Publication 28 ,
leum Geologists, Bulletin, v.69 ,
p. 1917-1930.
p.197-213. p. 123-137. c
C
l
C
r
C Dolomites - Chemistry and Precipitation 123
o
c Schmidt , v., 1965, Facies, diagenesis , and
o Machel , H.G. and Mountjoy, E.W., 1987,
Chemistry and environments of dolomi- related reservoir properties in the Gigas
Wigley, T.M.L. and Plummer, L.N., 1976,
Mix ing of carbonate wate rs : Geo-

o tization - a reappraisal (Reply): Earth


Science Reviews, v. 24, p. 213-215.
Macqueen, R.W., 1979, Base metal depos-
Beds (Upper Jurassic), northwestern
Germany, in Pray, L.C . and Murray,
R.C., eds ., Dolomitization and Lime-
chimica et Cosmochimica Acta, v. 40,
p.989-995 .
Ziegler, A.M ., Scotese , C.R., McKerrow,
its in sedimentary rocks : Some ap- stone Diagenesis: Society of Economic M.S., Johnson, M.E. and Bambach ,
( proaches: Geosc ience Canada, v. 6, Paleontolog ists and Mineralog ists, R.K., 1979, Paleozoic paleogeography :
p.3-9. Special Publication No. 13, p. 124-168. Annual Reviews of Earth and Planetary
o Mattes, BW. and Mountjoy, EW., 1980,
Burial dolomit ization of the Upper
Stoessell, R.K., 1987, Chemistry and en-
vironments of dolomitization - a reap-
Sciences, v. 7, p. 473-502.

Devon ian Miette Buildup , Jasper praisal (Discussion): Earth Science


National Park, Alberta, in Zenger, D.H., Reviews, v. 24, p. 211-212.
( Dunham, J.B. and Ethington , R.L., eds., Towe, K.M., 1975, Dolomite synthesis and

o Concepts and Models of Dolomitiza-


tion: Society of Economic Paleontolo-
crystal growth: Comment: Geology,
v. 3, p. 612.
o gists and Mineralogists, Special Pub-
licat ion 28, p. 259-297.
Veizer, J., Lemieux, J., Jones, B., Gibling,
J.R. and Savelle, J., 1978, Paleosalinity
o Pingitore, N.E., Jr. , 1976, Vadose and and dolomitization of a Lower Paleozoic

o phreatic d iagenesis: Processes ,


products and their recognit ion in corals:
carbonate sequence, Somerset and
Prince of Wales Island, Arct ic Canada:

o Journal of Sedimentary Petrology,


v. 46, p. 60-67.
Canadian Journal of Earth Sciences,
v. 15, p. 1448-1461.
c Radke , B.M. and Mathis, M.L., 1980, On
the formation and occurrence of sad-
Von der Borch, C.C., Lock, D.E . and
Schwebel, D., 1975, Groundwater for-
o dle dolomite: Journal of Sedimentary
Petrology, v. 50, p. 1149-1168.
mation of dolomite in the Coorong re-
gion of South Australia: Geology, v.3,
Originally published in
Geoscience Canada v. 9 Number 1
Reeder, R.J. and Wenk, H.R., 1979, Micro- p.283-285.
(March 1982)
o structures in low temperature dolo-
mites: Geophysical Research Letters,
Wardlaw, N.C. , 1976, Pore geometry of car-
bonate rocks as revealed by pore casts Revised 1988

o v. 6, p. 77-80.
Samoilov, O.Y., 1965, Structure of aqueous
and capillary pressure : American Asso-
ciation of Petroleum Geologists, Bul-

o electrolyte solutions and hydration of


ions: Consultants Bureau, New York.
letin, v. 60, p. 245-257.

o
o
o
o
o
(
o
o
o
()
(

e
r:

r
c
124 Diagenesis Geoscience Canada Reprint Series 4
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
(
SEM photomicrograph of a synthetic dolomite formed in a reaction vessel at 220 0 C. Rhombic dolomite crystals have formed from the
reaction of calcite with a CaCI2 - MgCl2solution. Loss of CO2 from the reaction vessel causedprogressive dissolution of this dolom ite. c
The etched surface of these euhedral dolomite crystals is an early manifestation of CO2 depletion in the reaction solution. Photograph
courtesy of D. W. Morrow (Geological Survey of Canada). c
c
c
e
(

c
c
C
L
C
c'
( Dolomites - Models and Ancient Dolostones 125
o
c'
o water by fresh groundwater which may
occur in a multitude of situations both
on inferences concerning the attributes
of these dolostones. These include
o penecontemporaneous with, or long
after sedimentation.
considerations of scale and spatial
relationships, major stratigraphic and
c A number of cond itions must be sat- paleogeographic relationships, inter-

o isfied for these models to act as agents


for dolomit ization (Figure 1). These
nal facies relationships, petrographic
relationships, and of geochemical data.
o conditions, in their simplest form are as
follows :
It is at this stage, where statements are
made concerning the application of
( (1) The amount of Mg2+ available for specific dolomitization models based

o Dolomite - Part 2: dolomitization must be adequate to


form a given mass of dolostone (i.e.,
on the physical and chemical attributes
of dolostone bodies, that the confusion
o Dolomitization Models
and Ancient
source of Mg2+).
(2) A mechanism is required to deliver
concerning the dolomitization process
becomes readily apparent. An attempt
o Dolostones
the available Mg2+ to the dolomitization is made here to determine the relative

c site. This mechanism may also be re-


quired to deliver a small amount of CO~'
degree of certainty that can be placed
on the diverse criteria used to substan-
o D.W. Morrow
ions to the dolomitization site and carry
away Ca2+ ions .
tiate the choices of dolomitization mod-
els that have been applied to many
o Institute of Sedimentary and
Petroleum Geology
(3) The composition of a proposed dolo-
mitizing solution must be conducive to
ancient dolostones in Canada (Figure
2) and elsewhere.
3303-33rd Street N. W dolomitization. The first paper of this
o Calgary, Alberta T2L 2A7 review series provided some criteria to Dolomitization Models

o INTRODUCTION
test this proposition.
Each model will be examined in the
The Hypersaline Lagoon and Reflux
Model.
o The first paper of this review series
(Morrow, 1982, this volume) was a syn-
light of these conditions to place con-
straints on their application to the strati-
One of the first models proposed for
dolomitization on a large scale was the
o thesis of what is presently known con-
cerning the chemistry of dolomitization.
graphic record and on their viability in
general. A variety of specific factors
Seepage Refluxion or more simply, the
Reflux Model (King, 1947 ; Adams and
In that paper, parameters of major im- may contribute to these conditions in Rhodes, 1960) . In this model (Figure 3),
portance to the dolomitization process particular instances. For example, the open marine water evaporates as it
were identified: the Mg/Ca solution delivery mechanism (condition 2) may passes landward across a hypersaline
ratio ; the ionic strength or salinity of depend on porosity and permeability shelf lagoon. The resulting increase in

o the solution; the C03/Ca solution ratio;


and the sulphate concentration. Other
relationships, the hydraulic head of the
solution and the time over which the
density of these evaporated waters
causes them to infiltrate the underlying
o factors, such as temperature, that influ-
ence the dolomitization process also
mechanism is operative.
The application of these models to
sediment and to move seaward by
seepage (i.e., reflux) through the sea-
o were discussed. individual dolostone masses depends ward-dipping beds. The cycle of fresh

o This paper focusses the reader's at-


tention on a different aspect of dolomi-
o tization - the great variety of models for
dolomitization that have been proposed
DOLOMITIZATION MODELS-
ESSENTIAL COMPONENTS
o to explain the origin of the wide spec-
trum of dolostone types. In approximate
1 2
~c=7
~
historical order of appearance , these g
are the Hypersaline Lagoon and Reflux
Model, the Burial Compaction Model,
the Solution Can nibalization Model, the
MgMg
Mg CO:! Mg
''0 d
Coorong Model, the Sabkha Model, and
the Mixed Water (Dorag) or Dilution
Model, the Organogenic Sea-floor 1. SUPPLY OF Mg 2. DELIVERY 3. DOLOMITE
Model and the Hydrothermal Convec- AND C03 MECHANISM CONSTRUCTION
tion Model. The Sabkha and Coorong SITE
Models are specific to well defined envi-
ronmental settings. The other models
Figure 1 A construction site analogue of the process of dolomitization illustrating the three
are more generalized and emphasize
essential elements of any dolomitization model. The external supply of magnes ium, and, to a
particular aspects of the dolomitizing lesser extent, the supply of carbonate must be sufficient to form the observed amounts of
process that may be operative in a dolom ite. There must be a delivery mechanism, commonly in the form of fluid flow, adequate to
variety of environmental settings. For deliver these ions to the dolomitization site and lastly there must exist chemical conditions
example, in the Mixed Water Model, favourable for the precipitation of dolomite at the "dolomite construction site ", Failure to meet
the emphasis is on the dilution of sea- any of these conditions results in an inadequate dolomitization model.
(
(
126 Diagenesis Geoscience Canada Reprint Series 4
(
(
(
DOLOMITIZATION MODELS· CANADIAN EXAMPLES (
Model Example (Formation and author) (
1. Hypersaline Basin Keg River· Pine Point - Presqu 'ile (Skall, 1975) (
and Seepage Reflux Muskeg - Keg River (Davies and Ludlum, 1973;
Bebout and Maiklem, 1973)
Prair ie Evapor ite - Winnipegosis (Wardlaw and Reinson, 1971)
(
Figure 2 Canadian examples of the dolo-
mitization models discussed in this paper.
Lodgepole (Young and Greggs, 1975)
Leduc (Wilson , 1975)
(
Some units, such as the Presqu 'ite Forma- (
tion have been assigned to more than one 2. Sabkha ch¥fie Lake (Roy, 1972)
model. SI. George (Co llins and Smith, 1975)
Turner Valley (Murray and Luc ia, 1967)
(
Muskeg-Winnipegosis (Shearman and Fuller, 1969) (
3. Mixed-Water Guelph (Sears and Lucia, 1980)
Nisku (Exploration Staff, Chevron Standard Lim ited , 1979)
(
Abenak i (Eluik. 1978)
Allen Bay (Land et a/., 1975: Veizer et al., 1978) C
Thumb Mountain (Morrow and Ker r, 1978)
SI. George? (Coll ins and Smith , 1975)
(
Stone (Morrow, 1975: Macqueen and Thompson. 1978)
Manetoe (Morrow, 1975) C
4. Coorong Belcher Group (Ricketts, in press)
(
5. Burial-Compaction Presqu'lle (Griffin , 1965; Beales and Jackson, 1969) C
Leduc (liling. 1959)
Miette (Mattes and Mountjoy, 1980)
(
Guelph (Jodry, 1969)
C
6. Solution
Cannibalization
Yeoman (Kendall , 1977)
(
7. Tectonic or Black River - Trenton (Sanford, 1962)
(
Hydrothermal Keg River - Rainbow (Lang ton and Chin , 1968)
Presqu'ile (Jones , 1980) C
C
DOLOMITIZATION MODELS C
2• . SABKHA. MODEL (REFLU X VARIANT)
w
o 1. REFLUX MODEL <
.tORM TIDEI
~ :) 3. COORONG MODEL
(
Figure 3 Major dolomitization models « EPHlMr:R.u

summarized in generalized representative IL.


a: 1'-""
LAKES
~:::S;;::::::;;;;;;::;;:~;;;;;;= (
;:) SABKHA. MODE L ( C A PIL L ARY
cross-sections . The patterned areas repre- T tO-1l

sent zones of active dolomitization during


CJ)
a:
-e I , lI . , II GCI
_ to ••
RECHARGE VARIANT)
EVjP0j"J'ON l""U.'
E
the operation of these models. The horizon-
tal dimensions of these cross sections is
rn zw ~ ...,caFo-'C [ao.] &AU!IITY
C
w • .·n •.•, 0 . " . .....00

proportional to their vertical dtmenston» so


that systems tens of metres thick may extend
z 0
~
... MIXED WATER-UNCONFINED COASTAL
AOUIFER MODEL
5. ORGANOGENIC SEAFLOOR
MODEL
Ja..h
,
. -11
0 ,.•-
0 .0'
O. I ~t
O'~~ii
'o~-
100-4. .
2-70
(
2 .... 0.000... 1"'.0
~
'UUVEl
0
several kilometres whereas systems thou-
sands of metres deep may extend hundreds N
0
..J


1 0~U .-u
. ; : - ....
O=-I
o .~~
- " ,0
"'-2.1 C
..J 7 ~~-. 1.' O.OO~- &0-'"
of kilometres laterally. Arrows correspond to -e
:I:
• I .' <C 1.0 0.004- 1O-2H (
directions of fluid movement. Inset table :I: CJ) ":::"-", I . ... 0.021 as

shows estimates of the values of chemical I-


a.. c,
6. MIXED WATER-DEEP CONFINED
AQUIFER WODEl
"'£I:""..,OE
1 BURIAL COMPACTION MODEL 8. ~~~~~THER"'Al CONVECTION C
parameters that characterize each of these w
(:
~ ---
w
W c \.. Coo"O'O

---
models. LA 0 • • •/ /

0 0
I- '-.... - ; ~ (
W

r..... ·· (
~
«
a: _ t •••
w
c
0 (
~

(
C
(
(
(
c Dolomites - Models and Ancient Dolostones 127
C'
(',
o marine replenishment of lagoon waters
and seaward seepage of brines is the
tions. Recentwork (Vonder Borch, 1976;
Von der Borch and Lock, 1979; Von der
more general ized mixed-water or di-
lution model. Only one documented
o mechanism by which Mg2+ is con-
tinually transported to the sediment.
Borch et al., 1975 and Muir et al., 1980)
has established the Coorong Lagoon
Canadian example of this model exists
(Figure 2), but more undoubtedly will be
C' The source of Mg2+ is the evaporated as a model for early near-surface dolo- found.

o seawater itself. The dolomitization


reaction probably occurs after a great
mitization in many ancient sequences of
aphanitic dolomite that are not asso-
The other well-documented setting
for penecontemporaneous dolomite,
o deal of the gypsum (or anhydrite) has
precipitated, sulphate has been re-
ciated with evaporites (Figure 3). The
lagoon and a series of ephemeral lakes
the sabkha environment , is restricted to
those dolomites with accompanying
c moved, and the MglCa ratio ap- extend 200 km parallel to the south evaporite minerals. Illing et al. (1965) in

o proaches 9.0 possibly overshadowing


the inhibiting effect of salinity (Morrow,
coast of Australia and are confined
between Pleistocene fossil dunes that
collaboration with geologists of the
Shell Oil Company provided the first
o 1978). The increase of the C0 3/Ca solu-
tion ratio that occurs during gypsum or
extend parallel to the coast. Surface comprehensive report on the Holocene

o anhydrite precipitation would also aid


drainage follows the existing topogra-
phy, but the subsurface groundwater
intertidal and supratidal dolomite that
had replaced aragonitic sediments
o dolomitization.
Modern examples of the seepage
flows seaward perpendicular to the sur-
face drainage (Figure 3). The ephem-
exposed on sabkha surfaces bordering
the Qatar Peninsulaon the PersianGulf.
o reflux ion hypothes is are small in scale eral lakes are filled during the humid This was followed by the studiesof Kins-

o and operate at or near the shoreline .


Muller and Teitz (1971) and Kocurko
winter months by groundwater see-
page and are evaporated to partial or
man (1966), Butler (1969), de Groot
(1973),Bush (1973), Hsu and Schneider
o (1979) have documented shoreline
dolomitization in the Canary Islands
complete dryness during the summer
months.
(1973), Patterson (1972) and Patterson
and Kinsman (1981, 1982) of the Abu
o and in San Andres Island by evaporated
sea water that collects in ephemeral
Extremely fine-grained calcian dolo-
mite (yoghurt) mud and magnesite
Dhabi Sabkhas east of the Qatar
Peninsula.
pools in the "spray zone", a few metres forms in the landward ephemeral lakes Dolomite in the sabkhas of the Per-
o above high tide. The shallow, but per-
manent, evaporating pool at Bonaire
under the influence of continental
groundwater or in the zone of mixing
sian Gulf is most abundant as 1 to 5 flm
euhedral crystals in the high intertidal
c (Deffeyes et al., 1965; Murray, 1969) is between seawater and continental zone close to the strand line and is

o perhaps the best modern analogue of


the large-scale reflux model envisaged
water. This dolomite is in the form of
0.5-1 flm , amorphous , spherular aggre-
strongly controlled by the network of
flood channels across the sabkhas .
by Adams and Rhodes (1960). gates and may have precipitated Storm driven flood tides reach furthest
The Mg2+ content of refluxing solu- directly as gel (Von der Borch and inland along these channel courses
o tions in the reflux model is extremely Jones, 1976).Aragonite and calcite pre- (Patterson, 1972). The frequency of

o high, but it is not clear what the rate of


subsurface flow of these dense solu-
dominates in the Coorong Lagoon itself
which is filled with seawater. Dolomite
flooding decreases landward across
the sabkha but the MglCa ratio of the
o tions is likely to be. Deffeyeset al. (1965)
calculated a rate of seaward reflux
(and magnesite) precipitation in the
ephemeral lakes is aided by ground-
floodwaters rises uniformly landwardby
means of gypsum precipitation so that
o flow of 2 x 10-6 cm3/s/cm 2 at Bonaire, water dilution, by a decrease in sul- the zone of optimum dolomite formation

o but subsequent work (Murray, 1969)


showed that the refluxing brines flow
phate concentration and by the high
CO~- concentration of the alkaline
is less than a kilometre wide straddling
the boundary between high intertidal
seaward for only a few weeks each year groundwater. The source of Mg2+ ions and supratidal areas (Patterson, 1972;
and most of this flow is confined to more has not been identified with certainty; Bush, 1973; and Figure 3). The dense
o permeable conduits bypassing most of dolomites forming close to the coast Mg2+-bearing hypersaline floodwater
the limestone. Model studies or com- may have derived their Mg2+ directly brines sink downward and flow seaward
puter simulations might shed light on from seawater, but dolomites forming through the sediment by seepage re-
o the feasibility of large-scale reflux sce-
narios such as that envisaged by Adams
farther inland probably utilize Mg2+ in
the groundwater, some of which may
fluxion . Dolomitization of the underly-
ing intertidal and subtidal sediments
o and Rhodes (1960). At present, the have been derived from the weathering occurs to a depth of 2 to 3 m beneath
dynamics of water movement beneath of basic volcanic rocks (Vonder Borch et the sabkha surface in regions landward
G and adjacent to evaporitic shelf lagoons al., 1975). In either case the delivery of the continuous algal mat (Patterson,
is unknown and a potentially fertile field mechanism is the continual subsurface 1972; Bush, 1973; de Groot, 1973). Hsu
of investigation. There are many exam- groundwater flow. and Siege nth alar (1969) , Hsu and
ples of Canadian dolostones explained Successive regressions of a Coo- Schneider (1973) and McKenzie et al.
by variants of the reflux hypothesis rong-type system of lagoons and (1980) have developed an alternative
(Figure 2). ephemeral lakes on a subsiding conti- model for sabkha dolomitization based
The Coorong and Sabkha Models. nental margin can build thick se- on a process which they term evapora-
The Coorong Lagoon was known to be quences of evaporite-free peritidal tive pumping. In this process, a con-
an area of dolomite formation since the dolomite (Muir et al., 1980). Because of tinual flow of seawater moveslandward
later 1920s (Mawson, 1929), but was the predominant role of fresh ground- through the sabkha sediments to re-
ignored until Alderman and Skinner water, the Coorong Lagoon Model may place groundwater lost by evaporation
(1957)inaugurated a series of investiga- be regarded as a specific type of the at, or near the sabkha surface. This flow
c
128 Diagenesis Geoscience Canada Reprint Series 4
c
(

c
pattern is the reverse of seepage re-
fluxion (Figure 3), butthe field evidence
Steinen, 1980). In most of these exam-
ples, thick platform dolomite sequences
mites . But recent developments in the
understanding of diagenetic changes in
c
for evaporative pumping in the sabkhas consist of many individual regressive clay minerals and associated amor- c
of the Persian Gulf is contradictory (see
Hsu and Schneider, 1973; McKenzie et
al. , 1980; Patterson, 1972; Patterson
carbonate sediment wedges that have
been penecontemporaneously dolo-
mitized by the shallow coastal fresh-
phous material, and the parallel matura-
tion of organic material to hydrocarbons c
during burial has led to a renewed inter- (
and Kinsman, 1981). It is unlikely that water aquifers that accompanied their est in this model (Davies, 1979; Mattes
evaporative pumping has contributed seaward progradation (Figure 3). The and Mountjoy, 1980). Clay minerals c
greatly to sabkha dolomitization be-
cause evaporation of sabkha ground-
vast differences in the chemical and
isotopic composition between dolo-
undergo a sequence of depth-related
mineralogical changes that provides c
water is slowed considerably by a num-
ber of factors such as absorption of
mites that have formed under the influ-
ence of freshwater and dolomites that
an additional source of pore water and
of a variety of ions, including Mg2+,
c
water at night and high relative humidity have formed from hypersaline brines released from clay minerals to the pore c
ofthe overlying air mass. Consequently,
this mechanism does not provide the
has led to an emphasis on these types of
data as criteria in choosing between the
fluids. These transformations have
been cited as additional causes for bur- c
volume of flow of ion-bearing ground- Mixed-Water Aquifer Models and other ial-compaction dolomitization. c
water necessary for dolomitization. The
Sabkha Model may be regarded as a
models. However, uncertainties in the
interpretation of chemical and isotopic
There is little doubt that the kinetic
inhibitions that bedevil the formation of c
specific example of the Reflux Model
modified slightly by the process of evap-
data often preclude their use in model
discrimination in the absence of other
dolomite at near-surface conditions are
greatly reduced in deep burial environ- c
orative pumping. Many Canadian data (Land, 1980). ments largely because ofthe increase of c
examples of dolomitization by the
Sabkha Model have been identified
(Figure 2).
In the Mixed-Water Aquifer Models
dolomitization occurs within the zone of
mixing of fresh groundwater with phre-
temperature with depth. Also, the time
available for dolomitization is much
greater in deep subsurface environ-
c
The Mixed·Water Aquifer Models. atic seawater. The Mg2+ ions for dolo- ments than in the near-surface environ-
These models arose in the period follow- mitization are derived primarily from ments of early dolomitization (Mattes c
ing 1970. Before that time, there were a
few reports of dolomite that formed in low
seawater and the delivery of mecha-
nism is the continual circulation of sea-
and Mountjoy, 1980).
However, the problem of the supply of c
salinity environments such as in lakes
(e.g., Klahn, 1928) or in caves (e.g., Hoi-
water induced by the flow of fresh
groundwater (Land, 1973). Dilution of
magnesium for dolomitization is an
important constraint in deep burial
c
land et al., 1964), but Hanshaw et al. saline solutions causes slow precipita- environments. About 5.5 x 10-3 moles c
(1971) documented the first large-scale
system of dolomitization under the influ-
tion and a lowering of the sulphate con-
centration which favour dolomite pre-
of Mg2+ are required to dolomitize 1 cm3
of calcite at 10% porosity. If this Mg2+ is c
ence of fresh groundwater in the deep
confined Tertiary carbonate aquifer of
cipitation (Folk and Land, 1975 ; Kastner,
1984) and the high CO~- concentration
supplied by compaction of adjacent
shales and if the pore solution has the
c
Florida (Figure 3). They emphasized the in many dilute continental ground- composition of seawater, then about 32 c
role of active groundwater circulation in
supplying marine-derived Mg2+ for
waters may also promote the precipita-
tion of dolomite (Lippman, 1973; Mor-
cm 3 of shale, compacted from 70%
down to 2% porosity, are required to c
dolomitization.
Land (1973) argued convincinglyfrom
row, 1982). These models have been
used to explain the origin of many Cana-
provide this amount of Mg2+. Th is
assumes that all the water of compac-
C
field relationships and petrographic dian dolostones (Figure 2). tion passes through the carbonates. In E
and chemical evidence, that the Middle The Burial Compaction Model. reality more than half of shale compac-
Pleistocene reef rocks of Jamaica were Compaction of fine-grained sediments tion water is lost vertically upward into C
dolomitized penecontemporaneously
by the interaction of marine and fresh
during burial involves the progressive
expulsion of pore water. Commonly,
the body of water from which the shale
was deposited and most of the re-
C
groundwater in a shallow coastal aqui- large shale masses contain carbonate mainder passes downward (Magara, C
fer. Ward and Halley (1984) provide reef bodies and are underlain by or are 1976, p. 92-95) . On a basin-wide scale ,
similar examples of mixing zone dolo- bordered by thick shelf carbonate therefore, a more reasonable estimate
C
mitization in the Upper Pleistocene of sequences. A part of the Mg2+-bearing would be that on the order of hundreds C
the northeast coastal limestones of
Yucatan. Land (1973) suggested that
compaction water may pass through
adjacent limestones and cause dolo-
of cubic centimetres of compacted
shale are required for the dolomitiza- c:
many ancient platform dolomites which mitization (Figure 3). The Mg2+ re- tion of 1 cm 3 of laterally adjacent lime-
lack evaporites and are depleted in both quired for dolomitization is derived pri- stone. Therefore, shale compaction
C
trace elements (e.g., Na+, Sr 2+) and marily from the pore water. IIling (1959), water is insufficient to form large C
heavy isotopes ('80, 13C) may have Jodry (1969) and Griffin (1965) were masses of dolomite such as the Paleo-
formed in a similar manner. This sug- early proponents of this model zoic platform dolomite sequences of C
gestion has been followed recently
by many authors (e.g., Badiozamani,
(Figure 2).
The popularity of the Burial Compac-
Western Canada and elsewhere. Open
space cementation imposes an even
C
1973; Land et al., 1975; Veizer et al., tion Model waned for a long period more extreme limitation on the volume C
1978; Randazzo and Hickey, 1977; Dun- because of the upsurge in studies of of solution required to form a given
ham and Olson, 1980; Choquette and Holocene penecontemporaneous dolo- amount of dolomite. This is apparent C
C.
C
r

Dolomites - Models and Ancient Dolostones 129

r:

when one considers that most solutions gressive loss of the raw material for marine-derived fluids only a few metres
saturated with dolomite contain the dolomitization (i.e., the pore fluids and beneath the sediment-water interface
o
r:
equivalent of only about 10-5 moles of
dolomite per litre of solution.
their ions) as burial compaction pro-
ceeds. Nevertheless, some workers
in offshore deeper marine continental
margin settings (Baker and Burns,
In environments of burial greater have suggested that large volumes of 1985). Unlike other models for early or

o than 2000 m, the transformation of


montmorillonitic clays to illite is accom-
marine-derived basinal fluids in large
basins can be focussed through more
penecontemporaneous dolomitization,
the magnesium required for dolomitiza-
r-t pantedbythereleaseot'Sr-.Fes" ,Ca 2 + , porous limestone layers by post-deposi- tion is supplied primarily by diffusion
and Mg2+ ions to the pore solution so tional regional ground-water systems from the overlying water massin a deep
that authigenic ankerite, ferroan dolo- dominated by gravity flow (Gregg , marine setting and dolomitization takes

o mite and chlorite are precipitated as


cements in some sand-shale sequen-
1985). This scenario might be regarded
as an extension of the simple burial
place in fluids with a nearly normal
marine Mg/Ca ratio and salinity. The
ces (Boles, 1981). In many instances, compact ion model in that connate bur- intrasediment diagenetic environment
however,there is an insuff icient volume ial compaction fluids are mobilized by is strongly reducing leading to sulphate
o of fluid at these depths to move these regional ground-water systems after depletion by sulphate reduction and the
ions laterally and to participate in the uplift of the region above sea level. oxidation of organic material. The
solution of large amounts of limestone The Hydrothermal-Convection Organogenic Sea-floor Model derives
u and contemporaneous precipitation of Model. its name from the fact that carbonate
dolomite. Shale porosity is less than This model has emerged from the ions generated from the organic mater-
o 20% at burial depths exceeding 2000 m recent application of the study of fluid ial are incorporated into the precipitated
and processes such as aquathermal inclusions to the origin of regional dolo- dolomites. Both the reduction in sul-
pressuring or the release of structured mite bodies in Canada. The essential phate concentration and the generation
o water from clays donot add significantly
to this volume of interstitial pore water
features of this model were outlined by
Aulstead and Spencer (1985) where
of carbonate alkalinity are thought to
enhance dolomitization (Kastner, 1984 ;
(Magara, 1976). The existing evidence they suggested that dolomite cements Baker and Burns, 1985). This model for
strongly indicates that the late diage- in the Keg River Formation of Alberta dolomitization is less significant in a
netic release of ions from clay minerals precipitated from evaporitic brines of volumetric sense but, as Baker and
o is accompanied by local cementation the Elk Point Basin which had been re- Burns (1985) pointed out, it is important
as an indicator of organic-rich source
o rather than the long distance transpor-
tation of ions to shelf carbonates facing
circulated by thermal convection from
great depths. Crustal involvement ofthe . rocks for hydrocarbon generation. This
shale basins. evaporitic brines that precipitated the model awaits application to many
Another factor limiting the dolomitiz- regionally extensive Manetoe Dolomite ancient deeper water dolostones.
o ing potential of these deep burial diage-
netic solutions is the fact that Ca2+ ions
ofthe NorthwestTerritories was inferred Solution Cannibalization (Goodell

o
.-...
are released to solution in amounts
by Morrow et a/. (1986) on the basis of
strontium isotope data which showed
and Garman, 1969) refers to the deriva-
tion of Mg2+ for dolomitization from the
nearly equal to, or greater than Mg2+ that the brines probably had interacted dissolution of magnesian calcite and
U
(Boles, 1981; Foscolos and Kodama, with crustal rocks. In this model, dense reprecipitation of low-magnesian cal-
o 1974).There is little, if any,excess Mg2+ hypersaline brines that have migrated cite. Some examples of partial dolo-
r-.
...., available for dolomitization . In the most to great depths in the earth's crust are mitization, such as dolomitized burrow
,. favourable situation, one might expect recirculated to shallow depths by fillings (Kendall, 1977) have been
the void spaces in porous carbonates thermal convection where they can explained by solution cannibalization,
facing shales (e.g., Wong and Older- dolomitize porous limestones. Dolomite but for more complete dolomitization
shaw, 1981) to be partly occluded with is supersaturated in such solutions, but other sources of Mg2+ are required
ferroan dolomite, but little actual dolo- the exact composition of these solu- (Hsu , 1966).
mitization of pre-existing limestone. tions can only be inferred from fluid Recently, the phenomenon of pres-
Although more work needs to be done inclusion data or by comparison with sure solution along solution seams and

o to quantify the many variables involved


in the Burial-Compaction Model, as a
first approximation it does not appear
evaporitic brines of other settings (Fig-
ure 3). Variants of this model have the
potential to explain the occurrence of
stylolites has been cited as a major
cause of dolomitization (Logan and
Semeniuk, 1976; Wanless, 1979). The
that regional bodies of dolomite can many regional late-stage dolomites, source of Mg2+ionsin pressuresolution
form by this mechanism. The observa- such as the late-stagedolomitesin some dolomitization is by solution cannibali-
tion that many deeper water slope and limestone petroleum reservoirsof Saudi zation of Mg2+ from pre-existing mag-
basinal carbonates commonly are not Arabia (Broomhall and Allan, 1985). nesian calcite during pressure solution
dolomitized even where they are over- Other Settings for Dolomitization. (Wanless, 1979). Complete dolomitiza-
lain by thick shale masses tends to con- The Organogenic Sea-floor Model for tion is thought to result from the con-
firm this impression (Wilson, 1975). penecontemporaneous to early dolo- centration of dolomite along solution
Small amounts of dolomite may be com- mitization (Figure 3), which has emer- seams as a relatively insoluble residue.
monly associated with this model, but in ged as a distinct model in only the past Intriguing as this dolomitization model
general the greater ease of dolomitiza- several years, is unusual in several re- is, it suffers from the difficulty in recon-
tion at the higher temperatures of spects. In this model, dolomite nodules ciling the deep burial setting of most
deeper burial is countered by the pro- and beds form by precipitation from stylolites (e.g., Mossop, 1972) with the
c
130 Diagenesis Geoscience Canada Reprint Series 4
c
(
c
common pre-burial conversion of mag-
nesian calcite to low-magnesiancalcite.
Associated evaporites and shales.
Laterally adjacent or overlying evapo-
common situation where early diage-
netic brine reflux may be suspected c
For large amounts of dolomite other
sources of Mg2+ are required.
rites provide sources of Mg2+-bearing
hypersaline solutions capable of dolo-
(e.g., Sears and Lucia, 1980).
Late diagenetic movements of Mg2+-
c
Many coarsely crystalline, white
sparry dolostones that have cross-cut-
mitizing by seepage-reflux ion par-
ticularly where shelf carbonates sepa-
bearing connate brines derived by
expulsion during burial compaction
c
(
ting relationships with the enclosing rate evaporite bodies from more open from evaporite masses into laterally
strata have been designated as "tec-
tonic" or "hydrothermal" dolomites in
marine sediments (e.g., Skall, 1975;
Wilson, 1975, p. 317). Dolomitized reefal
adjacent carbonates (Jodry, 1969;
Broomhall and Allan, 1985), or overlying
c
older studies, particularly in instances masses encased in evaporites is a carbonates (Jones, 1980) may also c
where these dolostones occur near
known faults (e.g., Sandford, 1962). c
However,the common absence of other c
hydrothermal minerals implies that
many of these dolostones have other c
origins. The relationship of some dolo-
stone masses to faults may merely
c
reflect the fact that ground-water move- c
ment in aquifers tends to be much more
rapid along subsurface fault zones (i.e., c
ground-water cascade zones), enhanc-
c
ing diagenesis.

ANCIENT DOLOSTONES -
CRITERIA FOR RECOGNITION OF
-
O.5mm
c
c
DOLOMITIZATION MODELS
Criteria that may guide the researcher in Figure 4 A hand specimen of a bright yellow, supratidal flat dolomicrite that has undergone
c
his choice of dolomitization models to synsedimentary folding after partial lithification, from the Rowatt Formation, a Precambrian c
apply to ancient dolostones can be
divided into three broad categories -
unit in the Belcher Islands, Hudson Bay. Thicker laminae are about one centimetre thick. The
photomicrograph on the left shows the aphanocrystalline character of this type of early c
stratigraphic, petrographic and geo-
chemical criteria. Few, if any, of these
replacement dolomite with preservation of microscopic detail. (Photographs suppliedby B.D.
Ricketts). c
criteria are unequivocal in themselves c
and it is only after the accumulation of
muchcomplementarydatathat a truly de- c
finitive choice can sometimes be made.
Stratigraphic and Facies Criteria
c
Size and shape. Small intraforma- (
tional bodies of dolomite may have local
sources of Mg2+, derived from the sedi- C
ment itself as in the Solution-Cannibal-
ization Model (e.g., Kendall, 1977; and
E
Gebelein and Hoffman, 1973), but large C
masses, such as entire formations or
major parts of a formation, invariably
C
require external sources of Mg2+. Dolo- C
stone masses that conform to rock
stratification may indicate that dolomiti- C
zation occurred before burial, but non-
conformable dolostone bodies that
C
intersect primary stratification and
facies at high angles strongly indicate
c:
that dolomitization is post-lithification C
and post-burial, particularly where l
these dolostones are associated with
solution-collapse breccias (e.g., Collins Figure 5 Medium to coarsely crystalline "late" diagenetic sucrosic dolomite in the Ordovi-
cian Allen Bay Formation of the Arctic Islands. Macroscopically identifiable Halysitid-type
C
and Smith, 1977; Morrow, 1975). The
form and location of some dolostone
colonial corals populate this outcrop from the south coast ofDevon Island. Thispreservation of
macroscopic textures indicates that no macroscopic voids were created before or during
C
masses conform to known faults indi-
cating a late post-burial model of origin
dolomitization. Microscopic details of these corals have been destroyedby dolomitization that C
formed the hypidiotopic fabric of subhedral crystals shown in the photomicrograph in the
(e.g., Skall, 1975; Jones, 1980). upper left with a field of view of 1.2 mm. (Photographs supplied by U. Mayr). C
(
C
c Dolomites - Models and Ancient Dolostones 131

c
o cause dolomitization. Similarly shales
adjacent to dolomitized carbonates are
teristic of these environments. The
sabkha depositional model with its peri -
correlation between paleogeography,
as expressed by rock facies, and dolo-
C' also suspect as sources of dolomitizing tidal and suprat idal vertical sequence of mitization reflecting a common tectonic
r solutions during their compaction. dolomite that culminates in an interval control (Wilson, 1975; Dunham and
Unconformities. Dolostone bod- of displacive anhydrite, forms a very Olson, 1980). Shelf areas tend to be
o ies are commonly developed beneath
regional unconformities (Sonnenfeld,
distinctive cyclic sequence of lithol-
ogies and sedimentary structures (e.g.,
exposedduring regression and become
the sites for freshwater recharge and
(J 1964). Many of these dolostones are Wood and Wolfe, 1969).Similarly, envi- mixed-water dolomitization. Deeper
best explained by the Mixed-Water ronmental conditions of the Coorong water carbonates which are never ex-
( Model generates an evaporite-free, posed, are not subject to this type of
freshwater aquifer (e.g., Collins and
Smith, 1975 and Figure 3). In other cyclic sequence of very finely crystal- dolomitization. Thick sequences of

o instances, such unconformities are


considered merely to represent a period
line, penecontemporaneous dolomite
with different sedimentary structures
shelf dolomite may be built up as a con-
sequence of multiple regressions. The
o of karst development that enhances the
porosity of the underlying carbonates
(Muir et al., 1980). In many instances,
reef buildups or carbonate mud mounds
seaward progradation of each regres-
sive cycle is accompanied by seaward
o so that dolomitizing solutions, what-
ever their origin , subsequently were
are facies that coincided with paleo-
topographic "h ighs" and thus were sus-
expansion of the coastal aquifer so
that a dolomitization front also moves
c localized in the strata beneath the ceptible to dolomitization by the Reflux seaward as progradation cont inues
unconformity (e.g., Skall, 1975). Model or by the Mixed-Water Model (Figure 3).
Facies development. Models for after exposure by relative changes in Petrographic and Textural Criteria
o penecontemporaneous dolomitization sea level (e.g., Eliuk, 1978; Sears and Crystal size. Previous rev iews

o such as the Sabkha and Coorong Mod-


els are verified most readily by the iden-
tification of associated facies charac-
Lucia, 1980;Exploration Staff, Chevron
Exploration Staff Ltd., 1979).
(e.g., Folk, 1973)have emphasized that
petrographically, dolostones are of
two basic types separated by a crystal
Paleogeography. There is a strong
size boundary of 10 to 20 ILm. 0010-
stones more finely crystalline than this
were characterized as primary or very
G "early", pre -burial replacements in
o which sedimentary and organic fabrics
are well preserved (Figure 4), whereas
more coarsely crystalline dolostones

c that occur mainly as stratform replace-


ments of limestone with poorly pre-
served fossil remains were considered
to be "secondary", "sucrosic" or "late
replacement" dolomites (Figure 5). A

o third major petrographic variety of dolo-


mite, which has received considerable
o attention in recent years, is the white,
very coarsely crystalline dolomite or
megacrystalline (i.e., ranging from milli-
metres to centimetres) that, in many
u places, is associated with lead-zinc min-
o B eralization (Figure 6). Much of this type
of dolomite is void-filling and displays
o curved crystal faces (e.g., Radke and
o Mathis, 1980).
Dolomicrlte. The very finely crys-
talline fabric preservation type of dolo-
( mite in many ancient dolostones is
directly analogous to the fine-grained
dolomitic sediments that form as early
A replacements of aragonite in the inter-
tidal and supratidal areas of modern
carbonate tidal flats such as in the
Figure 6 Megacrystalline white sparry dolomite of the Manetoe Facies (Formation) in the
Caribbean (dolomitic crusts), in the
,.- Nahanni Formation of the Yukon Territory. Near centimetre-sized crystals of white sparry
dolomite have partly filled spaces created by solution-collapse in the core slab (A). Photograph
sabkhas of the Persian Gulf and in the
B, at the same scale , is the exposedinner surface of one ofthese vugs displaying crystals with Coorong region of Australia . This
markedlycurved crystalfaces. This type ofdolomite is totally fabric destructive. This sample is petrographic type of dolomite usually is
a core specimen taken 11,707.0 feet below sea level in the gas-producing Columbia et al. inferred to havereplaced aragonite mud
Kootanee/ee H-38 well . before burial (e.g., Schmidt, 1966 and
Figure 4).
c
(
132 Diagenesis Geoscience Canada Reprint Series 4
C
C
Medium crystalline sucrosic dolo- host rock for lead-zinc deposits (e.g., Smith, 1975). Clearly, the processes
mite. The origin of the finely to me- Presqu'ile Dolomite) and hydrocarbon responsible for the emplacement of C
dium crystalline, suerosie dolomites
(generally hypidiotopic - an aggrega-
accumulations (e.g., Manetoe Dolo-
mite). The origin of megacrystalline,
widespread white dolomite masses
beyond the mineralized areas are not
C
tion ofsubhedra) ismuch moreproblem- white dolomite is the least certain of dependent on the processes of miner- C
atic because of the apparent absence of the three major petrographic types be- alization, although in some places the (
modern analogues. However,this type cause it has not been observed in re- converse may be true (e.g., Collins
of dolomite does occur as replacements cent sediments or in Quaternary rocks. and Smith, 1975;Davis, 1977). Probably
only the relatively small amount of
C
of Pliocene-Pleistocene limestones on However, the universal association of
some Caribbean Islands (Land, 1973; white dolomite, both as a void-filling and white sparry dolomite that is actually C
Supko, 1977; Sibley, 1982).Unlike simi- as a replacement mineral , with solution- intergrown with the ore mineralswasco-
lar dolostones in more ancient rocks, collapse breccias and solution cavities precipitated with these minerals.
C
the geological history of these Carib- indicates that it formed after lithification Variations of Mixed Water Aquifer C
bean dolostones is known with a high and probably after at least some burial. Models have been cited asthe modes of
degree of certainty and this history in Several workers have emphasized the origin of white sparry dolomites in many C
conjunction with other data, suggests
that most, if not all, of the Caribbean
common association of lead-zinc miner-
alization and white dolomite (e.g.,
studies (e.g., Lyle, 1977;Gorody, 1980;
Morrow, 1975) but the Reflux Model
C
dolomite originated by the Mixed-Water Beales and Hardy, 1980; Davis, 1979; (Davis, 1977) and the Burial Compac- C
Model (e.g., Land, 1973). Radke and Mathis, 1980) suggesting tion Model (Griffin, 1965; Jackson and
Crystals of this type of dolomite com- that both the sulphides and the dolomite Beales, 1967) have also been cited, in C
monly contain cloudy centres sur-
rounded by clear rims and the Carib-
precipitated together by means of a sin-
gle, overall-sulphate reduction reaction
addition to the model based on the late
diagenetic sulphate reduction reaction
C
bean dolostones are no exception. attemperatures between 600 and 150°C (Radke and Mathis, 1980). Recently, C
Sibley (1980)suggested thatthis pheno- (Barton, 1967; Radke and Mathis, 1980). also, the Hydrothermal Convection
menon, in the Caribbean examples at But any theory linking the origin of lead- Model has been adopted to explain the C
least, is due to the evolution ofthe diage-
netic pore fluids from a state of near
zinc mineralization with the associated
white sparry dolomite in specific areas
high temperatures of fluid inclusion
homogenization in some megacrystal-
C
calcite saturation to a state of calcite must also account for the widespread line white dolomites (Aulstead and C
undersaturation, as grain growth con- distribution of dolomite beyond the min- Spencer, 1985; Morrow et a/., 1986).
tinues under the influence of mixed- eralized area (e.g., Skall, 1975; Gorody, Unfortunately, it is evident that little
C
water diagenesis. it is likely that the 1980). It must also account for the fact overall agreement exists between C
interlocking "hypidiotopic" texture of that mineralization in most examples workers concerning the origin of
subhedra and anhedra that character- post-datedthe emplacement of much of megacrystalline white dolomite either C
izes ancient sucrosic dolostones is the the white dolomite, as, for example in general, or with regard to specific
result of grain growth from an initial in the Pine Point deposit (Skall, 1975) occurrences.
C
state where very finely crystalline dolo- and in the Viburnum Trend of the Missis- Paragenesis, texture and fluid C
mite euhedra are scattered throughout. sippi Valleydistrict (Gorody, 1980;Hagni inclusions. Detailed petrographic
These crystals grow and eventually join and Trancynger, 1977). The lead-zinc relationships and textural data in some C
along irregular compromise boundaries
(e.g., Morrow, 1978). The euhedral,
deposits in the St. George Formation in
Newfoundland are a notable exception
instances can be usedto inferthe timing
of dolomitization with respect to early
C
micrometre-sized dolomite rhombs that to this generalization (Collins and events such as the recrystallization of E
are scattered in the recent sediments
forming Andros Island (Gebelein at a/.,
THE NATURAL HISTORY OF DOLOMITE CRYSTALS
C
1980) may record the beginning of a
progression toward atotally dolomitized
C
c o
fabric of sucrosic dolostone (Figure 7). ¢¢¢¢¢¢
¢ ¢¢¢
¢
1 PARTIAL EARLY DOLOMITIZATION - BY SCATTEREO
MICROMETRE-SIZEO DOLOMITE EUHEORA THAT ARE
C
Although many ancient, stratiform,
platform dolostone sequences of
INFLUENCED BY THE CHEMISTRY OF MARINE FLUIDS
(NA, SR: 500-1500 PPM, 61RO: -1 to +4) C
sucrosic, dolostone have been inter-
I (
preted to be the consequence of mixed-
water diagenesis (e.g., Randazzo and
BURIAL
e
~ c
Hickey, 1978 ; Dunham and Olson, 2 COMPLETE LATE DOLOMITIZATION -
PROGRESSIVE GROWTH OF TRACE ELEMENT
1980), the Reflux Model has been DEPLETED, 16 0 ENRICHED SYNTAXIAL RIMS
c
~
invoked in situations where sucrosic . AROUND EARLY DOLOMITE EUHEDRA RESULTS IN
.....
. ..
.
TOTAL OOLOMITIZATION UNDER THE INFLUENCE
dolostones are adjacent to evaporites
(e.g., Sears and Lucia, 1980) or adjacent
OF DILUTE SUBSURFACE SOLUTIONS. POLYHEDRAL
CRYSTALS TEND TO HAVE CLOUDY CENTRES BUT
CLEAR RIMS.
c
to shales (Mattes and Mountjoy, 1980).
Megacrystalline white dolomite.
c
This type of dolomite is less abundant
than the more finely crystalline vari-
Figure 7 Many dolomites conform to this type of diagenetic history. The dilute subsurface
solutions are probably mixed-water or burial-compaction in origin. It is not known whether
trace element depletion in crystal rims could also be the result of slow precipitation from more
c
eties, but is economically important as a saline solutions.
(
c
c
c
(
Dolomites - Models and Ancient Dolostones 133
C
C'
n aragonite and high-magnesian calcite
(e.g.•Schmidt. 1965; Kendall , 1977;Sib-
related to the operation of specific dolo-
mitization models (e.g. , Sears and
that there is a correlat ion between the
degree of dolomite crystallin ity and the
o ley, 1980) or to later events such as the
development of stylolites (e.g., Mac-
Lucia, 1980; Mattes and Mountjoy,
1980), so that a given dolostone may
temperature at which the dolomite pre-
cipitated. Gregg and Sibley(1984)found
(
queen and Thompson , 1978; Wong and have been influenced by the operation that xenotopic crystal textures resulted
o Oldershaw, 1981). Iron-sensitive stains of a succession of such models . How- from limestone dolomitization at tem-

o (Figure 8) and cathodolominescent


techniques (Choquette and Steinen ,
1980) can reveal additional intra-
ever, it is not possible at present to relate
any of these petrograph ic types to any
particular model in the absence of other
peratures greater than 200°C.
Geochemical Criteria
Geochemical parameters. Geo-
(
crystalline textural details. Early dolo- data, butthepetrographic character of a chemical parameters include composi-
o mitization is often controlled by original given dolomite may help to limit the tional variations of the major elements

o permeability and the commonly noted


preferential dolomitization of finer
choice of models.
Analysis offluid inclusions in coarsely
Ca and Mg and the degree of concomi-
tant crystal disorder, variations in the
o grained sediments (Murray and Lucia,
1967) is probably due in large part to
crystalline dolomites (Figure 8) has
recently been shown to be effective in
content of minor and trace elements
such as Fe, Sr, Na, Mn and other less
their great abundance of nucleation determining precipitational tempera- commonly studied elements (Ba, Si, S,

o sites. Increasingly, multiple episodes of


dolomitization are being recognized
tures, salinities and some composi-
tional aspects of dolomitizing solutions
Zn, Pb),and the isotopic composition of
carbon and oxygen . A considerable
o based mainly on the recognition of a
wide variety of petrographic types of
(Aulstead and Spencer, 1985; Broom-
hall and Allan, 1985). This method is
body of literature has arisen in the past
two decades dealing with these param-
o dolomite within the three-fold pet-
rographic classification outlined above.
limited to those coarsely crystalline
dolomites with suitable inclusions.
eters. The most effective of these stud-
ies have combined stratigraphic and
Many of these varieties have been Some recent studies have ind icated petrographic data with geochem ical
o data. Stratigraphic and petrographic

o data provide a foundation of more read-


ily accessible facts upon which a frame-
o work of interpretations involving geo-
chemical data may be built.
o Compositional variations of major
elements and crystal disorder. Com-
0, positional variation of major elements
o in dolomites is commonly expressed as
a mole percent of CaC0 3 (Figure 9).
o Calcium is almost invariably present in

o excess of Mg because of the relative


ease with which Ca is incorporated into
o growing dolomite crystals. It is recog-
nized that the degree of enrichment of
o Ca in dolostones can reflect the Mg/Ca

o ratio of the precipitational solution


(e.g., Fuchtbauer and Goldsmith, 1965;
o Morrow, 1978; Lumsden and Chima-
husky, 1980). Typically, dolomicrites or
o finely crystalline dolostones that are

o assoc iated with evaporites have Ca


contents that are lower than for finely
o crystalline dolostones not associated
with evaporites (i.e., Groups 2 and 3 in
l Figure 9). Dolomites in both of these
-, groups are early diagenetic in that dolo-
mitization occurred within the influ-
r. ence of the depositional environment
(e.g., Patterson, 1972; Morrow, 1978;
and Lumsden and Chimahusky, 1980).
The relatively high Mg/Ca ratios of solu-
Figure 8 Staining textures and fluid inclusions in megacrystalline dolomites.
tions in evaporitic sett ings (e.g., Reflux
.>: (A) Successions of dolomite cement zones (numbered 9 to 13) in dolomite that fills a
gastropod pore in the Swan Hills Formation. Zones are revealed by staining with potassium and Sabkha Models) induces the for-
" . ferricyanide. (location: 10-3-67 at 8807 feet; photograph supplied by Christian Viau). mation of nearly stoichiometric dolo-
(8) Two phase aqueous liquid-vapour inclusions (arrows) in dolomite cement of the Man- mites, because the abundance of Mg
etoe Facies. These elongate inclusions are commonly less than 10 ?m long (location: ions compensates for their relative diffi-
.- 62.506°N let.; 122.991 oW long. at 710.3 m; photograph supplied by Kathy Aulstead). culty in precipitating from solution to
c
134 Diagenesis Geoscience Canada Reprint Series 4
c
c
C
form magnesium-bearing compounds
(see Morrow, 1982). On the other hand,
into how closely these parameters are
correlated. For example, crystal disor-
1980; Veizer et a/. , 1978) and direct
determinations from precipitation
r
the lower MglCa ratios of solutions in
more humid, non-evaporitic settings
der not associated with Ca enrichment
would reinforce the conclusion that
experiments are of course not possible
at reasonable temperatures.
C
(e.g., Mixed-Water and Coorong Mod- finely crystalline, stoichiometric dolo- The extreme difference in the con- C
els) results in the precipitation of more mite was rapidly precipitated from tents of trace elements in ancient versus (
calcium-rich dolomites. saline solutions with a high MglCa ratio. modern dolomites is the salient fact to
Medium to coarsely crystalline Trace element variations. The emerge from trace element studies.The (
ancient dolomites tend to be more stoi- concentration of trace elements in two most commonly studied elements,
chiometric (Group 1 in Figure 9). One dolomite ideally provides a means for Sr and Na, are present in concentra- C
explanation is that scattered, early dia-
genetic dolomite crystals in incom-
estimating the composition of the pre-
cipitational medium because the
tions approaching, orgreaterthan, 1000
ppm in modern dolomite but in ancient
C
pletely dolomitized limestones continue fractionation of an element , such as dolomites, they commonly are less than C
to grow very slowly in late diagenetic Sr, from a liquid phase into a solid a few hundred ppm (Land et a/., 1975;
subsurface environments, under the phase is proportional to its concentra- Mattes and Mountjoy, 1980). Other ele- C
influence of very dilute solutions and
possibly elevated temperatures . Slow
tion in the liquid phase (amongst a vari-
ety of other factors). This implies that
ments such as S, K, AI, Ba, Zn, Mn and
Fe have been analyzed only sporad-
C
precipitation may overshadow the influ- dolostones with greater concentrations ically in ancient dolostones and, little, if C
ence of low solution MglCa ratios and of trace elements, such as strontium or any data exist for modern dolomites.
cause the growth of the trace element sodium, precipitated from more saline The phenomenon of intracrystal vari- C
depleted, more stoichiometric, coarsely
crystalline rims that enclose Ca and
solutions; but quantitative interpreta-
tion of solution compositions based on
ations or zonations with respect to trace
elements within ancient dolomite crys-
C
trace element-enriched cores of dolo- dolomite trace element data are not tals is commonly observed, even in C
mite crystals (e.g., Land et al., 1975, feasible at present. Estimates of low crystals smaller than 10 /Lm (e.g., Cho-
Morrow, 1978). The net effect of con- temperature partition coefficients quette and Steinen, 1980). Studies of
C
tinued crystal growth during later dia-
genesis is the formation of dolostones
based on high temperature experi-
ments (Katz and Matthews, 1977; Jac-
element zonations in dolomite crystals
have also concentrated on the ele-
C
whose bulk composition approaches obson and Usdowski, 1976) or derived ments Na and Sr, and in addition, there C
from element concentrations in Holo- is some data for Fe and Mn. A general
that of stoichiometric dolomite (e.g.,
Fritz and Jackson, 1971, and Figure 7). cene dolomites (Patterson, 1972; Land pattern exists of high Na and Sr con-
C
Certainly this interpretation explains and Hoops, 1973; Behrens and Land, tents in the cores surrounded by rims C
the depletion in most trace elements 1972) have not been satisfactory (Land, with much lower contents. (Fritz and
that commonly occurs toward the C
periphery of dolomite crystals and TRENDS IN DOLOMITE C
implies that they are the products of
variants of the Mixed-Water Aquifer or STOICHIOMETRY C
the Burial-Compaction Models. How-
PRECIPITATIONAL
ever,it is now known from fluid inclusion
CONDITIONS MOLE 010 CaC03 C
evidence that some coarsely crystalline
late stage stoichiometric dolomites
Mg :Ca 50 52 54 56 58 60 62 C
were precipitated from hypersaline
rather than dilute solutions (e.g., Mor-
t
3:1
E
row et al., 1986). The reason for their C
stoichiometric composition is not appar-
. ent, but if these precipitating brines had
1 C
elevated MglCa ratios like the evapori-
tic brines on sabkhas then they might
t
2·5 -5:1
i
<35
C
C
precipitate stoichiometric dolomites in a
similar manner.
1 1 <-
Some data concerning the departure
from ideal cation ordering within dolo- t t e
mite crystals has been gathered, par-
ticularly for dolomites forming in mod-
6-22:1
I
»35
I c
ern environments (e.g., Patterson, l
1972). Unfortunately few ancient dolo-
stones have been analyzed for this
Figure 9 A summary diagram incorporating data compiled by Morrow (1978), Mattes and
Mountjoy (1980), and Lumsden and Chimahusky (1980) concerning the stoichiometry of
C
parameter. Comparisons of the degree dolomite both modern and ancient. Group 1 is composed of ancient sucrosic and sparry (..
of cation ordering as determined by the dolomites, Group 2 is composed of finely crystalline modern and ancient dolomites not
analysis of superstructure reflections associated with evaporites and Group 3 are finely crystalline modern and ancient dolomites
on x-ray patterns with the degree of Ca
enrichment might impart some insight
associated with evaporites. Group 3 also may include some late stage sparry dolomites that
contain hypersaline fluid inclusions . c
c
(
C Dolomites - Models and Ancient Dolostones 135
c
(\
o Katz, 1972; and Figure 7). On the other
hand, Fe, and possibly also Mn, tend to
Coarsely crystalline , ferroan and
non-ferroan, white, sparry dolomites
pointed out the considerable difficulties
in their interpretation. Qualitative inter-
o exhibit an opposite zonation with higher
concentrations toward the periphery of
directly associated with Pb-Zn miner-
alization or with hydrocarbons have
pretation of oxygen and carbon isotope
data involves an appraisal of the influ-
o crystals. Bulk sample analyses, of also been interpreted to have been pre- ence of the variables of temperature

c course, are weighted averages of these


zoned crystals. Some stud ies have
cipitated from saline host fluids , based
primarily on the occurrence of very
and solution compositions . Higher tem-
peratures and dilution by meteoric
( shown slight statistical differences in the saline flu id inclusions in associated water favour the incorporation of the
bulk trace element contents of a variety minerals (Radke and Mathis, 1980 ; light 160 isotope into the solid phase so
o of dolostone types (Veizer et al., 1978). Gregg, 1985) and in the dolomite crys- that dolomites that are greatly enriched
o Any explanation of dolomitization
must account for both the element
tals themselves (Aulstead and Spencer,
1985). Certainly subsurface prec ipita-
in 160 may have been influenced by
high subsurface temperatures (Mattes
o zonation of ancient dolomite crystals,
and their reduced trace element con-
tion of dolomite at the inferred tempera-
ture of greater 100 D C is less subject to
and Mountjoy, 1980) or by dilute 160 _
rich ground water (Land et al., 1975).
o tents , particularly for the aphanocrys- kinetic inhibitions. However, it is puz- The interplay of these factors is compli-
talline and fine- to medium-crystalline, zling that the few occurrences of white, cated by the probable existence of sec-
sucrosic replacement dolomites that sparry dolomite associated with Pb-Zn ular changes in the isotopic composi-
o commonly have cloudy centres and mineralization which have been ana- tion of ancient seawater (Veizer and

o clear rims. It is difficult to avoid the con-


clusion that as dolomite crystal growth
lyzed systematically for their trace ele-
ment contents (e.g., Fritz and Jackson,
Hoefs, 1976).
One certainty with regard to oxygen
o continues, it does so under the influ-
ence of progressively more dilute solu-
1971) are characterized by low trace
element contents in conformance with
isotopes in ancient dolostones is that
their bulk 0180 is much lower than that
tions that dissolve pre-existing calcite the general rule regarding trace ele- of modern dolomite crystals (Land,
and precip itate dolomite . It seems likely ments in dolostones. Saline solut ions 1980). Probably dolomite crystals are
that the cores of ancient dolomite crys- should precipitate dolomites markedly zoned with respect to their 160 content
o tals, in largely or totally dolomitized
rocks, represent individual crystals that
enriched in trace elements. This major
contradiction concerning the origin of
in a manner analogous to that
described for trace elements. Although
o formed in shallow early diagenetic white megacrystalline, sparry dolomite intracrystal variations in 160 have not

o environments under the influence of


seawater or modified seawater solu-
cannot fail to stimulate further research
and the correlation of trace element and
been described, there does appear to
be a correlation between increasing
c tions. Subsequent burial of these rocks
into deeper subsurface environments
fluid inclusion studies will undoubtedly
playa key role in resolving this paradox.
crystal size and decreasing alSOvalues
for dolomite crystals (Fritz and Jackson,
o may have been accompanied by the Distribution coefficients for some ele- 1971; Land et a/. , 1975; Mattes and

o continued precipitation from more


dilute solutions of dolomite overgrowths
ments , such as strontium (Jacobson
and Usdowski, 1976) have been deter-
Mountjoy, 1980) which is consistent with
the peripheral enrichment of 160 . This
o that are relatively inclusion-free, more
stoichiometric and lower in Sr and Na
mined for the high temperature
(> 1DO D C) precipitation of dolomite
may corroborate the interpretation that
the growth of dolomite crystals con-
o (Figure 7). Such dilute and subsurface
solutions are consistent with the opera-
which might enable quanititative mod-
elling of trace element distributions.
tinues under the influence of pro-
gressively more dilute solutions or it
(, tion of either the Mixed-Water Model or Trends of trace element concentra- may record progressive temperature
the Burial-Compaction Model. Ion filtra- tions within dolostone bodies have also increases during dolomite precipita-
tion. Regional trends of 0180 within
o tion during burial compaction of shales
can yield dilute solutions that may par-
been used as indicators of the direction
of fluid migration during diagenesis dolostones may also corroborate trends
o ticipate in the dolomitization of nearby
carbonates, although there are limita-
(Land, 1980). This type of data may
allow discrimination between models
in their trace element distributions
(Land et al., 1975).
o tions on the potential amount of dolo- for dolomitization that require different In contrast to oxygen isotopes, the

o mite that can be formed.


The commonly observed high Fe con-
centration of up to several mole per cent
directions offluid migration during dolo-
mitization, such as the Burial-Com-
paction Model versus the Mixed-Water
ratio of stable carbon isotopes (013C) in
most ancient dolostones is virtually the
same as in Holocene dolomites with
in the rims of large crystals, particularly Model. Correlations between ratios of perhaps only a slight tendency for
8 in those that have precipitated as open
space fillings with complex zonation (as
major and trace elements with strati- ancient dolostones to be enriched in
graphic position have been shown to 12C (Land, 1980). This may simply
C revealed by staining and cathodolumin- be more useful in the discrimination reflect the fact that the amount of car-
escence, Figure 8) have been related between dolomitization models than bon in dissolved species in natural solu-
qualitatively to diagenesis in the reduc- the absolute concentrations of these tions is very small compared to the
ing subsurface phreatic zone, with fluc- elements themselves in some cases amount of carbon in the carbonate
tuations in the supply of Fe2+ (Wong (Sass and Katz, 1982) . rocks that are being replaced. There are
and Oldershaw, 1981; Gorody, 1980). Oxygen and carbon isotopes. a few dolostones enriched in 12C that
These observations are also consistent Land (1980) has recently summarized may have been involved in bacterial
with either a Mixed-Water or Burial- the status of stable isotope studies reduction reactions.
Compaction Model. (0180 , 013C) of dolomite and has
c
(
136 Diagenesis Geoscience Canada Reprint Series 4
C
C
SUMMARY AND CONCLUSIONS bility. The other models are certainly Murray, R.C., 1969, Hydrology of south
The description and classif ication of viable but perhaps not to the same Bonaire , N.A. - a rock selective dolo- C
dolostones previous to about 1960wasa
comparatively simple matter as dolo-
degree and in less regional settings.
The importance of a model such as the
mitization model: Journal of Sedimen-
tary Petrology,.v. 39, p. 1007-1013. C
stones were commonly classified as Burial-Compaction Model lies not in its
BurIal-Compaction and Hydrothermal
C
"primary" or " secondary" depend ing potential for forming vast amounts of
primarily on whether the sedimentary dolomite but rather in its capacity for
Conl/ection Models C
fabric of the rock was preserved or
destroyed by dolomitization . The addi-
modifying pre-existing porosity.
Unfortunately, the criteria for choos-
Aulstead, K.G. and Spencer, R.J., 1985, C
Diagenes is of the Keg River Formation,
tional category of"hydrothermal" dolo- ing between models are not asdefinitive northwestern Alberta: fluid inclusion C
mite was used is still used (Jones, 1980) as could be desired and many of these evidence : Bulletin of Canadian Petro-
occasionally to characterize masses of criteria have been interpreted in more leum Geology, v. 33, p. 167-183. C
coarsely crystalline, space-filling white
dolomite. Little was understood con-
than one way. Indeed it could be argued
that the same criteria in some dolo-
Broomhall, R.W. and Allan , J.R., 1985,
Regional caprock-destroying dolomite
C
cerning processes of dolomitization stones such as the Presqu'ile Forma- on the Middle Jurassic to Early Creta-
ceous Arabian shelf: Society of Petro-
C
and consequently most dolostones tion (or facies) have been used to sup-
were subjected to comparatively casual port a succession of different models
leum Engineers , SPE 13697, p. 157-163. C
Gregg, J.M ., 1985, Regional epigenetic
investigations in spite of their economic as these models successively rose in dolomitization in the Bonneterre Dolo- C
importance. popular esteem. Hopefully, the time of mite (Cambrian) , southeastern Mis-
The decades following 1960 were fads is past and the choice of a model for souri: Geology, v. 13, p. 503-506. C
marked by the discovery of many exam-
ples of modern dolomitization in a vari-
dolomitization by present day workers is
based on an equitable consideration of
Griffin, D.G., 1965, The Devonian Slave
Point, Beaverhill Lake, and Muskwa For-
C
ety of environmental settings (e.g., all available criteria and by practicing mations of northeastern British Colum- C
sabkha, ephemeral lake, deep carbon-
ate aquifer) and the characterization of
the spirit embodied in the phrase "multi-
ple working hypothesis".
bia and adjacent areas: British Colum-
bia Department of Mines and Petroleum
Resources, Bulletin, v. 50, p. 90.
c:
the chemistry of these environments
has generated a greatly increased ACKNOWLEDGEMENTS
IIling, L.V., 1959,Deposition and diagenesis C
of some upper Paleozoic carbonate
understanding of the chemistry of dolo- Douglas Kent of the University of sediments in western Canada: 5th World C
mitization. At the same time, new ana- Saskatchewan and Alan Kendall of
lytical techniques (e.g., x-ray fluores- Amoco Canada Ltd. critically read the
Petroleum Congress, New York, Pro-
ceedings, Section 1, p. 23-52.
C
cence, electron microprobe, etc.) have
permitted a better overall characteriza-
manuscript and offered many useful
suggestions. I would also like to thank
Jodry, R.L., 1969, Growth and dolomitiza-
tion of Silurian reefs, S1. Clair County,
C
tion ofthe mineral dolomite itself in both A.E. Foscolos (Technical University of Michigan: American Association of C
ancient rocks and modern occurrences. Crete) and R.J. Spencer (University of Petroleum Geologists, Bulletin, v. 52,
The rapid increase in knowledge of Calgary) for discussions that contrib- p.957-981. C
Mattes, BW. and Mountjoy, E.W., 1980, Bur-
other aspects of geoscience such as uted to this review.
ial dolom itization of the Upper Devonian C
fluid dynamics and chemical changes
during the burial compaction of sedi- REFERENCES Miette Buildup, Jasper National Park,
Alberta, in Zenger, D.H., Dunham , J.B.
C
ments and the hydrology and chemistry
of coastal aquifers have had a profound Reflux Model
and Ethington, A.L., eds., Concepts and
Models of Dolomitization: Society of
C
influence on the development of theo-
Adams, J.E. and Rhodes, M.G., 1960,Dolo-
Econom ic Paleontologists and Miner-
alogists, Spec ial Publication 28,
E
ries concerning dolomitization . This
multidirectional increase in knowledge
mitizat ion by seepage reflux ion: Ameri-
can Association of Petroleum Geolo-
p.259-297. C
Morrow, D.W., Cumming, G.A. and Koep-
has resulted in the development of a
variety of dolomitization models and an
gists , Bulletin, v. 44, p. 1912-1920. nick, A.B ., 1986, Manetoe Facies - a C
Deffeyes, K.S., Lucia, F.J. and Weyl. P.K.,
increase in the number of criteria avail- 1965, Dolomit ization of recent and Plio-
gas-bearing, megacrystalline, Devo-
nian dolomite, Yukonand Northwest Ter-
C
able to discriminate between models. Pleistocene sediments by marine evap-
The objectives of this review have orite waters on Bonaire, Nethe rlands
ritories, Canada: American Association
of Petroleum Geologists, Bulletin, v. 70,
C
been twofold. First, to outline clearly the
models for dolomitization that have
Antilles, in Pray, A.C. and Murray, R.C.,
eds., Dolomitization and Limestone Dia-
p.702-720. c
arisen and to review the criteria com- genesis: Society of Economic Paleon-
Wilson , J.G., 1975, Carbonate Facies in
Geologic History: Springer-Verlag, New e
monly employed in choosing between
these models. The multitude of models
tologists and Mineralogists, Special
Publication 13, p. 71-88.
King, R.H., 1947, Sedimentation in Permian
York, p. 471 .
Wong, P.K. and Oldershaw, A., 1981, Burial
cementation in the Devonian, Kaybob
c
for dolomitization that are now recog- Castile Sea: American Association of Reef Complex, Alberta, Canada : Jour-
nized are moderately to well defined. It
seems evident to this reviewer that vari-
Petroleum Geologists, Bulletin, v. 31,
p.470·477.
nal of Sedimentary Petrology, v. 51,
p.507-520.
c
ants of the Mixed-Water Aquifer Models
are the most widely applicable - the
Morrow, D.W., 1978, The influence of the
Mg/Ca Ratio and salinity on dolomitiza-
c
first among equals - although the tion in evaporite bas ins: Canadian c
Hydrothermal Convection Model may
prove to have a similar broad applica-
Society Petroleum Geologists, Bulletin ,
v. 26, p. 389-392 . c
c
c
c'
( Dolomites - Models and Ancient Dolostones 137
c
(
r Coorong and Sabkha Models

Bush, P. , 1973, Some aspects of the diage-


Mixed Water Model

Badiozamani, K., 1973, The Dorag dolo-


Ancient Dolostones - Stratigraphic and
Petrographic Criteria

( netic history of the sabkha in Abu Dhabi, mitization model-application to the Beales, F.W. and Hardy, J.L., 1980,Criteria

r Persian Gulf , in Purser, B.H., ed., The


Persian Gulf-Holocene Carbonate Sedi-
Middle Ordovician of Wisconsin: Jour-
nal of Sedimentary Petrology, v. 43,
for the recognition of diverse dolomite
types with an emphasis on studies on
( mentation and Diagenesis in a Shallow p.965-984. host rocks for Mississippi Valley - type
Epicontinental Sea : Springer-Verlag , Choquette, P.w. and Steinen , R.P., 1980, ore deposits , in Zenger, D.H., Dunham,
C New York, p. 471.
Hsu, K.J. and Siegenthaler, C., 1969, Pre-
Mississippian non-suprat idal dolomite,
Ste. Genevieve Limestone , Illinois
J.B. and Ethington , R.L., eds., Concepts
and Models of Dolomitizat ion: Society of
liminary experiments on hydrodynamic Basin: evidence for mixed-water dolo- Economic Paleontologists and Mineral-

o movement induced by evaporation and


their bearing on the dolomite problem:
Sedimentology, v. 12, p. 11-25.
mitization, in Zenger, D.H., Dunham ,
J.B . and Ethington, R.L., eds., Concepts
and Models of Dolomitization: Society
ogists, Special Publication 28, p. 197-213.
Collins, J.A. and Smith, L., 1977, Zinc de-
posits related to diagenesis and in-
( IlIing , G.U., Wells, A.J. and Taylor, C.M., of Economic Paleontologists and Min- trakarstic sedimentation in the Lower
o 1965, Penecontemporary dolomite in
the Persian Gulf, in Pray, A.C. and Mur-
eralogists, Spec ial Publication 28 ,
p. 163-196.
Ordovician St. George Formation, west-
ern Newfoundland: Canadian Society of
( ray,R.C., eds., Dolomitization and Lime- Folk, R.L. and Land, L.S. , 1975,Mg/Ca ratio Petroleum Geologists, Bulletin , v. 23,
stone Diagenesis: Society of Economic and salinity: two controls over crystalli- p.393-427.
o Paleontologists and Mineralogists, Spe- zation of dolomite: American Associa- Davis, J.H., 1977, Genesis of the southeast

o cial Publication 13, p. 89-111.


Kinsman , D.J.J., 1966, Gypsum and an-
tion of Petroleum Geolog ists, Bulletin ,
v. 59, p. 60-68.
Missouri lead deposits: Economic Geol-
ogy, v. 72, p. 443-450.

o hydrite of recent age, Trucial Coast, Per-


sian Gulf, in Rau, J.L., ed., Second Sym-
Hanshaw, B.C., Back, W. and Deike, R.G.,
1971, A geochem ical hypothesis for
dolomitization by groundwater: Eco-
Eliuk, L.S., 1978, The Abenaki Formation,
Nova Scotia Shelf , Canada - A deposi-
tional and diagenetic model for a Meso-
posium on Salt , v. 1: Northern Ohio
Geological Society, p. 302-326. nomic Geology, v. 66, p. 710-724. zoic carbonate platform : Canadian
Muir, M., Lock, D. and Von der Borch, C., Land, L.S., 1973, Contemporaneous dolo- Society of Petroleum Geologists, Bul-
1980, The Coorong Model for penecon- mitizat ion of Middle Pleistocene reefs by letin, v. 26, p. 424-514.
o temporaneous dolomite format ion in
the Middle Proterozoic McArthur Group,
meteoric water, North Jamaica: Bulletin
of Marine Sciences , v. 23, p. 64-92.
Exploration Staff, Chevron Standard lim-
ited, 1979, The geology geophysics and
Northern Territory, Australia, in Zenger, Land, L.S., Salem, M.R.!. and Morrow, DW., significance of the Nisku Reef discov-
D.H., Dunham,J.B. and Ethington, R.L., 1975, Paleohydrology of ancient dolo- eries , West Pembina area, Alberta, Can-
( eds., Concepts and Models of Dolomiti- mites - Geochemical evidence : Ameri- ada: Canadian Society of Petroleum
zation : Society of Economic Paleon- can Association of Petroleum Geol- Geologists, Bulletin, v. 27, p. 326-359.
tologists and Mineralogists, Special ogists, Bulletin, v. 59, p. 1602-1625. Folk, R.L., 1973, Carbonate petrography in
Publication 28, p. 51-68. Lippman, F., 1973, Sedimentary Carbonate the Post-Sorbian age, in Ginsburg, R.N.,
Patterson, R.J., 1972, Hydrology and car- Minerals: Springer-Verlag, New York, ed., Evolving Concepts in Sedimentol-
bonate diagenesis of a coastal sabkha in p.228. ogy: The John Hopkins University, Stud-
the Persian Gulf, Ph.D. Thesis, Prin- Ward,W.C.and Halley, R.B., 1984,Dolomiti- ies in Geology, no. 21, p. 118-158.
ceton University, Princeton , New Jersey, zation in a mixing zone of near-seawater Gebelein, C.D., Steinen, R.P., Garrett, P.,
498 p. composition , Late Pleistocene, North- Hoffmann , E.J., Queen, J.M. and
Patterson , R.J. and Kinsman, D.J.J. , 1981, eastern Yucatan Peninsula: Journal of Plummer, L.N., 1980, Subsurface dolo-
Hydrologic framework of a sabkha along Sedimentary Petrology, v. 55, p. 407- mitization beneath the tidal flats of cen-
Arabian Gulf: American Association of 420. tral west Andros Island, Bahamas, in
Petroleum Geolog ists , Bulletin, v. 65, Zenger, D.H., Dunham , J.B. and Eth-
p. 1457·1475. Solution-Cannibalization and Pressure- ington, R.L., eds., Concepts and Models
Patterson, R.J. and Kinsman, D.J.J., 1982, Solution of Dolomitization: Society of Economic
Formation of diagenetic dolomite in Paleontolog ists and Mineralogists, Spe-
coastal sabkha along Arabian (Persian) Goodell, H.G. and Garman, R.K., 1969,Car- cial Publicat ion 28, p. 31-49.
Gulf: American Association of Petro- bonate geochemistry of Superior deep Gregg,J.M. and Sibley,D.F.,1984, Epigenetic
leum Geologists, Bulletin, v.66, test well, Andros Island, Bahamas: dolomitization and the origin of xenotopic
p.28-43. American Association of Petroleum dolomite texture: Journal of Sedimentary
l Von der Borch, C.C., 1976, Stratigraphy and Geologists, Bulletin, v. 53, p. 513-536. Petrology, v. 54, p. 908-931.
formation of Holocene dolomitic carbon- Hsu, K.J., 1966, Origin of dolomite in sedi- Jodry, R.L., 1969, Growth and dolomitiza-
ate deposits of the Coorong area, South mentary sequences: a critical analysis: tion of Silurian reefs, St. Clair County,
Australia : Journal of Sedimentary Mineralium Deposita, v. 2, p. 133-138. Mich igan: American Association of
Petrology, v. 46, p. 952-966. Logan, B.W. and Semenu ik, V., 1976, Petroleum Geologists, Bulletin , v. 52,
Von der Borch, C.C. and Jones, J.B., 1976, Dynamic metamorphism ; processes p.957-981 .
Spherular Modern dolomite from the and products in Devonian carbonate Jones, R.M.P., 1980,Basinal isostaticadjust-
Coorong area, South Australia: Sedi- rocks Cann ing Basin, Western Aus - ment faults and their petroleum signifi-
mentology, v. 23, p. 587-591. tralia: Geological Society of Australia , cance: Canadian Society of Petroleum
Von der Borch, C.C. and Lock, D.E., 1979, Special Publication 6, 138 p. Geologists, Bulletin, v. 28, p. 211-251.
Geological significance of Coorong Wanless, H.R., 1979, Limestone response Lyle, J.R., 1977, Petrography and carbonate
dolomites: Sedimentology, v.26, to stress : Pressure solut ion and dolo- diagenesis of the Bonneterre Formation
p.813-824. mitization : Journal of Sedimentary in the Viburnum Trend Area, Southeast
Petrology, v. 49, p. 437-462. Missouri: Economic Geology, v.72,
p.420-434.
(
(
138 Diagenesis Geoscience Canada Reprint Series 4
C
C
Macqueen, R.w. and Thompson, R.I., 1978,
Carbonate-hosted lead-zinc occurren-
Fritz, P. and Jackson, SA, 1971, Geochem-
ical and isotopic characteristics of Mid-
Barton, P.B., Jr., 1967, Possible role of
organic matter in the precipitation of the
C
ces in northeastern Brit ish Columbia
with emphas is on the Robb Lake
dle Devonian dolom ites from Pine Point,
northern Canada: 24th International
Mississippi Valley areas, in Brown, J.S.,
ed., Genesis of Stratiform Lead-Zinc-
C
deposit: Canadian Journal of Earth Sci-
ences, v. 15, p. 1737-1762.
Geological Congress , Montreal, Sec . 6,
p.230-243.
Barite-Fluorite Deposits : Economic
Geology, Monograph 3, p. 371-378.
C
Radke, B.M. and Mathis R.L., 1980, On the Fritz, P. and Katz, A., 1972, The sodium Beales, F.W. and Jackson, SA, 1969,Pine C
formation and occurrence of saddle distribution of dolomite crystals: Chemi- Point - a stratigraphic approach : Cana-
dolomite: Journal of Sedimentary cal Geology, v. 10, p. 237-244. dian Institute of Mining and Metallurgy,
(
Petrology, v. 50, p. 1149-1168. FOchtbauer, H. and Goldschmidt, H., 1965, Transactions, v. 61, p. 1-12.
Ricketts, B.D., 1983,The evolution of a Mid- BeZiehungen Zwishchen calciumgehalt Bebout , D.G. and Maiklem, W.R., 1973, C
dle Pre-Cambrian dolostone sequence -
a spectrum of dolomitization regimes :
und bildungsbed ing-ungen der dolo-
mite : Geologische Rundschau , v. 55,
Ancient anhydrite facies and environ-
ments, Middle Devonian Elk PointBasin,
C
Journal of Sedimentary Petrology, v. 53, p.29-40. Alberta : Canadian Society of Petroleum (
p.565-586. Land, L.S., 1980, The isotopic and trace Geologists , Bulletin, v. 21, p. 287-343.
Schmidt, V., 1965, Facies, diagenesis and element geochemistry of dolomite: the Boles, J.R., 1981, Clay diagenesis and C
related reservoir properties in the Gigas state of the art, in Zenger, D.H., Dun- effects on sandstone cementation (case
Beds (Upper Jurassic), northwestern ham, J.B. and Eth ington, R.L. , eds. , histor ies from the Gulf Coast Tertiary), C
Germany, in Pray, L.C. and Murray, R.C., Concepts and Models of Dolom itization : in Longstaffe , EJ ., ed., Clays and the
eds., Dolomitization and Limestone Dia- Society of Economic Paleontologists Resource Geologist: Mineralogical C
genesis : Society of Economic Paleon- and Mineralogists, Special Publication Association of Canada, Short Course (
tologists and Mineralogists, Special 28, p. 87-110. Handbook, v. 7, p. 148-168.
Publication 13, p. 124-168. Land, L.S. and Hoops, G.K., 1973, Sodium Butler, G.P., 1969, Modern evaporite depo- (
Sears, S.O. and Lucia, EJ., 1980, Dolomiti - in carbonate sediments and rocks: a sition and geochemistry of co-existing
zation of northern Michigan Niagara
reefs by brine refluxion and freshwater/
possible index to the salinity of diage- brines, the sabkha, Trucial Coast, Ara- C
netic solutions: Journal of Sedimentary bian Gulf: Journal of Sedimentary Pe-
seawater mixing, in Zenger, D.H., Dun- Petrology, v. 43, p. 614-617. trology, v. 39, p. 70-89. C
ham, J.B. and Eth ington , R.L. , eds., Land, L.S., Salem, M.R.1. and Morrow, D.W., Davies, G.R ., 1979, Dolomite reservoi r
Concepts and Models of Dolomitization : 1975, Paleohydrology of ancient dolo- rocks processes , controls , porosity C
Society of Econom ic Paleontologists
and Mineralogists, Special Publication
mites: geochemical evidence: American
Association of Petroleum Geologists,
development, in Geology of Carbonate
Porosity: American Association of
C
28, p. 215-235.
Sibley, D.E , 1980, Climat ic control of dolo-
Bulletin, v. 59, p. 1602-1625.
Lumsden, D.N . and Chimahusky, J.S.,
Petroleum Geologists, Short Course
Note Series no. 11, Houston, p. C1-Cl7.
C
mitization, Seroe Domi Formation (Plio-
cene), Bonaire, N.A., in Zenger, D.H.,
1980, Relationship between dolomite
nonstoichiometry and carbonate facies
Davies, G.R. and Ludlam, S.D., 1973,Origin C
of laminated and graded sediments,
Dunham, J.B. and Ethington, R.L., eds., parameters, in Zenger, D.H., Dunham, Middle Devonian of Western Canada: C
Concepts and Models of Dolomitization: J.B. and Ethington , R.L., eds. , Concepts Geological Society of America , Bulletin ,
Society of Econom ic Paleontologists and Models of Dolomitization: Society v. 84, p. 3527-3546. C
and Mineralogists, Special Publication
28, p. 247-258.
of Economic Paleontologists and Min-
eralogists , Special Publication 28 ,
De Groot, K., 1973, Geochemistry of tidal
flat brines at Umm Said, Qatar, S.E.,
C
Sibley, D.F., 1982, The origin of common
dolomite textures: Clues from the Plio-
p. 123-137.
Morrow, D.W., 1978, The influence of the
Persian Gulf, in Purser, B.H., ed., The
Persian Gulf - Holocene Carbonate
C
cene: Journal of Sedimentary Petrology,
v. 52, p. 1087-1100.
Mg/Ca ratio and salinity on dolomitiza-
tion in evaporite basins: Canadian
Sedimentation in a Shallow Epiconti- C
nental Sea: Springer-Verlag, New York,
Skall , H., 1975, The paleoenvironment of Society of Petroleum Geologists, Bul- p.377-394. E
the Pine Point lead-zinc district: Eco- letin, v. 26, p. 389-392. Dunham, J.B . and Olson, E.R., 1980, Shal-
nomic Geology, v. 70, p. 22-47. Sass, E. and Katz, A., 1982, The origin of low subsurface dolomitization of sub- C
Supko, P.R., 1977, Subsurface dolomites,
San Salvador, Bahamas:Journal of Sedi-
platform dolomites: new evidence :
American Journal of Science , v. 282,
tidally deposited carbonate sediments
in the Hanson Creek Formation (Ordovi-
C
mentary Petrology, v. 47, p. 1063-1077.
Wong, P.K. and Oldershaw, A., 1981, Burial
p. 1184-1213.
Veizer, J. and Hoefs, J., 1976, The nature of
cian-Silurian) of Central Nevada, in
Zenger, D.H., Dunham, J.B. and Eth-
C
cementation in the Devonian, Kaybob 180 / 160 and 13C/12C secular trends in ington, R.L., eds., Concepts and Models C
Reef Complex, Alberta, Canada: Jour-
nal of Sedimentary Petrology, v. 51,
sedimentary carbonate rocks: Geo-
chemica et Cosmochimica Acta, v. 40,
of Dolomitization: Society of Economic
Paleontologists and Mineralogists , Spe- c
p.507-520.
Wood, G.V. and Wolfe, M.J., 1969, Sabkha
cycles in the Arab-Darb Formation off
p. 1387-1395.
Veizer,J., Lemieux, J., Jones, B., Gibling, M.
and Savelle, J., 1978, Paleosalinity and
cial Publication 28, p. 139-161.
Foscolos, A.E. and Kodama, J., 1974, Dia-
genesis of clay minerals from LowerCre-
e
the Trucial Coast of Arabia : Sedimentol- dolomitization of a Lower Paleozoic car- taceous shales of northeastern British
(
ogy, v. 12, p. 165-191. bonate sequence, Somerset and Prince Columbia: Clays and Clay Minerals, \.
of Wales Islands, Arctic Canada: Cana- v. 22, p. 319-335.
Ancient Dolostone - Geochemical
Criteria
dian Journal of Earth Sciences, v. 15,
p. 1448-1461.
Gebelein, C.D. and Hoffman, P.,1973,Algal
origin of dolomite laminations in stroma-
C
tolitic limestones : Journal of Sedimen- (
Behrens, E.W. and Land, L.S., 1972, Sub- Other References Cited in Text tary Petrology, v. 43, p. 603·613.
tidal Holocene dolomite, Baffin Bay, C
Texas: Journal of Sedimentary Petrol- Alderman, A.R. and Skinner, H.C.W., 1957,
ogy, v. 42, p. 155-161. Dolomite sedimentation in the southeast l
of South Australia: American Journal of
Science , v. 255, p. 561-567.
C
C
( Dolomites - Models and Ancient Dolostones 139

Gorody, A.W., 1980, Dolomitization and Kendall, A.C., 1977, Origin of dolomite mot- Morrow, D. and Kerr, J.W., 1978, Strat igra-
( paleo-hydraul ic history of the Lower tling in Ordov ician limestones from phy and sedimentology of Lower Paleo-

o Ordovician Mascot Formation , Upper


Knox Group , in north central Tennes-
Saskatchewan and Manitoba: Canadian
Society of Petroleum Geologists, Bul-
zoic Formations near Prince Alfred Bay,
Devon Island: Geological Survey of Can-

r see : Geological Society of America ,


Abstracts with Program , v. 12, p. 435.
letin, v. 25, p. 480-504.
Klahn , H ., 1928 , SOsswasserkalkmag-
ada, Bulletin 254, 122 p.
Mossop, G.D., 1972,Originofthe peripheral
c Hagn i, R.D. and Trancynger, T.C., 1977,
Sequence of deposition ofthe ore miner-
nes ia Gesteine und Kalkmagnesia-
sOsswasser: Chemie der Erde, v. 3,
rim, Redwater Reef, Alberta: Canadian
Society of Petroleum Geologists, Bul-
( als at the Magmont Mine, Viburnum p.453-587. letin, v. 20, p. 238-280.
Trend, southeast Missouri: Economic Kocurko, J.M ., 1979, Dolomit ization by MOiler, S. and Teitz, G., 1971, Dolomite
c Geology, v. 72, p. 451-464.
Holland, H.D., Kirsipu, T.V., Heubner, J.S.
spray-zone brine seepage San Andres ,
Columbia : Journal of Sedimentary
replacing " cement A" in biocalcaren-
tiles from Fuerteventura, Cana ry Is-
O· and Oxburgh, U.M. , 1964, On some Petrology, v. 49, p. 209-214. lands, Spain, in Bricker, D.P., ed., Car-
aspects of the chemical evolution of Langton, J.R . and Chin, G.E., 1968, Rain- bonate Cements: John Hopkins Press,
( Baltimore, 376 p.
cave waters : Journal of Geology, v. 72, bow Member facies and related reser-
o p.36-67.
HsO,K.J. and Schneider, J., 1973, Progress
voir properties, Rainbow Lake, Alberta:
Canadian Soc iety of Petroleum Geolo-
Murray, R.C. and Lucia, F.J., 1967, Cause
and control of dolomite distribution by
report on dolomitization hydrology of gists, Bulletin, v. 16, p. 104-143. rock selectivity : Geological Society of
Abu Dhabi Sabkhas, Arab ian Gulf, in Magara , K., 1976, Compaction and flu id America , Bulletin, v. 78, p. 21-36.
o Purser, B.H., ed., The Persian Gulf- migration: practical petroleum geology: Randazzo, A.F. and Hickey, E.w., 1978,

o Holocene Carbonate Sedimentation in a


Shallow Epicontinental Sea : Springer-
Elsevier, Amsterdam , Developments in
Earth Science , v. 9, 319 p.
Dolomitization in the Floridan Aquifer:
American Journal of Science , v. 278,

o Verlag, New York, p. 409-422 .


Jackson , SA and Beales, F.w., 1967, An
Mawson, 0 ., 1929, South Australian algal
limestones in the process of formation:
p. 1177-1184.
Roy, K.J., 1972, The Boundary Member; a

o aspect of sedimentary bas in evolution:


The concentration of MississippiNalley-
Quarterly Journal of the Geological
Society of London, v. 85, p. 613-621.
buried erosional remnant of Triassic age
in northeastern British Columbia : Cana-
type ores during late stages of diagene- McKenzie, J.A., HsO , K.J. and Schneider, dian Society of Petroleum Geologists,
J.F., 1980, Movement of subsurface Bulletin, v. 20, p. 27-56.
o sis: Canadian Society of Petroleum
Geologists, Bulletin, v. 15, p. 383-433. waters under the sabkha , Abu Dhabi; Sanford , B.V., 1962, Sources and occur-

o Jacobson, R.G. and Usdowski , H.E., 1976,


Partit ioning of strontium between cal-
UAE, and its relation to evaportive dolo-
mite genesis , in Zenger, D.H., Dunham ,
rences of oil and gas in the sedimentary
basins of Ontario : Geological Associa-

c cite dolomite and liquids : Contributions


to Mineralogy and Petrology, v.59 ,
J.B. and Ethington, R.L., eds., Concepts
and Models of Dolomit ization: Society
tion of Canada, Proceedings , v. 14,
p.59-89.
of Economic Paleontologists and Min-
( p. 171·185.
Katz, A. and Mathews, A., 1977, The dolo- eralogists , Special Publication 28,
o mitizat ion of CaC03 : an experimental
study at 252°C - 295°C: Geochemica et
p. 11-30.
Morrow, D., 1975, The Florida Aquifer : a Originally published in
Cosmochimica Acta, v. 41, p. 297-308. possible model for a Devonian paleoa- Geoscience Canada v. 9 Number 2
quifer in northeastern British Columbia: (June 1980)
Geological Survey of Canada, Paper Revised 1988

o 75-1 B, p. 261-266.

o
o
o
o
o
c
r,

". .

'-...
c
140 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
c
c
c
c
c
c
c
c
c
c
c
(
(
C
c
c
c
(
c
c
c
c
C
SEM photomicrograph of an assemblage of delicate and fibrous authigenic Illite in the Lower Silurian Whirlpool Sandstone Formation of
E
Southeastern Ontario. This illite has partly filled pore spaces between planar crystals of detrital smectite and may have formed by direct
precipitation from saline pore fluids after leaching microcline feldspars. Photograph courtesy ofK.J. O'Shea andS.K. Frape (University of
C
Waterloo). C
C
C
c
e
c
(
c
c
c
c
c
c
r:

Evaporites 141

;JtJfi:-
ever, extent of this contribution may be Much of the controversy over the ori-
controversial (compare the interpreta- gin of evaporites ang the influence of
tions of Hitchon et al. (1971) with those of diagenesis or burial metainorphism~
Spencer (1987) forthe origin offormation fwtres around potash deposits. I Pot-
waters in the WesternCanada Sedimen- ash deposits are economica lly irlrpor-
tary Basin). Residual evaporite brines tant as a raw material used in the pro-
have also beencalled upon asasourceof duction offertilizers. The largest potash
Mg for the dolomitization of limestones reserves in the world are in the Prairie ,
( in shallow settings (the solution reflux FO rmat ion of Saskatchewan. Mayr-C 0 ~J
model of Adams and Rhodes, 1960)or in hofer (1985) gives estimates of 522 bil-
deeper circulating systems (Aulstead lion tons in situ and 37 billion tons of
Evaporites and Spencer, 1985; Morrow et al., 1986; mineable K2 0 worldwide. Of this, 507
Aulstead et al., 1988; inthe Western Can- billion tons in situ and 34 billion tons of
Ronald J. Spencer ada Sedimentary Basin). Similarities in mineable K2 0 are from the Prairie For-
Department of Geology and r: I the sulphur isotopic composition of mation. We address the origin of potash
Geophysics anhydrites from Devonian evaporites deposits, in terms of depositional and
The University of Calgary and anhydrite cements in carbonate diagenetic processes, using textural~
Calgary, Alberta, Canada T2N 1N4 ( units of western Canada (Nahnybida et criteria and fluid inclusion data. A brief
,...J T.K. Lowenstein
aI., 1982;Uedaetal., 1987) also suggest a
connection between these evaporites
discussion of the use of fluid inclusions
in the stud y of evapo rites is al so
Department of Geological Sciences and carbonate diagenesis. • inciudeQ,..
and Environmental Studies .- It has long been reco gnized that
State University of New York at ~evaporite minerals are easily altered on PRIMARY VERSUS SECONDARY
Binghamton burial by even modest increases in FEATURES: DEF.INITIONS
Binghamton, New York, U.S.A. 13901 .temperature. As a consequence, much There is no consensus on the meanings
attention in the past was given to such Ef the terms primary and secondar y as
) burial metamorphism (see Stewart, applied to evaporites. At the 1962Inter-
r: • Much of the material presented here
1963, p. 42-43; Borchert and Muir, natIOnal Conference on Saline Depos-
was originally published in the Sixth
1964, p.93-147, 158-159, 237-254; its primary minerals were defined as - -
International Symposium on Salt; we
Braitsch, 1971, p. 108-130, 173-195). those :'lJre.£!.f,1itated directly,from tne
, thank L.A. Hardie and the Salt Institute
Unfortunately, little agreement eme~ so lutiol;l":': and se£2,.ndarY-'l!inerals as
for permission to use the material here.
ged as to which features were due t !!:!Qgl.;19LITIgQ, later than the j:lrimary.
burial alteration and which were deposi- ~(Ingerson, 1968, p. 671). Stewart
INTRODUCTION tionalfeatures. However,in recent years held similar views in that he dealt with .....~71
Evaporites are rocks formed by pre- there has been considerable progress both "penecontemporaneous changes" f) ll' .....
7'\ cipltatlon of salts from aqueous soru- <.t in the recognition of primary and early and J2,Q§Lconsolidation changes" / ......
VQ9ns..MJNateris romo'/oEi ano:tGAlG'§p8S diagenet~features in ' .e va p o r i t e~ under secondary changes (Stewart,
cies become more concentrated. Apart throu gh studies of modern envi ron- 1963,p. 42). Braitsch (1971, p. 92), on the
from their economic value, evaporites ments. In contrast, little is currently other hand, included early diagenetic ~ ~ J
~_ are significant indicators of l3aleeeli- known about the detailed diagenetic alteration in his definition of "primary
j'J
UF" mate and of rift-vallgy tectonic settings... processes involved in the alteration of precipitation". These differences are in
In terms of the global chemical budget b evaporites during burial. If we are to one sense merely semantic, since all
they are massive subsurface "ware- properly exploit the information con- acknowledge that initial precieitates
houses" tOr storage of the soluble by- tained in evaporites, particularly those may be altered soon after deposition, soltr7o/-J1
products of chemical weathering of the involving paleochemistry and paleoen- it becomes a matter of ereference as to
crust. Most significantly, of all deposits vironments, it is absohItely essential to whetheL!Q iocl'lde early aUeratioFlo
in the sedimentary record, evaporites be able to separate those minerals, tex- .!:!.Dder erimary (as does Braitsch) or
~ are the premierrecorders ofthe chemjs- ~es and structures that are of primary under secondary (as does Stewart). On
.0/1 ':tr~ of ancient s..e..E!...YtaleI.5, lake w~ epositional origin from th ose that are. the other hand, the distinction between
and other surface waters. IYl tJ-'I ~ ue to diagenetic alteration. The ma~.n early diagenetic changes and later bur-
.it m.addltton.evaporttes may be major urpose 0 IS paper is to present a se ial changes is a truly. pivotal decision
, { " sources of solutes for deep-circula- f working criteria for distinguishing and we need terms that explicitly
ting hydrothermal brines and sedi- between syndepositional and later bur acknowledge the timing of such
mentary basin formation waters, both . I features in evaporites. Early diage- changes. In terms of timin g, a mineral,
of which may be involved in the dia- netic features are emphasized beca'iSe mineral assemblage. texture, fabric,
genetic alteration of other basinal sedi- they are best documented. The criteria be
1!.uid inclusion or ~.t[lJe.tllre COl lid
ments. 1JJ-e-e0ntribution of solutes from fCiri5i:mat alteration are more uncertain (1) depositional, i.e., formed at the time
evaporites in sedimentary basin form.a:.. because they must be inferred without of deposition of a sedimentation unit or
l ion waters associated with ore d~osits • the aid of active modern systems. These deposited in its existing form;
and oil fields is discussed by Ritten- criteria are updated from those .pre- (2) post-depositional but pre-burial,
house(1967)an~.f!!]~enter (197a)...l:foW:: sented by Hardie et al. (1985). i.e., formed diagenetically soon after
(
142 Diagenesis Geoscience Canada Reprint Series 4 (
r
(
deposition by processes controlled by tion is extensive but where it has still ( Sedimentary Structures
the existing depositional environment; been possible to "read through" the It is well documented that mechanical (
or (3) post-burial, i.e., formed by late alteration. Secondary evaporites would sedimentary structyres typical of clastic (
diagenetic or metamorphic-metasoma- be those deposits so thoroughly altered deposition are common in evaporite
tic processes controlled by the subsur- on burial that few if any syndeposi- deposits, particularly those involving (
face burial environment. tional features can be unambiguousl gypsum-anhydrite and, to a lesser
~ The first two classes, one primary identified. extent, halite (Dellwig, 1968; Dellwig (
- ~" (depositional) and the other secondary and Evans, 1969; Hardie and Eugster, (
(diagenetic), both depend on processes CRITERIA FOR SYNDEPOSITIONAL 1971; Parea and Ricci-Lucchi, 1972; ,'i
operating in the depositional environ-
ment. They both house valuable infor-
mation about primary environmental
parameters and for this reason we have
grouped them together under syn-
FEATURES
Criteria for syndepositional features
comprise (a) mechanical sedimentary
structures with detrital textures and fab-
rics formed by deposition from bedload
Ricci-Lucchi, 1973; Schreiber et a/.,
1976; Schlager and Bolz, 1977; Schrei-
ber and Hsu, 1980). These are essen-
tially stratification and bed form struc-
tures, but other primary structures such
Q

f :f (
(

depositional features, as distinguished or suspended load; (b) crystal textures ~ m p foldin g _(Schlager and Bolz, (
from post-burial features. In a deposi- and fabrics produced as chemically pre- 1977, p. 602), sole markings (Parea
tional context, then, we could regard cipitated minerals grew in situ on and and Ricci-LucChi, 19(' , fi gure 24), C
all syndeggsjtioAaUeatufes....inch .ding within bottom sediment; and (c) fea- mudcracks. and flat pebble con lomer- C
e!!'ly diagenetic (penecontemporane:. tures indicative of syndepositional dis- ates (Hardie and Eugster, 1971, figure
ous) alteration ~Rtimar~ Post-burial SOlution, reprecipitation and cementa- 20) have been reported. The preserva-
features would be " secondary". How- tion of evaporite minerals. The first two tion of all these structures in evaporite

r
ever, we prefer to emphasize the timing types of information (a and b above) are sedimentation units not only testifies
(
aspect of the problem and so in com- summarized in brief. The reader is re- against pervasive destructive recrY.§- ~
Pili ng criteria we have followed the ferred to Hardie et at. (1985) for further tallization, replacement and deforma-

t syndepositional versus post-burial


classification.
But there remains a class of features
that are equivocal in that there are no
details. The latter (c) can be considered
evidence for early diagenetic changes,
and is discussed more completely
below.
tion oft e eposit, bUtitaIlQWS.\laIUabl1
interpr~tations .to .be made about-depe
sitional processes and -the -envleen- 11
~s in Wtftc.5Jhey operated.
~

(
decisive criteria that point to their time
of origin. We have grouped these under

(])
ambiguous features.
"[Q. complicate matters. it is common c
to find extensive secondary changes iQ.
mineralo.,gy_wiJb-no..cbange..io..tbe..pJ:·-
c
~-lll.xtur.e_(e. g. , pseudomorphous
replacement by halite of vertically ori-
ented gypsum euhedra, Lowenstein, c
1988, figure 6) or alteration of texture
that does not entirely obliterate tfie
~Jnal depOSItional structure (e.g., Dell-
(
wig, 1955, figure 2; Hardie and Eugster,
1971, figure 11 A). !?espite the alteration
overprints we regard S'lch recogniz-
able primary textures and structyres as
syndepositional features ~ca~ c
carry legibJejnf.ounatioo.about.depgsi-
tional prgcass.es..aod C;:llViLQnmflDl~.
l
~
Finally, the terms primary and sec-
ondary are not easily applied to evapo-
rite deposits as a whole because many
(
deposits carry both syndepositional (
and secondary alteration features (and
commonly in the same bed or crystal , as (
just discussed above). Should the need
lllise to use such terms for the overm) l
Figure 1 Thin-section photomicrograph of part of a wave ripple composed of prismatic
deposits, then we suggest "primar\!
gypsum pseudomorphs, viewed perpendicular to the strike of the ripple crest. Clear crystal
_evaporite" might he ••sed to desC[i~
fragments with gypsum morphologies butnow composed of halite, are aligned along foresets.
those deQositsnot sufficiently altered to Dark surrounding sediment is microcrystal/ine anhydrite and polyhalite. Vertically oriented
a
oDscureJl:ul_ptima c.y....sYRdeposiiion I prismatic gypsum pseudomorphs (bottom), composed of halite and some sylvite, are the same
,mati 'res. Or perhaps "modified primary size and shape as the gypsum pseudomorphs comprising the wave ripples. Sample from
evaporite" might be better where altera- Salado Formation laminated anhydritelpolyhalite rock. Scale bar is 5 mm long.

l
(
.----------...
( - --:==-::- ~ ._=:::,-:~'
Evaporites --- -------:\ / -> 143
(od ~ -
<,

~.I/// ./'
<:>
Detrital Framework Textures. two types: (a) mechanical accumula- Crystalline Framework Fabrics .
As with other sedimentary rocks, the tions of cubes that precipitated in the Fabrics diagnostic of in situ! open-space
classic criterion of a framework of grains water column and settled to the bottom crystal growth on the bottom of brine-
( with point contacts should firml¥-estab- such as those preserved in modern pools are commonly preserved in mOd~
Iish a primary detrital texture in evapo- saline pans (Lowenstein and Hardie, ern and ancieQt evaporites particularly
rites For example, in gypsum grain: 1985,figure 11)and in certain beds in the for gyp sum and halite (Schaller and
stones the detrital framework may be Permian Salado Formation of New Mex- Henderson, 1932; Stewart, 1949, 1951;
( made up of abraded fragments of single ico (see Lowenstein , 1988, figure 14); Hardie and Eugster, 1971; Schreiber
selenite crystals (e.g., Hardie and Eug- and (b) frameworks of abraded crystals and Kinsman, 1975; Caldwell , 1976;
ster, 1971, figures 15and 16)or of stacks sorted by bottom currents, as for exam- Schreiber and Schre iber, 1977; Arakel ,
of gypsum needle euhedra or iented ple, those reported byWeilereta/. (1974) 1980; Warren, 1982; Lowenstein, 1982,
parallel to foreset laminae (Figure 1; along the shores of the South Basin of for gypsum, and Gottesmann, 1963;
Lowenstein, 1988, figure 9). Halite detri- the Dead Sea (see their figures 2 Jones, 1965; Wardlaw and Schwerdt-
tal textures are subtle features easily through 6). ner, 1966; Shearman, 1970; Arthurton ,
overlooked. Such textures may be of 1973 ; Handford, 1981; Lowenstein,
1982, 1988; Hovorka, 1987; Brodylo and
( Spencer, 1987 for halite). Such fabrics
for other salts have been reported (see
Eugster, 1970, for trona, and Wardlaw,
1972, for carnallite), but, unfortunately,
there are no complete descriptions.
The dominant fabric of open-space
prec ipitation is a layered, syntax ially
grown crystalline framework consisting
of vertically oriented and vertically elon-
gated crystals. In essence, this fabric
represents competitive crystal growth
upward into a free-standing, saturated
brine, a process identical in style to
void-filling cement crystallization . There-t
fore, the cement criteria carefully docu-
mented by carbonate petrographers
(see Bathurst, 1975, p. 416-425~
as guides to the recognition of open
o space bottom rowtb_oLa..crystaliine

c ramework fabric in evaporites. When


specifically applied to the evaporite
o minerals gypsum and halite as viewed
in thin section, the basic fabric crltesia
for syndepositional bottom growth are
as follows :

r
(1) for gypsum, verticall y oriented
prisms with Auhedral terminations
(commonly " swallow-tail" twins) , and
for halite , vertically directed "chevrons"
(syntaxia'i overgrowths on upward-fae;..
*
ing cube coigOS) and " cornets" (syntax-
ial overgrowths on upward-facing cube
faces) with euhedral terminations and
fluid inclusionbanding parallel to cry~
tal growth faces (Figure 2);
(2) I,Jpward-coarsenin and widenin of
crys a s Figure 3; Hardie and Eugster,
,- I 1971, figure 21 ; Arakel, 1980, figure 9)
,-,' where , during competitive growth, crys-
r\ tal bottoms abutthe substrate and sides
Figure 2 Photomicrograph of vertically oriented halite chevrons (upward-directed edges
of crystals abut one another along com-
and corners) and cornets (upward-directed cube faces) , Within single crystals, dark bands promise boundaries (Shearman, 1970;
".-
rich in fluid inclusions alternate with lighter bands containing few fluid inclusions, White areas Bathurst, 1975, p. 421-425 and figure
'--. are clear inclusion-poor halite, usuallypresent as rims on chevrons and cornets. Sample from 303). Crystal growth is therefore most
\.....
Salado Formation mud-free halite. Scale bar is 3 mm long. rapid on upward-directed faces . For
c
144 Diagenesis Geoscience Canada Reprint Series 4 (

C
example, for halite, the upward-facing plate 3, figure 4; Shearman, 1970,figure 1966,plate 3, figure 4; Arthurton, 1973, C
cube faces and coigns of foundered
hoppers that settled randomly on the
6; Arthurton, 1973, figure 9; Hovorka,
1987;Brodylo and Spencer, 1987, figure
figure 9);
(2) rounding ofeuhedral terminations of
C
bottom become the dominant growth 3; Lowenstein, 1988,figure 13)indicate single crystals followed by syntaxial C
directions, producing "cornets" and dramatic fluctuations in solution com- rehealing (Figure 6). For example,large
"chevrons", respectively. position during crystal growth and layer selenite crystals have been found with C
Additional textural evidence that sup-
ports a syndepositional origin of verti-
accumulation .
Evidence of syndepositional dissolu-
rounded terminations draped by thin
mud laminae and rehealed by renewed
C
cally oriented crystal fabrics is tion is discussed by Lowenstein and syntaxial growth that preserves both the C
(3) growth originating from a common, Hardie (1985) and is basically of two rounded faces and the mud laminae
laterally continuous substrate, par- types: within the vertically grown crystals
C
ticularly where the basal zone of the (1) sharp but smooth truncations paral- (Hardie and Eugster, 1971, figure 21; C
growth layer consists of detrital seed- lel to bedding of vertically oriented crys- Schreiber and Kinsman, 1975,figure 7).
crystals; tal frameworks overlain in turn by layers More complex dissolution and re~­ C
(4) mud drapes or crystal cumulates of detrital mud, crystal cumulates or cipitation features accoJD.Qan~
C
immediately above vertically oriented
crystal layers thicken in depressions
and thin over tops of the framework
vertically oriented crystals (e.g., Figure
5; see also Wardlaw and Schwerdtner, ----
abOVe Qllil.n..o..r.rnma...i.o..moJ:l..er.n.epbem-
eral salt pans where halite cr ystalline C
C
crystals (Figure 4). This demonstrates
that vertically directed growth must
nave occurred before deposition of
C
overlying layers (e.g. , Hardie and Eug- C
ster, 1971, figure 21).
(5) dissolution or erosion surfaces that C
truncate vertical crystals and act as sub- ~
stratesforgrowthofa newcrystallinelayer
(see Lowenstein and Hardie, 1985). C
Crystalline framework fabrics pro-
duced by syndepositional open-space C
growth on the bottom of a brine body
preserve a wealth of information on pri-
C
mary environmental conditions. We C
believe that syntaxially grown crystal-
line frameworks are not only primary
C
features but strong evidence for shallow C
unstratified evaporite environments.
The presence of dissolution - repreci- C
pitation features provide additional
confirmation of this view because
C
such features require either ephemeral C
conditions or shallow enough brines to
allow significant brine dilution by under- E
saturated flood water influxes. The
abundance of crystalline frameworks
C
showing dissolution features in modern C
salt pans (Lowenstein and Hardie, 1985)
amply support this contention. Finally, C
the fluid inclusions that outline growth
layering in halite crystalline frame-
C
works, for example, can add significant
information about the syndepositional
physicochemical conditions (see later). e
Dissolution - Reprecip/tation c
Features.
Syndepositional dissolution - repreci- c
pitation features in gypsum-anhydrite
(e.g., Hardie and Eugster, 1971, figure c
21;Schreiber and Kinsman, 1975,figure Figure 3 Photomicrograph (crossed nicols) of upward-coarsening and widening halite c
7; Warren, 1982, figures 12, 15B) and
halite deposits (e.g., Dellwig, 1955, fig-
ure 11; Wardlawand Schwerdtner, 1966,
crystals (black) outlined by gray microcrystalline polyhalite. Halite cornets (centre), with
upward-facing cube faces, are flat-topped (arrow) and overlain by smaller vertically oriented
crystals. Sample from Salado Formation mud-free halite rock. Scale bar is 2 mm long.
c
c
c
0
( . Evaporites 145


(
0
0
( Figure 4 Photomicrograph of halite and sylvite
from the lower potash zone (Couche inferieure),
( Mulhouse Basin, Tertiary Rhine Graben. Halite
layer (H) is composed of centimetre-size, vertically
(. oriented chevrons that contain fluid inclusion
C growth-banding (dark gray to black). Sylvite layer
(5) contains millimetre-size crystals of sylvite with
(' equigranular mosaic texture. Millimetre-size cumu-
late halite crystals occur in sylvite layers. Minera-
C logical sequence of dolomitic mudstone (black) ->
halite + minor anhydrite -> sylvite + minor halite.
C Note that sylvite crystals form a drape above pro-
jecting crystals of chevron halite; the top of the
( sylvite layer is nearly flat.

0
0
0
0
0
0
0
(
C
0

0
0
0
0 Figure 5 Photomicrograph of halite crust
(depth < 0.5 m) from Salina Omotepec, Baja
0 California, Mexico (collected 1972). Dark
areas are rich in fluid inclusions. Dissolution
0 surface (between arrows) truncates tops of
vertically oriented chevrons. Subsequent
0 syntaxial overgrowth rebuilt the chevrons
0 above the dissolution surface. Verticallyori-
ented voids (V) are partly filled with clear
(\ halite cement. Scale bar is 2 mm long.

8
C
('

,~

'-...
r-
'--

L.-
146 Diagenesis Geoscience Canada Reprint Series 4
c
(

C
frameworks are forming . Ephemeral pans, Shearman, 1970; Lowenstein and primary framework is enclosed by C
salt pans go through a repeating three- Hardie, 1985)oron burial. Insome cases, (1) intergranular cements and (2) vug
stage cycle of events: (1) an initial flood- it may be possible to decide on the timing and cavity cements. C
ing stage when undersaturated flood
waters inundate the pan after a storm,
of cementation from petrographic evi-
dence. For example, meniscus cements
Intergranular cements usually con-
sist of a mineral lining or filling the pore
C
(2) a saline lake stage when evaporative surely call for a vadose setting and this in spaces ofa primary crystalline or granu- C
concentration leads to growth of a crys- turn implies a syndepositional origin . lar framework. For example, in Figure 7
talline framework layer, (3) a desicca- Also, if erosion or dissolution surfaces coarse sylvite cement fills the voids C
tion stage when the pan surface dries up cut across cements, or if internal sedi-
ment overlies a cement, then there can
between cubes of halite in the Permian C
and only subsurface, intracrustal brines Salado Formation . These voids are
remain (Lowenstein and Hardie, 1985). be little doubt about the syndepositional identical in size and morphology to pri- C
The initial flood stage, in addition to nature of the cements. mary unfilled voids so typical of porous
producing dissolutional truncation of We have recognized two basic stYle~ crusts of halite in modern salt pans (Fig- C
the framework and rounding of individ-
ual halite crystals, causes extensive
of cementation in modern and ancient
evaporites which we interpret J!§ sYO=.
ure 8; Lowenstein and Hardie, 1985).
Other common features of this type of
C
tubular networks of vertical and hori- de os' . These are cases where cementation are isopachous colour C
,fA." ~c \,-a ontal dissolution cavities that follow
C
I

): (ht.\~ grain boundaries between verticallyori-


ll)"'P ented crystals and along bedding C
lU U- Planes (Figure 5). Subsequent evapora-

--
tive concentratlofi'Bt t e troodwaters
results in halite saturated brines and
C
C
renewed crystal growth. DissoluiiCi'i'1'
~ C"aVitiesbeccimeTIned with inward grow- C
ing clear halite crystal cements and
rounded and dissolved euhedra are C
rehealed by syntaxial growth. At the
desiccation stage, the brine sinks below
C
the pan surface and the voids in the C
upper halite crust become partly filled
with a cement of clear halite (Lowen- C
stein and Hardie, 1985). All these fea-
tures are syndepositional , formed con-
C
currently with deposition of the halite C
framework layers, but they may not be
easy to distinguish from some burial C
dissolution-reprecipitation features in
ancient evaporites. Burial dissolutipn,
C
cementation and re ~r~aUization could C
give rise to rounded voids filled with
clear halite cements as well as to
C
pateheSOf clear halite mosaics. Care E:
must be taken to look for other evidence
of the timing of dissolution and cemen- C
.fjJt::-
tation, such as internal sediment over-
lx!!Jg cement, truncation of void fills by
C
primarl.!ayering, etc. C
-Cements.
Cements have gone essentially un- C
noticed in evaporites despite the fact that c
undeformed and uncompacted buried
salts typically have negligible porosities, e
and yet their analogous unburied pri-
mary deposits may contain more than c
50% void space (e.g., Lowenstein and
Hardie, 1985). This anomaly suggests
c
that cementation must be an important
process in evaporite diagenesis.
c
Figure 6 Photomicrograph of dark gray fluid inclus ion-banded vertically oriented halite.

~
Cements are post-depositional fea-~ Chevron halite crystal contains internally rounded cube coigns that have syntaxially rehealed
tures, but they could form either syn- (arrow). Clear, inclusion-poor halite located between chevrons and cornets. Sample from
depositionally (as is common in salt Salado Formation mud-free halite rock. Scale bar is 3 mm long.
c
c Evaporites 147

c
c bands within cement crystals thatfollow
c original void boundaries and coarse
poikilotopic crystals that may enclose
( many framework grains.

c Cavities and vugs lined or filled with


cement are common in modern evapo-
c rite deposits. In halite salt pans, vertical
and horizontal networks of dissolution
c cavities and shelter vugs are lined

o with euhedral cement crystals made of


clear halite (Lowenstein and Hardie,
c 1985, figure 16). In modern gypsum
pans, shelter vugs beneath rumpled
( surface crusts may be lined with
masses of gypsum "swallow-tail" twins
(J (ct. Warren, 1982, p. 628). Such cavity
C cementation has not been commonly
reported from ancient evaporites (see
o however Hovorka, 1987; Casas and

o Lowenstein, in press).It isalso likely that


the clear rims of halite on cloudy chev-
(? rons and cornets so common in ancient

o halite rocks (Wardlawand Schwerdtner,


1966, plate 2, figure 4; Lowenstein,
o Figure 7 Photomicrograph of muddy halite rock. Clear halite crystals contain incorporated
1982,figure 6C) are cavity cements (ct.
Shearman, 1970). In modern salt pans,
clear halite rims form syndepositionally
mud and few fluid inclusions. Dark areas between halite cubes are composed of zoned
o crystals of sylvite cement and minor mudstone. Scale bar is 3 mm long.
as overgrowths on porous chevron and
cornet frameworks during the saline
o lake and desiccation stages (Lowen-
stein and Hardie, 1985). However, simi-
c lar textures can just as easily be pro-

o duced on burial, assuming the open


framework of halite can survive burial.
o A strong case for syndepositional
halite and potash cements may be
c made based on porosity profiles from

o modern salt pans (Casas and Lowen-


stein, 1987, in press).The high porosities
c. of surface salt crusts from modern salt
pans decrease sharply in the upper few
o metres from 50% to less than 10%; po-

o rosity is negligible below 30 m. It ap-


pears that the open framework of salt
c pan halite is cemented very early in the

o burial history. Therefore, based on com-


parison with modern deposits, we con-
clude that cements which line or fill a
C primary granular or crystalline frame-
l\ work in ancient halite deposits probably
formed early, and are included as syn-
b depositional features.
C CRITERIA FOR BURIAL
L Figure 8 Photomicrographs of halite in a muddy halite layer from just beneath the surface of
ALTERATION FEATURES

c: the modern salt pan of Saline Valley, California. The halite occurs as randomly oriented
interlocking cubes with incorporated mud (black) and cloudy patches dense with fluid
Our concern here is to identify features
that clearly reflect alteration,poth dia-
genetic and metamorphic, due to the
inclusions (arrows). Primary voids (V) surround halite crystals. These voids are equivalent to
~ .. the space occupied by sylvite and carnallite cements in the Salado and Prairie Formations Increased pressyres and temperatures
L (compare with Figures 7 and 22). Aggregates of interlocking small rhombs of glauberite and Of burial. as well as changes due to
mud (black) are also present. Scale bar is 5 mm long. m etasomatism by invading subsurface
c
148 Diagenesis Geoscience Canada Reprint Series 4
c
C
waters . We are on somewhat uncer- limestones. More insight into the signifi- anhedral mosaic consists of clear r
tain ground here because roaoy...o.Ub.e cance of sutured mosaic textures in grains that meet at triple junctions that
Cflteria must be inferred . raJb.~~ r~ evaporites must await future work. approach 1200 angles in typical anneal- C
obtained direG-tlv. frOl!LG-Qmp'ar:~tW ~ Polygonal Mosaic Textures. ling recrystallization polygonal mosaic
dies of active modern systems. None- Polygonal mosaic textures have long fashion (Stanton and Gorman, 1968,fig-
C
the ess, we aveputtogetheratentative been documented in experimentally ures 2,3 and 7). The crystals have few (
working set of criteria, some of which we treated metals and metallic ore minerals inclusions (large rectangular fluid-filled
have listed more as a basis for discus- (Buckley, 1951; Burgers , 1963; Stanton cavities and blebs of mud), as most of C
sion than as accomplished facts . In the
main the criteria involve textures and
and Gorman, 1968). Similar textures
are typical of metamorphic rocks (VolI,
the "foreign " matter appears to have
been purged to the halite crystal bound-
C
structures that record disruption, defor- 1960). There is a consensus that these aries during recrystallization (cf. Kuhn, C
mation and destruction of primary polygonal mosaic textures are a product 1968, plate 2, figure 2): These are all
features. of annealling recrystallization whereb y features typical of "foam structure" C
0' Disruption and Destruction of Sedi- ,gr~ins optiMize:' their §Ize, snaReand produced by experimental rscrystalllz- C
V mentary Structures. orientation to minimize the energy in the ation of metals and ores and attests to a
The absence of primary beddin~ or the .nannerof bubbles in foam (Stanton and destructive burial recrystallization pro- C
/\. ,~ ~esence of only scattered rem ants of Gorman, 1968). cess that leads to complete loss of any
, v V IC/'primary beddin g or other sedimentary Evaporites, because of the ease with primary signature. However, such re- C
structures in massivecrystalline mosaic
salts points to destryctive seGGFlgefy
which they are altered at the tempera-
tures and pressures of even mode~
crystallization may be very patchy, as
we have seen in the Permian Salado
C
crystal growQ!...];he early stages of this burial, should be very susceptible to. evaporite of New Mexico and Devonian C
destructive growth will be seen as irreg- SiiCli'anneaIljOQ-f.EtCLY..stallizatlao.. We Prairie evaporite of Canada where pri-
ular isolated crystalline mosaic patches have found halite in the Permian Sa- mary, unaltered "chevron" halite co- C
(see next section) that cross-cut pri-
mary sedimentary structures (e.g.,
lado formation of New Mexico and the
Devonian Prairie evaporite of Canada
exists at the same or greater burial
depths as "foam" structured halite.
C
Schreiber et al., 1976, figure 18). This with equigranular mosaic texture (Fig- ~ Deformation Features. C
criterion is most persuasive of burial
alteration when found in monomin-
ure 9; see also Lowenstein and Hardie,
1985).This halite notably lacks vertical
Apart from the obvious macroscopic
deformation structures such as folds,
t
erallic (or essentially monominerallic)
rocks because then the crystalline
orientation, cumulate textures, banded
fluid inclusions or any other feature dia-
fractures, veins, flow banding, pressure
solution sllrfaces, etc. (e.g., Balk, 1949;
c
mosaics must surely be the result of gnostic of primary growth. Instead, the Goldman, 1952;Mulleretal., 1981)there C
destructive recrystallization. Such
crystalline mosaics will have suturecror
C
polygonal grain boundaries see below) C
quite distinct from porphyroblasts and
from-tl;e--isolated disp.lacive, incorpora- C
tive or poikilotopic growthofeuhedra and
nodules typical of syndepositional intra-
C
~ sediment crystallization (see below). C
'® Sutured Mosaic Textures. C
Crystalline mosaic textures in which
)It.~~ 3i n boundaries ar sutured in the
7 G
fw 'lj manner of neomor hlc s r of c -
a e roc s compare Hardie and Eugster, C
"jf~ 1971, figure 11A, with Bathurst , 1975, C
figures 336 and 338) clearl y indicate a
secondary grain growth origin. How- C
ever, the conditions under which this
secondary mosaic formed are Rot C
~SuChan interpenetration of
grains may represent a low tempera-
c
ture , non-equilibrium texture (VolI, e
1960); it certainly stands in marked con-
trast to the equilibrium polygonal c
mosaic textures formed experimentally
by annealling recrystallization (next
c..
section). Supportive of this contention Figure 9 Photomicrograph ofhalite with equigranularmosaic texture ("foam" texture). Note c
are the contrasts between the polygonal
texture of marbles and the tortuously
the number of curved crystal boundaries that meet at triple junctions with angles approaching
120°. Mud (black) is included within halite or located at halite crystal boundaries. Small gray
c
sutured boundaries of most diagenet-
ically altered, but unmetamorphosed,
bubbles scattered throughout were (artificially) trapped during thin-section preparation.
Sample from Salado Formation muddy halite rock. Scale bar is 5 mm long.
c
C
\.
C
(
( Evaporites 149
(
c: are more subtle microscopic deforma-
o tion features to look for in thin section or

c Tn etched, polished slabs of evaporites


~ (Schlichta , 1968). Stanton and Gorman
1I~ ( 1 9 6 8) have discusssed the main types
(
of deformation textures recognized in
( metallurgical studies and applicable to

c rocks (see also VolI, 1960, 1976). These


deformation textures are (1) deforma-
o tion twins, (2) slip lines and slip bands,
....-r:t. _ (3) lattice distortion features such as
( fJ 0 ' -- .!:!Ddu!ose extinct ion, bent cleavages,
o etc., (4) SUb-graindomains and (5) flat-
tening of grains leading to formation of
o foliation. We leave the reader to seek
help from the above and other works
( (e.g., Prucha, 1968; Mossop, 1979) in

o recognizing deformation features in


evaporites.
t AMBIGUOUS FEATURES
o There are a number of features that
could have formed either syndeposi-
tionally or after bllW3J..Lo.tbe"~sence of
o -otFiercriteria to aid intheir interpretation

o the time of origin of such featllCes !llY§t


~main uncertain. To this class of am-

o biguous features belong (1) mineral


growth within the sediment as euhedra
o Figure 10 Core slab photograph of halite cubes which have displaced the surrounding
or nodules,(2) pseudomorphous replace-
ments, (3) coarse crystalline salt, and
carbonate-rich mud. Mud is also incorporated within some of the growth bands in the halite (4) certain cavity cements.
o crystals. Sample from the Prairie Formation.
(0 Intrasediment Growth of Euhedra.
Evaporite minerals that have grown
o within sediment commonly occur as
randomly oriented , isolated or interlock-
ing crystals with a euhedral or sub-
o hedral habit. Such crystals may incor-
porate sediment during growth or they
o may form displacively by pushing aside
the host sediment during crystalliza-
tion . The Devonian Prairie Formation .
o contains examples of gypsum (anhy-
drite) and halite (Figure 10)with displac-
c ive or incorporative growth habits. The
Permian Salado evaporite of New Mex-
C ico (Lowenstein, 1982, 1988) carries
(1 many good examples of this style of
intrasediment growth by the minerals
O· gypsum (Figure 11), halite, glauberite
(Figure 12) and langbeinite (Figure 13).
Incorporative growth provides un-
l equivocal evidence of post-deposition-
al crystallization, but the difficulty is~.n
distinguish ing between early-syri-
aepositional growth and later meta- '-i:-
morph ~ ' ~rp hyr~astisg rowth. Intra- 'I'
sediment growth of minerals such as
r- Figure 11 Photomicrograph of mud-incorporative gypsum crystals (pseudomorphously gypsum, halite and mirabilite as euhe-
'-- replaced by microcrystalline anhydrite). Surrounding mud contains magnesite and anhydrite. dral crystals is a common near-surface
,'.
Sample from Salado Formation laminated anhydrite rock. Scale bar is 2 mm long. feature in many modern playas and
"-..
r:
'-..

c
c
150 Diagenesis Geoscience Canada Reprint Series 4 c
(-

c
c
c
c
c
c
c
c
c
Figure 12 Photomicrograph (crossed
nicols) of randomly oriented, zoned, incor- c
porative glauberite euheare, now pseudo-
morphously replaced by halite (dark gray to c
black) and anhydrite (light er gray). Sur-
rounding sediment is microcrysta lline an- c
hydrite and magnesite-rich mud. Sample
from Salado Formation laminated anhydrite
c
rock. Scale bar is 5 mm long.
c
c
c
c
c
c
c
c
c
c
c
C
E
Figure 13 Photomicrograph of isolated,
randomly oriented tetrahedral langbeinite C
crystals with incorporated mud in crystal
cores. The larger crystal contains lang-
C
beinite in its core (light gray). Therim and the
entire smaller crystalhavebeenpseudomor-
C
phously replaced by microcrystalline leonite C
plus kainite. Surrounding area is mud(black)
and halite (light gray). Sample from Salado c
Formation muddy halite rock. Scale bar is
5mmlong. e
c
c
c
c
c
c
c
c
c
( Evaporites 151
c.
C',
sabkhas (Hardie, 1968; Butler, 1970a; Red Sea hot brines in the Atlantis II placement rests on the identification of
C" Thompson, 1968; Logan et al., 1970). Deep under 200000 of water (see the crystal morphology of the parent
We could argue in favor of a syndeposi- Degens and Ross, 1969, colour plate mineral, and such replacements have
( tional origin for similar intrasediment between p. 366 and p. 367). One major been widely observed in ancient evapo-
( growth textures in ancient evaporites by mechanism for tREl ~eRel alib" of ror- rites for gypsum (Schaller and Hender-
analogy. However, porphyroblastic min- hydrite nodules is t ~~ti.o!J...of. son, 1932; Stewart, 1949, 1951, 1953;
( erai growth might occur on burial, pro- 9YRsum cr stals to make orous lastic Borchert and Baier, 1953; Kerr and

c' ducing similar textures. On the other


hand, intrasediment growth of euhedra
masses of tiny anh r.9.d~..JaJb.§..t.ba1.ar.e
easilydeformedintonQ.!!.y larslug§.:. This
Thompson, 1963; Jones, 1965; Nurmi
and Friedman, 1977; Handford, 1981;
( of such elevated temperature minerals conversion may just as easily occur on Presley and McGillis, 1982; Crawford

c as langbeinite (Figure 13) and loewite


probably indicates burial crystalliza-
deep burial as during primary surface
deposition, The same reasoning holds
and Dunham, 1982; Lowenstein, 1982,
1988; etc.) as well as a number of other
(. tion, although as we have pointed out for all other evaporite minerals that are salts (Schaller and Henderson, 1932;
below, temperatures high enough to preserved as nodules composed of Stewart, 1963, p. 41; erc.). Pseudo-
c. reach the langbeinite stability field masses of small crystals embedded in morphs commonly preserve a crystal-

c have been reported from some modern


evaporite surface sediments.
a host sediment, such as, for example,
the displacive nodular kieserite shown
line framework and other primary fea-
tures of the parent mineral and thus
o G;) /ntrasediment Growth of Nodules.
It was the discovery of nodules of
in Figure 14.
Without independent evidence, then,
allow interpretation of the original min-
eralogy, primary processes and deposi-
c anhydrite in the Holocene sediments of
the Persian Gulf (Curtis et al., 1963;
nodules may not give unambiguous
information about their time, mode or
tional environment, despite the minera-
logical alteration. For example, the
C- Shearman, 1966; etc.) that essentially environment of formation. fI.l..i'N w-fl<J'ermian Salado deposit of New Mexico
rekindled interest in evaporites among ~seudomorPhs. )J rr~ fc",fvvJ- contains pseudomorphs after gypsum
sedimentologists. Since then there Pseudomorphs are unequivocal evi- (now composed of anhydrite, polyhalite,
o have been an astonishing number of dence of secondary replacement. How- halite and sylvite) as vertically oriented

c. papers published that have called on


nodular anhydrite, or its presumed
ever, the reason t hat we put such
pseudomorphous replacement under
stubby prisms and as foreset laminae
in wave-rippled cross-stratified grain-
c pseudomorphs, as a criterion for syn-
oepositional growth of evaporites in a
ambiguous criteria is that it may not be
possible without additional evidence to
stones (Figures 1 and 15). Clearly, we
can read through the alteration and
( sabhka environment. But we must be decide whether the replacement was of extract important information aboutsyn-
c very wary here because anhydrite nod-
ules can form under a variety of condi-
syndepositional or later burial origin (ct.
Stewart, 1963, p. 42).
depositional processes. However, the
timing of the pseudomorphous re-
o tions, such as, for example, from the Recognition of pseudomorphous re-
i:... ~ T. ' : ';7":"'
placement itself is not directly legible.
Several different types of pseudo-
c' ; ' ; ~,'
..~. >, "f"
morphous replacements havebeen rec-
ognized in evaporite deposits. These
(,
are (1) "dehydration eair" replacement
( (e.g., gypsum - anhydrite), (2) "reaction

c pair" replacement involving a common


component (e.g., gypsum - polyhalite),
c and (3) "non-reaction pair" replace-
ment wherein the original and replacing
o minerals have no common components
(e.g.,gypsum - halite). Borchert andMuir
L (1964, p. 126-144) ~onsider all types of
r pseudomorphous replacement to be
L
metamorRhic but it has been une uiv-
( ocally established that both de_h dration
~l!.cJLQ1l.P~ I§cgment§ G.ml
C form by synde ositional inte !WJion
8 oetween ao..eac1y foc m e d mioecal aod
the evaporati her-Ii uors in the
normal course of evolution of evapo-
rite brines. For example, both anhydrite
and polyhalite can be synthesized at
~~ low temperatures (Hardie, 1967, for
~ ~~
Figure 14 Photomicrograph of displacive kieserite nodules (gray) encircled by mud (black). anhydrite and Autenreith, 1958,for poly-
Kieserite in nodules is a fine-grained granular mosaic. The uncertainties involved in interpreting halite), both are predicted from thermo-
this texture involve the timing ofkieserite growth andwhetherkieserite is a dehydration product of dynamic considerations to form from
a more hydrated magnesium sulphate mineral (l.e., epsomite); and if so, what was the timing of gypsum with progressive evaporation
dehydration? Sample from Salado Formation muddy halite rock. Scale bar is 5 mm long. of seawater (Harvie et al., 1980) and

c
r
152 Diagenesis Geoscience Canada Reprint Series 4 (
C
C
C
C
(
C
Figure 15 Slab photograph of anhydrite
rock. Vertically oriented, elongate gypsum C
pseudomorphs, now composed of halite
(dark gray) originate from a common sur-
C
face. Laminated anhydrite at bottom of pho-
tograph. Scale bar is 5 mm long.
C
C
C
C
C
C
(
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
c
e
c
(
c
Figure 16 Core slab photograph of carnallite-halite rock. Small Figure 17 Core slab photograph of halite rock. Bedded chevron c
halite cubes and irregular blebs (arrows, smooth surfaces) float in
coarser carnallite crystals (gray textured areas). Sample from the
halite (light-dark bands define bedding) is abruptly truncated perpen-
dicular to bedding by coarse, clear halite. Sample from the Prairie
c
Prairie Formation. Formation.

c
(
c
c Evaporites 153
(
c
c both have been found as replacements
of gypsum in modern sabkhas (see
this replacement process is that it
cannot occur during simple equilibrium
"alien" brines are prerequisites for this
type of pseudomorphous replacement.
c Butler, 1970a, for anhydrite and Holser,
1966, for polyhalite). Nonetheless, we
evaporative concentration of a single
solution, as is predicted for chemically
Coarse Crystalline Salt.
Some evaporite deposits contain
r still have no direct and unambiguous related reaction pairs. Thus, for the coarse clear crystalline salts. An exam-

r. way to determine in an ancient evapo-


rite whether such replacements were
pseudomorphous replacement of gyp-
sum by halite we must call on the intro-
ple of this is the carnallite from the Prai-
rie Formation shown in Figure 16,which
c early or late.
The third pseudomorph type, the
duct ion of a new solution capable of
dissolving gypsum without chemically
poikilitically encloses clear euhedral
cubes of halite. The distinction between
( "non-reaction pair" replacement, in- reacting with it (i.e., without forming a the fabric of this halite-carnallite rock
volves minerals totally unrelated chem- reaction pair). Replacement by halite and the halite-sylvite rock in Figure 7 is
l ically to each other. For example, a most may either be simultaneous with gyp- important in allowing the timing of the
o common non-reaction pair pseudo-
morph in ancient evaporites is the
sum dissolution (i.e., a halite saturated
but gypsum undersaturated solution) or
carnallite or sylvite growth to be deter-
mined. The halite in Figure 7 forms a
C replacement of euhedral gypsum
prisms by halite (Figures 1 and 15)
may occur later. Again the question of
timing, whethersyndepositional or after
primary crystalline framework for the
sylvite cement. The halite in Figure 16
(
(Stewart, 1963, p. 41 ; Lowenstein, 1982, burial, for this replacement sequence occurs as isolated cubes and lacks a
( figures 4 and 5; Brodylo and Spencer, observed in ancient evaporites is primary crystalline framework. The tim-
1987, figure 10). We have no reported ambiguous. However, no matter what ing of this halite growth, and of the
examples of this pseudomorph type in the timing, a new solution must come carnallite growth around the halite is
modern evaporites so the conditions into contact with a previously crystal- unclear.
necessary for such replacement must Iized mineral. Thus, fluctuating solution The timing of large-scale cavity or
c be inferred. All we can really say about compositions and introduction of cavern fillings such as the coarse clear
halite in Figure 17 is also unclear. The
coarse halite crystals clearly formed
after deposition of the bedded halite as
well as after the intergranular cements,
c as the boundary of the cavity truncates
these features. However, as we have
( already discussed. cementation of pri-
mary bedded halites probably occurs
very early. Dissolution pockets in bed-
o ded halite may form syndepositionally
(salt karst) or upon later burial (the
cemented bedded halite framework
could withstand significant burial). The
coarse clear halite may grow near the
surface (as in the case of the coarse
euhedral halites which fill cavities in
modern salt pans), or at depth.
o cavity Cements.
A type of cavity cement which differs '
o from cements discussed as syndeposi-
tional features has been commonly
l observed in ancient evaporites. This is
r:
where pseudomorphous replacement

c takes the form of a void lining and void


filling cement. For example, in the Per-
( . mian Salado Formation, gypsum molds
that exquisitely preserve the "swallow-
b tail" twin morphology are lined with
an isopachous, euhedrally terminated
fringe of anhydrite and polyhalite,
which, in turn, are covered by a void-
filling halite cement (Figure 18;see also
Figure 18 Photomicrograph of vertically oriented gypsum "swallow-tail" twin pseudo- Schaller and Henderson, 1932,Plate 9).
morphs with void-filling cement texture. From the pseudomorph rim to the core are: (1) a mud These spectacular features demon-
band, (2) anhydrite stUbby prism lining, (3) microcrystalline polyhalite lining, (4) inward strate that gypsym was first dissolved
projecting polyhalite prisms, and a clear halite core. This cement texture is interpreted as without destro~n; the external form of
having formed after a gypsum crystal dissolution event. Sample from the Salado Formation. the gypsym crystals and th§ mold was~
........ Scale bar is 3 mm long . then filled successivelykJ:lrecipitation

r
(

154 Diagenesis Geoscience Canada Reprint Series 4


(
(

of anhydrite, then polyhalite and then record a partly displacive, partly incor- -¥: The temperature of formation of salts
C
halite. This sequence provides impor- porative growth style occur in the Mio- may be estimated from observation of C
tant information on the nature and com- cene of Russia (Lobanova, 1953), Per- multi-phase homogenization with in
position of cement-depositing brines mian of Germany (Borchert and Muir, fluid inclusions using a heatin g-freezing C
(Lowenstein, 1983), butthetim ing ofthe 1964, figure 20) and Permian of New sta ge on a getLogr:apbic.Jllicroscope,... (
cementation is unresolved. Mexico (Figure 13, see also Rempe, The most common observation is the
Temperature Dependent Salts. 1981). homogenization of liquid plus vapour C
-Phe use of salts that have restricted with in the fluid inclusion to a single liq-
/(' temperature stability ranges is an FLUID INCLUSIONS uid phase . Manyfluid inclusions in halite C
attractive option in deciding a ~
depositional or burial origin. However, a
Fluid inclusions are extremely abun-
dant in many evaporites,.egrtiC' !Iady i.A
crystals conta in , or nucleate on cooling ,
a solid daughter crystal. The final dis-
C
difficulty arises here because there is halites with a cr ystalline framework fab- solut ion temperature of the solid daugh- C
a large overlap in temperatures experi- JE.. Fluid inclusions may be used to ter crystal gives a minimum tempera-
C
'*
enced by primary depositional environ- determine the temperature of forwa1ioD ture of formation of the fluid inclusion .
ments and secondary burial environ-
ments.AlthoughmaD~
of salts antLtbe-compositiQr.l -of-fluids
from whicb..tbe.salt&.grAW.~eRoedder
Studies of fluid inclusions in halite,
which on the basis of petrographic evi-
C
evaporite settings remain at tempera- 1984a,b, for an overview of fluid inclu- dence appear to be syndepositional C
tures below 40°C the y-eararound (e.g., sion studies). Fluid inclusions not only (e.g., " raft s" and "chevrons") from the
Persian Gulf sabkha, Butler, 1970a, p. provide valuable information on t he Permian Salado Formation, New Mex-
C
125), temperatures near 50°C due to Physical and chemical environments of ico (Roedder and Belkin, 1979) show C
solar heating have been measured in salt formation , but also may aid in the liqu id-vapour homogenization temper-
shallow stratified brine ponds (HUdec clarification of the QrigilLoJ_s.alts..w.ith. atures with in the range of modern salt C
and Sonnenfeld, 1974). Stewart (1963)
reports temperatures in the 60-70°C
ambiguous pet[Qgrap,bicJ eatur.a:i... pans. Roedder and Belkin (1979)report
C
range for some shallow brine bodies, C
which is consistent with some of our own
field measurements, and values of over C
100°C are reached in hot spring brine
pools (Holwerda and Hutchinson, 1968).
C
Temperatures of surface sediments on C
salt flats commonly go above 50°C in
the summertime (e.g., Butler, 1970b).J!L
.)j )vll'
') ~
C
the normal geothermal gradient tem pera- 1>v...Jv..lIV"-" C
tures of 50°C are reached at about 900 00
dep-th and 100°C at about 2400 m d.ep..tDv -/-t II J l·ll /..J./I/' }tv C
This overlap inenvironment temperatures
.J1L means that "high temperature" salts such .S~J~l/\.\N fO{ C
~ It' as langbeinite, loewite, vanthoffite, etc.,
f'l ~l tI-~ - C
stable only at temperatures greater than
40·50°C (Stewart, 1963,figure 10),could C
be of either syndepositional or bur ial
origin. Nonetheless. despite th is ambi-
C
guity, the presence of such salts in a C
eposit tell us that temperatures were
a ove at least 40·50 0C_(lhey are " mini- C
mu m temperature" geothermometers).
These "high temperature" salts have
C
been found in many of the world 's pot- c
ash deposits as (1) unbedded fine- to
coarse-grained mosaic patches corn- c
posed of anhedral crystals, (2) isolated
nodules consisting of single crystals or
-e
crystalline mosaics, and (3) isolated
euhedral crystals. Most important of
c
the magnesium sulphate "high temper- l
ature" minerals is langbeinite which is
found in mineable amounts in several
l
evaporites (Rempe, 1981). Spectacular C
examples of large (em-scale) isolated Figure 19 Photomicrograph of fluid inclusions outlining primary growth bands in a halite C
langbeinite tetrahedral crystals that cornet (P) and fluid inclusions within relatively clear halite cement (5). Themelting behavior of
each set of inclusions is different, indicating two chemicallv distinct brines.
.csr "'-
<..

C
C
(
( Evaporites 155
(
c more than 300 inclusions , the majority tals. They may therefore be an accurate 3. Systematic changes in the melting
of which homogenized between 20 and reflect ion of depositional temperatures. behavior of inclusions from crystal core
r 50°C. Fluid inclusion liquid-vapour
homogenization temperatures in syn-
We must be cautious in using Iiquid-
vapour homogenization data from fluid
to rim (also indicates shallow setting)
4. For crystals with an ambiguous ori-
( depositional halites (crystalline frame- inclusions in minerals such as halite gin, similar behaviour (1, 2 and 3) to
work fabrics) from the Devonian tele- which stretch easily, but we also do not demonstrably primary syndepositional
( graph salts of Alberta range from 15to want to discard possibly valuable data fluid inclusions from the same area. We
( 40°C (Brodylo and Spencer, 1987). on the physical and chemical environ- stress that syndepositional salts may
Although the homogenizat ion tempera- ments of salt formation . contain both primary and secondary
c tures are within the range of modern
evaporite basins and salt pans , there is
Brine compositions may be deter-
mined by extraction of fluids from a
fluid inclusions.
The criteria for identifying fluid inclu-
( some question as to the reliability of large number of inclusions, a technique sions in evaporites that were trapped
the results. Roedder (1984a,b) discus- used by Knauth and Beeunas (1986) to under burial conditions arebased on the
ses the tendency of fluid inclusions in determine stable isotopic compositions nature of secondary evaporite brines.
c halite to "stretch" during heating, and of fluid inclusions in halite, or by extrac- Secondary evaporite brines are iso-

o for inclusions heated to temperatures


greater than the homogenization tem-
ting fluids from relatively large (250 JLm
diameter) single inclusions for major
lated from the Earth's surface. Temper-
ature in secondary brines may fall in the
o perature to homogenize at higher tem-
peratures during subsequent runs.
element analyses (Holser, 1963; Lazar
and Holland, 1988; Stein and Krum-
same range as primary brines, or may
be higher. Temperature and pressure
o Solid-liquid homogenization temper- hansl, 1988).A major drawback to these conditions may allow miscibility offluids

o atures are not affected by volume


changes due to stretching . The majority
techniques is that the vast majority of
fluid inclusions which are demonstrably
that are immiscible under laboratory
conditions. Fluids may be multicompo-
c of sylvite daughter crystals in halites
with syndepositional growth fabrics
primary on the basis of petrographic
information are very small (most are
nent or simple salt systems (e.g., mater-
ial obtained by dissolution). Tempera-
from the Devonian Prairie Formation of less than 20 JLm on a side) and in many ture and pressure changes are the
r: Saskatchewan, Canada, the Permian instances are intimately associated with primary drive for crystallization; there-
Salado Formation of New Mex ico, USA, larger fluid inclusions in halite cements fore, fluid composition remains nearly
c and the Oligocene Rhine Graben of
Alsace, France, studied by Lowenstein
or with secondary inclusions (Figure
19).These small primaryfluid inclusions
constant.
Fabricius (1985) studied fluid inclu-
and Spencer (in press) dissolve com- are beyond the reach of the techniques sions in halite and quartz crystals within
pletely by 50 to 80°C . These tempera- of Lazar and Holland (1988). Further- salt from the Zechstein 1 and 2 of the
tures are within the range of brine tem- more, extraction of multiple inclusions Norwegian-Danish Basin. Quartz grew
r peratures reached in modern evaporite leads to problems of mixing fluids from between 75 and 180°C from concen-
settings as a result of solar heating. We inclusions with different origins and trated (>30 wt.%) Ca-Mg-CI brines.
l believe that they are an accurate re- compositions. Liqu id -vapour homogenization tem-
r: flection of minimum surface brine tem- The origin of some salts with ambig- peratures and halite daughter crystal
r:
peratures during the formation of these uous petrographic textures may be homogenization temperatures from
halites. determined by comparing homogeniza- fluid inclusions within the quartz crys-
r: The results from the Prairie Forma- tion temperatures and the melting tals also allowed calculation of the pres-
tion are of particular interest when behaviour of fluids in inclusions with sure ( - 90 MPa) during quartz growth.
The fluid inclusion data le..d...t.P.iolEm~re~
r:
compared to an earlier study of liquid- those from demonstrably primary or
vapour homogenizationtemperaturesby secondary salts . Observation of the tions of the depth and timin g of salt-
D Hartzell (1963). Hartzell (1963) meas- melting behaviour of inclus ions allows pillow for mation in these salt domes.
ured temperatures between 51 and data to be obtained from even small Fluid inclusions in evaporites altered ~
104°C in more than 400 fluid inclusions single fluid inclusions. As frozen fluid by burial may havethe following charac-
in halite, but generally discarded the inclusions are warmed a number of dif- teristics that are different from inclu-
data as unreliable because the temper- ferent solid phases melt. Comparison of sions of syndepositional deposits:
c atures were too high. These halites con-
tain well-preserved chevron and cor-
the melting points of these phases gives
information on the chemical composi-
1. Vapour under pressure
2. High homogenization temperature
net fabrics typical of syndepositional tion of the inclusion brines. 3. Uniform melting behaviour of inclu-
halites. It is possible that heatin on Fluid inclusion data may be used in sions.
burial has caused the primary inclu- conjunction with petrographic informa-
sions to stretch see oe er an tion to determine the syndepositional or POTASH DEPOSITS
B elkin, 1979) without obliterating the post depositional origin of salts. A sum- A long recognised problem in evaporite
original syndeposit ional fabrics .The fill- mary of the characteristics expected of geochemistry is the failure of ancient
ing temperatures would then reflect fluid inclus ions in syndepositonal salt evaporites that contain the very soluble
burial temperatures, but the host would crystals are as follows: " potash" or "bittern " salts to match the
still retain its syndepositional texture. 1."Normal shrinkage bubbles" or vapour mineralogical sequences predicted by
However, the majority of Hartzell's bubbles that do not change on crushing the evaporation of modern seawater.
determinations overlap with our deter- 2. Low homogenization temperature Yet, ~tically every ancient potash I.
){/l'
minations from sylvite daughter crys- «100°C) ~Qor iten as been [:nteTpYeteCas )/I J
,~ .
c
156 Diagenesis Geoscience Canada Reprint Series 4 (
(

marine and there is a general con- Halite crystals associated with the many cases, sylvite layers drape the
C
sensus that the mai~me[lt.ebem.is­ potash salts in these deposits contain irregular surfaces of underlying chev- C
try of seawater.bas Dot changed signifi- fluid inclusion bands which outline syn- ron halite. Sylvite crystals commonly
cantly duriOQ..tb.eYhMerozoic (Rubey, depositional growth fabrics. Based on form mm-sized anhedral mosaics that C
the distinct banding, parallel to growth lack fluid inclusion banding. In some
1951; Chave, 1960; Kramer, 1965; HoI-
land, 1972; Holland et al. , 1986). The faces, and similarity with modern salt cases, sylvite crystals are flattened and
C
discrepancy between the predicted pan and laboratory grown halites , these bent around large chevron halite crys- (
versus observed potash-bearing min- inclusions are primary features .The flu- tals (Figure 20). Sylvite crystals in a
erai sequences has been explained by: ids contained in these inclusions are given layer are commonly equigranular C
(1) syndepositional modification of
seawater composition by biologic pro-
syndepositional brines. Fluid inclusions
in halite associated with potash salts in
(well sorted). It is important to note that
halite crystals that occur in sylvite layers
C
cesses, such as sulphate reduction the Salado, Prairie and Rhine Graben are about equal in size to the sylvite C
(Borchert and Muir, 1964; Braitsch, evaporites contain daughter crystals of crystals. The halite crystals in these
1971; Wardlaw, 1972; Sonnenfeld, sylvite. layers display cumulate textures and C
1984);
(2) syndepositional modification of sea-
Oligocene Rhine Graben.
Halite of the lower potash zone (Couche
may contain well-preserved fluid inclu-
sion banding .The homogenization tem-
C
water by non-marine inflow, either Inferieu re)shows remarkable preserva- peratures of sylvite daughter crystals in C
meteoric (D'Ans, 1933; Stewart, 1963; tion of depositional textures ,fabrics and fluid inclusions from halite range from
Wardlaw, 1972;Valyashko, 1972),diage- primary fluid inclusion banding. Halites 20 to 80°C and average 63°C from a
C
netic, volcanogenic, or hydrothermal commonly exhibit vertically oriented total of 92 measurements. C
waters (Hardie, 1984); chevron and cornet textures with cloudy Petrographic features of the Rhine
(3) non-marine parent waters (Hardie, fluid inclusion bands outlining crystal Graben evaporites and fluid inclusion C
1984); growth faces. Other halite layers are data from associatedhalitesconfirm ear-
(4) metastable equilibrium or non-equi- made of well-sorted mm-sized equi- lier interpretations that the potash min-
C
librium conditions that prevented pre- granular cumulate crystals or larger erai sylvite is of syndepositional origin C
cipitation of the normal seawater se- randomly oriented hoppers, with fluid in- (Braitsch, 1966, 1971; Kuhn and Roth,
quence (Valyashko, 1972); clusion banding, that were originally 1979). Sylvite layers with fine-grained C
(5) syndepositional or post-deposition-
al processes (thermal metamorphism,
skeletal but are now filled with clear
halite cement.
mosaic textures are interpreted as pri-
mary cumulates. The sylvite crystals
C
metasomatic alteration , complex min- The sylvite of the Couche Inferieure probably formed as small cubes during C
erai replacements, recrystallization, occurs in well-defined layers which may cooling of the warm surface brines as
replacement by high-temperature salts) also contain halite and anhvdrite. In orooosed bv Sturmfels (1943) and C
that have modified the primary marine
sequence (Stewart, 1963; Borchert and
C
Muir, 1964;Wardlaw,1968; Evans, 1970; C
Braitsch, 1971; Holser, 1979; Hardie et
al., 1985). In fact, Stewart (1963, p. 4) C
concludes that "most large evaporite
bodies have suffered widespread meta-
C
somatic changes since their original C
formation".
We have examined the timing of pre- C
cipitation of potash evaporites based on C
petrographic textures , fluid inclusions
in associated halites , sedimentary ([
structures and comparison with modern
and Quaternary evaporites (Lowen-
C
stein and Spencer, in press). A syn- C
depositional origin has been estab-
lished for some potash salts in the Per-
(
mian Salado Formation of New Mexico ,
Oligocene Rhine Graben of Alsace,
e
France and Devonian Prairie Formation (
of Saskatchewan, Canada. Further-
more, a mechanism of forming syn-
(
depositional diagenetic potash ce-
ments by cooling of surface brines (Sal-
Figure 20 Photomicrograph of halite and sylv ite from the lower potash zone (Couche C
inferieure), Mulhouse Basin, Tertiary Rhine Graben . Halite layer(H) is composedof centimetre -
ado and Prairie) is presented in addition size, vertically orientedchevrons that contain fluid inclusion growth bands (dark areas). Sylvite C
to the formation of bedded subaqueous
potash deposits (Rhine Graben).
layer (S) contains millimetre-size crystals of sylvite with equigranular mosaic texture. Milli-
metre-size cumulate halite crystals occur in the sylvite layer. Crystals of sylvite are flattened
C
and bent around the underlying chevrons. Scale bar is 10 mm long. C
C
C
Evaporites 157

Braitsch (1971). The mosaic textures of encased in a single sylvite or carnallite Figures 7 and 8). I he monomineralic
the sylvite crystals were probably pro- crystal (Figure 7). sylvite and carnallite cements, to§ettier
duced by post-depositional modifica- In ore zones containing sylvite, pri- With the fluid inclusion data in asssocl-
tion. Sylvite crystals which are flattened mary fluid inclusions in the associated ated syndel?ositional halites allow for
and bent around adjacent halite crystals halites contain sylvite daughter crys- aeta:iiediriterpretation of the mecha-
attest to the ease with which sylvite may tals. Data on carnallite are limited to one nisms of potash minerai formaM n. ihe
be deformed. ore zone in which clear halite crystals sylVite (laughter crystalliomogeniza-
Permian Salado Formation. contain large isolated fluid inclusions tion temperatures from the fluid inclu-
Sylvite and carnallite of the Salado For- with carnallite daughter crystals. In con- sions in primary halites establish that
mation are most common and volumet- trast, sylvite and carnallite daughter the surface brines from which the halite
rically abundant in muddy halite rock of crystals are not found in halites away crystallized were saturated with respect
o the McNutt Zone (Lowenstein, 1988). In from areas of potash mineralization. to sylvite at moderate temperatures .

o these rocks, halite occurs as isolated


euhedral and subhedral cubes and sub-
Homogenization temperatures of syl-
vite daughter crystals from fluid inclu-
Following desiccation of the surface
brine lake, sylvitecementsformed asthe
hedral crystalline aggregates. These sions which outline syndepositional interstitial brines cooled. Based on
halite crystals contain incorporated growth fabrics in halites range from 28 petrographic textures, a similar synde-
D mud and thin bands of fluid inclusions to 150°C and average 71°C for 119 positional origin is suggested for car-

o aligned parallel to crystal faces. Sylvite,


carnallite, siliciclastic mud and small
determinations.
The sylvite and carnallite in the Sal-
nallite. We, however, have no indepen-
dent evidence from fluid inclusions for
o amounts of polyhalite occur among the
halite crystals. Ore zones in the McNutt
ado Formation occupy areas equivalent
to the void spaces in modern salt pan
syndepositional carnallite saturated
brines.
Potash Zone with up to 50% sylvite and halites. Thus they are interpreted as Devonian Prairie Formation.
carnallite display poikilitic textures void-filling cements surrounding a pri- Halite from the Prairie Formation gener-
where several halite crystals may be mary crystalline framework (compare ally contains well preserved syndeposi-
tional textures and fabrics. Crystalline
growth fabrics, mainly vertically elon-
gated chevrons and cornets, are pre-
sent in 50 to 90% of the halite from many
intervals (Wardlaw and Schwerdtner,
1966 ; Wardlaw and Watson, 1966;

o Brodylo and Spencer, 1987). The halite


conta ins many features, particularly
syndepositional dissolution textures ,
that are typical of modern salt pans
described by Lowenstein and Hardie
(1985). Convincing evidence that sylvite
of the Prairie Formation formed at the
expense of carnallite is the lateral
change in stratigraphic thickness be-
tween sylvite and carnallite-bearing
halites (Wardlaw, 1968). However,
Wardlaw (1968) also presents petro-
graphic evidence that some of the car-
nallite has formed at the expense of
sylvite.
Halite associated with potash salts of
the Prairie Formation is atypical , and
generally lacks well-defined syndeposi-
tional textures and fabrics. Sylvite-
halite rocks are coarsely crystalline and
,. commonly display equigranular polygo-
o nal mosaic textures (Figure 21). Sylvite
in some cases occupies areas equiv-
alent to void spaces in modern salt pan
halites, and is similar to the sylvite in the
Salado Formation that cements a pri-
mary crystalline framework (compare
Figures 7 and 8 with Figure 22). Grada-
Figure 21 Halite-sylvite rock from the Devonian Prairie Formation of Saskatchewan displays tions between the two "end member"
coarse, equigranular polygonal mosaic texture. Individual crystals are outlined by hematite sylvite textures shown in Figures 21 and
concentrated along grain boundaries. 22 are also found in the Prairie Forma-
tion. In many cases, sylvite grain bound-
aries are highlighted by concentrat ions
(
158 Diagenesis Geoscience Canada Reprint Series 4 (
(

of blood-red hematite . Hematite is less


C
abundant, or absent, in grain interiors
which are also clear of fluid inclusions.
C
However, some halite crystals in the C
polygonal mosaics and primary crystal-
line frameworks contain cloudy fluid
C
inclusion-rich cores. The fluid inclu- C
sions outline remnant syndepositional
crystal growth (Figure 23).
(
Carnallite-halite rocks of the Prairie (
Formation display several textures.
Many samples contain isolated cen- C
timetre-scale cubes of halite, which are
enclosed by large poikilitic carnallite C
crystals (Figure 16). Most halite cubes
are clear, but some contain cloudy, fluid
C
inclusion banded cores, similarto those C
in Figure 23, which contain patches of
syndepositional crystal growth tex- C
tures . The euhedral, clear halite which
overgrows these cloudy cores contains
C
large isolated fluid inclusions with car- (
nallite daughter crystals, and is inter-
preted as a cement.
C
A second type of carnallite-halite rock C
consists of alternating centimetre-thick
beds of halite and carnallite (Figure 24). Figure 22 Photomicrograph of halite-sylvite rock from the Prairie Formation. Halite is
present as clearcubes (H), poikilitically enclosedby syivtte (5, gray in photograph). Scale baris
C
The halite layers contain some remnant
syndepositional growth fabrics . How-
3mmlong. C
ever, most crystals are clear. Minor C
amounts of carnallite are present as a
void filling cement within the halite beds C
(Figure 25). The carnallite beds contain
centimetre-scale isolated cubes of
C
halite . This type of bedding is similar to C
halite-sylvite rocksofthe Rhine Graben.
The Prairie Formation also contains C
intergrowths of large (several cen-
timetre) clear halite and carnallite crys-
C
tals (Figure 26). Neither the halite or C
carnallite contain any remnant syn-
depositional growth fabrics. C
Fluid inclusions in halite from the C
Prairie Formation contain an aqueous
phase and may also contain daughter C
crystals of sylvite, carnallite, or chloro-
calcite (onesample; Figure 27). All three
C
daughter minerals are found in isolated C
fluid inclusions from clear halite . Sylvite
daughtercrystals are found in mostfluid
(
inclusions which outline syndeposi-
tional growth banding in the chevron
C
and cornet halite associated with syl- (
vite or carnallite. Carnallite daughter
crystals have been observed in fluid
inclusions outlining syndepositional
growth fabrics associated with inter- Figure 23 Photomicrograph of halite-sylvite rock displaying coarse, equigranular polygonal
c
bedded halite and carnallite such as mosaic texture. Halite crystals (H)contain fluid inclusion bands (dark areas within halite) outlining
primary growth structures. Sample from the Prairie Formation. Scale bar is 2 mm long.
c
those shown in Figures 24 and 25.
'laughter erystals are Ret present at c
room tern erature in an fluid inclusions

l
c
C Evaporites 159
r:
\

('
r:

G
C
C
("
(

Figure 24 Coreslab photograph of bedded halite-carnallite rock. A Figure 26 Core slab photograph of coarse crystalline halite-car-
thin carbonate-sulphate layer is present at the base of each halite nallite rock. Large halite crystals (h) are clear and do not contain any
layer. Halite (h) beds are composedof clearinterlocking crystals with remnants of primary growth fabric. Carnallite crystals (c) contain
some remnants of chevron growth banding. Carnallite beds (c) inclusions of hematite, but do not display primary growth fabrics .
contain isolated halite crystals poikilitically enclosed in coarser Sample from the Prairie Formation.
carnallite crystals. Sample from the Prairie Formation.

Figure 25 Photomicrograph of halite bed


from bedded halite-carnallite rock. Fluid
inclusion bands outline primary cornet
growth fabric halite crys tal at lower left.
Carnallite (gray) fills void among clear halite
crystals. Sample from Prairie Formation.
Scale bar is 3 mm long.
(
160 Diagenesis Geoscience Canada Reprint Series 4 (
(
(
awayfrom the potash zones, nor do any appear to have been modified by or porites and the results of these pro-
of the above daughter minerals nucle- formed by post-depositional processes. cesses have been more extensively (
ate on cooling. These rocks may have originated as studied than those related to the burial
Sylvite daughter crystals from fluid syndepositional bedded subaqueous environment. Some bias toward inter-
inclusions in the cloudy cores of halite deposits or as void filling cements pretation of petrographic features as '"' (
crystals associated with sylvite and with around a framework of crystalline halite being the result of syndepositional,
the poikilitic carnallite dissolve between which has since recrystallized. How-
ever, most of the halite-carnallite rocks
rather than burial, processes may be C
55 and 61°C. Note that sylvite daughter present, especially for petrographicfea-
crystals and not carnallite daughter examined from the Prairie Formation tures which might form either syn-
(
crystals are present in syndepositional contain no remnant syndepositional depositionally or as a result of burial. r:
fluid inclusions in halite-sylvite and fabrics indicative of bedded sub- There is clearly a need for further study '--
most halite-carnallite rocks. Fluid inclu- aqueous deposition. Another problem of the burial environment.
r
sions in clear halite cements associated is that much of the potash in the Prairie Syndepositional sedimentary fea-
with carnallite do contain carnallite Formation iscarnallite, butthedaughter tures which might be found in evapo-
(
daughter crystals. Most of the carnallite crystals in fluid inclusions from most rites include sedimentary structures*
daughter crystals dissolve between 50 remnant syndepositional growth bands and crystalline framework fabrics.
and80°C, approximately the same tem- in associated halites are sylvite. Car- Syndepositional alteration or early dia- (
perature range as the sylvite daughter nallite daughter crystals are found in genetic modification of evaporites in-
crystals. clear halite associated with the car- clude dissolution-reprecipitation fea-
(
Sylvite-halite rocks in which the syl-
vite occurs as a void filling within a syn-
nallite. However,the inclusions and the
clear halite in which they are found may
tures and cement formation. Extensive
cementation of modern evaporites oc-
C
depositional crystalline framework of have formed syndepositionally or dur- curs within a few metres of the surface. C
halite (Figure 22) probably formed as ing burial. Therefore, the origin and tim- Burial alteration features that might be (
warm surface brines cooled during des- ing of much of the carnallite from the present in evaporite deposits include
iccation, as proposed for similar rocks Prairie formation is unclear. disruption and destruction of sedimen-
from the Salado Formation. Coarse
mosaic textures in halite-sylvite rocks SUMMARY
tary structures, sutured or polygonal
mosaic structures and deformation c
appear to have been produced by
recrystallization. The present s~lvite..:
In this paper, we have presented a set
of petrographic criteria aimed at dis-
features. In addition to these features,
there are_se~etal_reatur.e'S ound in
c
~t~tul:ElS-may..r;ap~sJm! t.i!lQ.Y.i.S.b.D.Q..Synde.p.asuionaJ..featur.es evaporites whose timing and/or origin (
.!lqlj!~.-r.ock,..cemented..b.y. e.al;l¥_s~~,
and recrystallized upon later burial.
from burial features found in evaporites.
The criteria are- -based pnman y on
is ambiguous. These include intrasedi-
-ment grow!.., of euhedral crystals or c
Fluid inclusions which outline pri- observations from modern near-sur- nodules, coarse crystalline salt pseu-
mary growth fabrics in halite record a face evaporite environments. Near- ~m-orpbQus rep acem~n~s a~d_ some
progressive increase in the potassium
content of the syndepositional surface
surface processes which influence eva- ~s _ c
brines. The increase is seen on a cen-
timetre-scale within individual deposi-
tional sequences and on a larger (sev-
eral metre) scale immediately below
potash salt ore zones. As in the case of
the Salado Formation, the surface
(
brines were saturated with respect to (
sylvite at moderate temperatures.
Interbedded carnallite-halite rocks (
contain halites with fluid inclusions (
which outline syndeposional growth
bands. These fluid inclusions contain (
daughter crystals of carnallite. Interbed-
ded carnallite-halite rocks were proba- l
bly formed as bedded subaqueous de-
posits. Carnallite may have formed as
C
cumulate crystals, similar to the sylvite
from the Rhine Graben, and as intersti-
tial cements within the halite framework.
(
Cooling of warm surface brines is a r:
likely mechanism for the carnallite crys-
tallization. The original textures were (
modified post-clepositionally.
The other types of carnallite-halite
Figure 27 Photomicrographs of daughter crystals in fluid inclusions in halite from the (
Devonian Prairie Formation. The daughter crystals indicate highly concentrated brines with
rocks from the Prairie Formation also diverse chemical compositions were present. (
l
C
( 00 0 yt,.\) n ( I c- (
c ~ ( U v ---..
\
I '" 11/1.' \
Evaporites IVI) y\,..R. _ r;A./\ 161

c
c ~ Data obtained from fluid inclus,i0nsin Braitsch, 0 ., 1966,Brom ine and rubidium as Curtis , R., Evans, G., Kinsman, D.J.J. and
C If' evaporite minerals can De used In con- indicators of environment during sylv ite Shearman, D.J., 1963, Association of
jUfiCtlo n with the p.At rog r.~pl1i..9J!Jfc>'"rriia.:-~ and carnallite deposit ion of the Upper dolomite and anydrite in the Recentsedi-
G tion to hel p--deterJD ine..the ~timir:1g~ar:1d Rhine Valley evaporites, in Rau, J.L.,
ed., Second Symposium on Salt: North-
ments of the Persian Gulf: Nature, v. 143
(3607), p. 679-680.
possible ..!!Jg~J:\an isms_oLm io.~@Lfllit.
C cipitation. Fluid inclusion studies from
ern Ohio Geological Society, Cleveland, D'Ans, J., 1933, Die losungsgleichgewichte

o potas n aeposits have helped to deter-


mine the timing of potash mineral
Ohio, p. 293-301.
Braitsch, 0 ., 1971, Salt Deposits . Their Or i-
gin and Composition: Springer-Verlag,
der systeme der salze ozeanischer salz-
blagerungen: Kali-Forschungsanstalt,
Verlagsgesellschaft fiir Ackerbau ,
( growth in some deposits. The analysis New York, 297 p, Berlin, 254 p.
of brine compositions from fluid inclu- Brodylo , L.A. and Spence r, R.J., 1987, De- Degens, E.T. and Ross, D.A., 1969, 1969, Hot
C- sions may also yield information on positional environment of the Telegraph Brines and Recent Heavy MetalDeposits
O chemical environments evaporites
have encountered during burial. Brine
salt: Bulletin of Canadian Petroleum Ge-
ology, v. 35, p. 186-196.
in the Red Sea: Springer-Verlag, New
York, 600 p.
composition and hydrologic factorsare Buckley, H.E., 1951, Crystal Growth : John Dellwig, L.F., 1955,OriginoftheSalinaSaltof
Wiley and Sons, New York, 571 p. Michigan : Journal of Sedimentary Petrol-
( important f~ta1UJ:esjD~tt!.MJ.jrla.Ldi~g~
Burgers , W.G., 1963, Principles of re- ogy, v. 25, p. 83·110.
esis of evapoLiteswbjcb.reguire fyr.tb~r
crystallization, in Gilman, J.J., ed., The Dellwig, L.F., 1968, Significant features of
stud~ Art and Science of Growing Crystals: deposition in the Hutchinson Salt, Kan-

c REFERENCES
John Wiley and Sons , New York,
p.416-450.
sas, and their interpretation, in Mattox,
A.B., ed.,SalineDeposits:GeologicalSo-
c Adams, J.E. and Rhodes, M.L., 1960, Dolo-
Butler, G.P., 1970a, Holocene gypsum and
anhydri te of the Abu Dhabi sabkha, Tru-
ciety of America, Special Paper 88 ,
p.421-426.
o mitization by seepage refluxion: Ameri-
can Association of Petroleum Geolo-
cial Coast: an alternative explanation of Dellwig, L.F. and Evans, R., 1969, Deposi-
tional processes in Salina salt of Michi-
o gists , Bulletin, v. 44, p. 1912-1921.
Arakel , A.V., 1980, Genesis and diagenesis
origin: Third Sympos ium on Salt, North-
ern Ohio Geological Society, Cleveland , gan, Ohio and New York: AmericanAsso-

o of Holocene evaporitic sediments in


Hutt and Leeman Lagoons, Western
Ohio, p. 120-152.
Butler, G.P., 1970b, Secondary anyhydrite
ciation of PetroleumGeologists, Bulletin,
v. 53, p. 949-956.

o Australia: Journal of Sedimentary Pe-


from a sabkha, northwest Gulfof Califor-
nia, Mexico: Third Symposium on Salt ,
Eugster, H.P., 1970, Chemistry and origin of
brines of Lake Magadi, Kenya:American
o trology, v. 50, p. 1305-1326.
Arthurton, R.S., 1973, Experimentally pro-
Northern Ohio Geological Society,
Cleveland , Ohio, p. 153-155.
Mineralogical Society,SpecialPaperv. 3,
p.213-235.
duced halite compared to Triassic layered Caldwell , A.H., 1976,Holocene gypsum de- Evans, R., 1970, Genesis of sylvite and car-
halite-rocksfromCheshire,England:Sedi-
c mentology, v. 20, p. 145-160.
Aulstead, K.L. and Spencer, R.J., 1985, Dia-
posits of the Bullara Sunkland, Carnar-
von Basin, Western Australia, Ph.D .
nallite-bearing rocks from Wallace, Nova
Scotia, in Rau,J.L. and Dellwig, L.F.,eds.,

o genesis of the Keg River Formation ,


northwestern Alberta: fluid inclusion ev-
thesis, University of Western Australia,
Nedlands, Western Australia, 123 p.
Third Symposium on Salt: Northern Ohio
Geological Society, Cleveland , Ohio

o idence: Bulletin of Canadian Petroleum


Carpenter A.B., 1978, Origin and chemical
evolution brines in sedimentary basins :
p.239-245.
Fabricius, J., 1985,Studies of fluid inclusions
c Geology, v. 33, p. 167-183.
Aulstead, K.L., Spencer, R.J. and Krouse,
Oklahoma Geolog ical Survey Circular,
v. 79, p. 60-77.
in halite and euhedral quartz crystals
from salt domesin the Norwegian-Danish
c H.A., 1988, Fluid inclusion and isotopic
evidence on dolom itization, Devonian of
Casas, E., 1988, Diagenesis of salt pan
halite , unpublished Masters thesis ,
Basin, in Schreiber,B.C., ed., Sixth Inter-
national Symposium on Salt: Salt In-
( Western Canada : Geochimica et State University of New York at Bing- stitute , Alexandria, Virginia, p. 247-255.
CosmochimicaActa, v. 52, p. 1027-1035.
o Autenr ieth, H., 1958, Untersuchungen am
Sechs-Komponenten-System KO, Nao,
hamton , 82 p.
Casas, E. and Lowenste in, T.K., 1987, Shal-
Goldman , M.I., 1952, Deformation, metamor-
phism , and mineralizat ion in gypsum-

o Mg· , Ca·, S04'" (CI'), H 20 mit -


low burial diagenesis of Quaternary
halite rocks, Basin and Range Province,
anhydrite cap rock, Sulphur Salt Dome,
Louisiana: Geological Society of Amer-

o
,
Schlussfolgerungen fUr die Verar-
beitung der Kalisalze: Kali und Stein-
salz, v. 2, p. 181-200.
U.S. (abstr.): Society of Economic Pale-
ontologists and Mineralogists, Annual
ica, Memoir 50, 163 p.
Gottesmann , W. von., 1963, Eine Haufig
Midyear Meeting , v. 4, 14 p. auftretende struktur des Halits in Kalifloz
Balk, R., 1949, Structure of Grand Saline Chave, K.E., 1960, Evidence on history of Stassfurt: Geologie, v. 12, p.576-58t
salt dome, Van Zandt County, Texas: sea water from chemistry of deeper sub- Handford, C.R., 1981, Coastal sabkha and
American Association of Petroleum surface waters of ancient basins: Ameri- salt pan deposition of the Lower Clear
C Geologists, Bulletin , v. 33, p. 1791-1829.
Bathurst, R.G.C., 1975, Carbonate sedi-
can Association of Petroleum Geolo- Fork Formation (Permian), Texas: Jour-
gists , Bulletin, v. 44, p. 357-370. nal of Sedimentary Petrology, v. 51,
b · ments and their diagenesis, Second Edi-
tion : Elsevier, Amsterdam, 658 p.
Crawford , G.A. and Dunham , J.B. , 1982, p.761-778 .
Evaporite sedimentation in the Permian Hardie, L.A., 1967, The gypsum-anhydrite
Borchert, H. and Baier, E., 1953, Zur meta- Yates Formation, Central Basin Plat- equilibirum at one atmosphere pressure:
morphose ozeaner Gipsablagerungen: form, Andrews County, West Texas, in American Mineralogist, v. 52, p. 171-200.
Neues Jahrbuch fiir Mineralogie Ab- Handford, C .R ., Loucks , R.G. and Hardie, L.A., 1968, The origin of the Recent
handlungen, v. 86, p. 103-154. Davies, G.R. , eds ., Depositional and non-marine evaporite deposit of Saline
'-"'
Borchert, H. and Muir, A.O ., 1964, Salt De- Diagenetic Spectra of Evaporites- A Core Valley, Inyo County, California: Geo-
posits: The Origin, Metamorphism and Workshop: Society of Economic Paleon- chimica et Cosmochimica Acta, v. 32,
Deformation of Evaporites: D. Van tologists and Mineralogists, Core Work- p. 1279-130t
Nostrand, Princeton, NJ, 300 p. shop No.3, Calgary, Canada, 1982,
p.238-275.
c
162 Diagenesis Geoscience Canada Reprint Series 4 c
c
Hardie, L.A., 1984, Evaporites: marine or Jones , C.L., 1965, Petrograp hy of evapo- Lowenstein , T.K., 1983, Depos it ion and c
non-marine? American Journal of Sci-
ence, v. 284, p. 193-240
rites from the Wellington Formation near
Hutchinson , Kansas : United Sta tes
alteratio n of an ancient potash evapo-
rite: the Permian Salado Formation of c
Hardie, L.A. and Eugster, H.P., 1971, The
depositional environment of marine
Geological Survey, Bullet in, v. 1201-A,
70 p.
New Mexico and West Texas, Ph.D. dis-
sertation, The Johns Hopkins Univer-
c
evaporites : a case for shallow, clastic Kerr, S.D. and Thompson, A., 1963, Origin sity, Baltimore , MD, 411 p, c
accumulation: Sedimentology, v. 16,
p.187-220.
of nodular and bedded anhydrite in
Permian Shelf sediments, Texas and
Lowenstein , T.K., 1988, Origin of deposi-
tional cycles in a Permian " saline giant" : c
Hardie, L.A., Lowenstein, TK and Spencer,
R.J., 1985, The problem of distinguishing
New Mexico: American Association of
Petroleum Geolog ists , Bulletin , v.47,
The Salado (McNu tt Zone) evaporites of
New Mexico and Texas : Geological c
between primary and secondary features
in evaporites , in Schreiber, B.C., ed.,
p. 1726-1732.
Keys, D.A. and Wright, J.Y., 1966, Geology
Society of Ame rica , Bulleti n, v. 100,
p.592-608. c
Sixth International Symposium on Salt:
Salt Institute, Alexandria, Virginia .
of the I.M.C. potash depos it, Esterhazy,
Saskatchewan, in Rau, J.L., ed., Second
Lowenstein , T.K. and Hardie, L.A., 1985,
Criteria for the recognition of salt-pan
c
p. 11-39.
Hartzell, W.G., 1963, Liquid inclusions in
Symposium on Salt: Northern Ohio Geo-
logical Soc iety, Cleve land, Oh io ,
evaporites : Sed imentolog y, v.32,
p.627-644.
c
halite, B.Sc. thesis, University of p.95-101. Mayrhofer, H., 1985, World reserves of c
Saskatchewan, Canada.
Harvie, C.E., Wear, J.H., Hardie, L.A. and
Kramer, J.R., 1965, History of sea water.
Constant temperature-pressure equilib-
mineable potash salts based on struc-
tural analysis , in Schreiber, B.C., ed., c
Eugster, H.P., 1980, Evaporation of sea
water : calculated mineral sequences :
rium models compared to liquid inclu-
sion analyses: Geoch imica et Cosmo-
Sixth Internat ional Symposium on Salt:
Salt Ins titute , Alexandria, Virg in ia, c
Science, v. 208, p. 498-500.
Hitchon, B., Billings, G.K. and Klovan, J.E.,
chimica Acta, v. 29, p. 921·945.
Kuhn, R., 1968, Geochemistry of the Ger-
p. 141-160.
Meijer Drees, N.C., 1986, Evaporitic depos-
c
1971, Geochemistry and origin of forma-
tion waters in the western Canada sedi-
man potash deposits, in Mattox , R.B.,
ed. , Saline Deposits: Geological So-
its of western Canada: Geological Sur-
vey of Canada , Paper 85-20, 118 p.
c
mentary basin - III. Factors controlling ciety of Amer ica , Spec ial Paper 88 , Mossop, G.D., 1979, The evaporites of the c
chemical compos ition : Geochimica et
Cosmochimica Acta, v. 35, p. 567·598.
p.427-504.
Kuhn, R. and Roth, H., 1979, Beitrage zur
Ordovician Baumann Fjord Formation,
Ellesmere Island, Arctic Canada: Geo- c
Holland, H.D., 1972, The geologic history of
sea water - an attempt to solve the pro-
kenntnis der salzlagerstatte am Ober-
rhein: Z. Geol. Wiss., v. 7, p. 953-966.
logical Survey of Canada, Bulletin No.
298,52 p. c
blem: Geochimica et Cosmochimica
Acta, v. 36, p. 637-651.
Knauth, L.P. and Beeunas, M.A., 1986, Iso-
tope geochemistry of flu id inclusions in
Morrow, D.W., Cumming, G.L. and Koep-
nick, R.B., 1986, Manetoe Facies - a gas-
c
Holland, H.D., Lazar, B. and McCaffrey, M., Perm ian halite with implications for the bearing , megacrystall ine , Devon ian
dolomite , Yukon and Northwest Territo-
c
1986, Evolution of the atmosphere and
oceans: Nature, v. 320, p. 27-33.
m .,
isotopic history of ocean water and the
origin of saline formation waters: Geo- ries , Canada: American Association of c
Holser, 1963, Chemistry of brine inclu-
sions in Permian salt from Hutchinson,
chimica et Cosmochimica Acta , v. 50,
p.419·433.
Petroleum Geologists, Bullet in, v. 70,
p.702-720. c
Kansas, in Symposium on Salt: Northern
Ohio Geological Survey,Cleveland, Ohio,
Lazar, B. and Holland, H.D., 1988, The ana-
lysis of fluid inclusions in halite: Geo-
Muller, W.H., Schmid, S.M. and Briegel, U.,
1981, Deformat ion experiments on c
p.86-95.
Holser, W.T. , 1966, Diagenetic polyhalite in
chimica et Cosmochimica Acta, v. 52,
p.485-490.
anhydrite rocks of different grain sizes:
rheology and microfabrics : Tectono-
c
recent salt from Baja California: Ameri-
can Mineralogist, v. 5, p. 99-109.
Lobanova, V.V. , 1953, On the genesis of the
langbeinite in the Sub-Carpathian pot-
physics, v. 78, p. 527-544.
Nahnybida , C., Hutcheon, I. and Kirker, J.,
c
Holser, W.T., 1979, Trace elements and iso- ash deposits: Proceedings Academy 1982, Diagenesis olthe Nisku Formation c
topes in evaporites, in Burns, R.G., ed.,
Marine Minerals: Mineralogical Society
of Science , U.S .S .R ., v.88, no . 1,
p. 145-148. [ in Russian]
and the orig in of late stage cements:
Canadian Mineralogy, v. 20, p. 129-140. c
of America, Short Course Notes Volume
6, chapter 9, p, 295-346.
Logan, B.W., Davies, G.R., Read, J .R. and
Cebulski, D.F., 1970, Carbonate sedi-
Nurm i, R.D. and Friedman, G.M., 1977,Sed-
imentology and depositional environ- c
Holwerda, J.G. and Hutchinson, RW., 1968,
Potash·bearing evaporites in the Danakil
mentation and environments, Shark
Bay, Western Australia: American Asso-
ments of basin-center evaporites, Lower
Salina Group (Upper Silurian), Michigan
c
Area, Ethiopia: Economic Geology, v. 63,
p.124-150.
ciation of Petroleum Geolog ists, Memoir
13,223 p.
Basin, in Fisher, J.H., ed., Reefs and
Evaporites: Concepts and Depositional
c
Hovorka, S.D., 1987, Depositional environ- Lowenstein, T.K., 1982, Primary features in Models: American Association of Petro- c
ments of marine-dornlnated bedded ha-
lite, Permian San Andres Formation,
a potash evaporite deposit, the Permian
HanSalado Formation of West Texas
leum Geolog ists, Studies in Geology,
v. 5, p. 23-52. c
Texas: Sedimentology, v. 34, p. 1029-
1054.
Hudec, P.P. and Sonnenfeld, P., 1974, Hot
and New Mexico, in Handford, C.R. ,
Loucks, R.G. and Davies, G.R., eds.,
Depositional and Diagenetic Spectra of
Parea, G.C. and Ricchi-Lucch i, F., 1972,
Resedimented evaporites in the Peri-
adriatic trough : Israel Journa l of Earth
e
brines on Los Roques , Venezuela: Sci- Evaporites· A Core Workshop: Society Sciences , v. 21, p. 125-141.
ence, v. 185, p. 440-442. of Econom ic Paleontologists and Presley, MW. and McGillis, K.A., 1982,
Ingerson, E., 1968, Deposition and geo- Mineralogists, Core Workshop No.3, Coastal evaporite and tidal-flat sedi-
chemistry work sessions (International
Conference on Saline Deposits), Mat-
Calgary, Canada, 1982, p. 276-304 . ments of the Upper Clear Fork and
Glorieta Formations, Texas Panhandle:
c
tox, R.B., ed., Saline Deposits : Geologi- University of Texas at Austin, Bureau of
cal Society of America , Special Paper
88, p. 671-681.
Economic Geology, Report of Investiga-
tions No. 115, 50 p. c
c
c
c
c
C' Evaporites 163

C
c. Prucha, J.J., 1968, Salt deformation and Schreiber, B.C. and Hsu, K.J., 1980, Evapo- Stewart, F.H., 1963, Marine evaporites:
C. decollement in the Firtree Point anticline
of central New York: Tectonophysics,
rites, in Hobson , G.D., ed., Develop-
ments in Petroleum Geology - 2: Appl ied
United States Geological Survey, Pro-
fessional Paper 440-'(, 53 p.
G v. 6, p. 273-299 . Science Publications, Barking, Essex, Sturmfels, E., 1943, Das kalisalzlager von
Rempe , N.T., 1981, Langbeinite in potash England , p. 87-138. Buggingen (Sud baden): Neues Jahr-
C deposits: 17th Annual Forum on the Schreiber, B.C. and Kinsman, K.J.J ., 1975, buch fur Mineralogie, Geologie und Pal-
Geology of Industrial Minerals, Albu - New observations on the Pleistocene aontoloqle, v. 78, p. 131-216.
( querque, New Mexico, May 1981. evaporites of Montallegro, Sicily, and a Thompson, R.W., 1968, Tidal flat sedimen-
( Ricci-Lucchi, F., 1973, Resedimented evap- modern analogue: Journal of Sedimen- tation on the Colorado River delta, north-
orites : Indicators of slope instability and tary Petrology, v. 45, p. 469-479. western Gulf of California: Geological

c' deep-basin conditions in Periadriatic


Messinian (Apennines fore-deep, Italy),
Schreiber, B.C., Roth, M.S. and Helman,
M .L. , 1982 , Recognition of primary
Society of America , Memoir 107, 133 p.
Ueda, A., Campbell, FA , Krouse , H.R. and
( in Drooger, C.w., ed., Messinian Events facies characteristics of evaporites and Spencer, R.J., 1987,34S/32S variations in

o in the Mediterranean: North-Holland,


Amsterdam , p. 142-149.
the differentiation of these forms from
diagenetic overprints, in Handford,
trace sulf ide and sulfate in carbonate
rocks of a Devonian reef, Alberta, Can-

o Rittenhouse, G., 1967, Brom ine in oilfie ld


waters and its use in determining pos-
C.R., Loucks, R.G. and Davies , G.R.,
eds., Depositional and Diagenetic Spec-
ada and the Precambrian Siyeh Forma-
tion, Montana, U.S.A.: Chemical Geol-
( sibilities of origin ofthese waters: Ameri- tra of Evapor ites - A Core Workshop: ogy, Isotope Geoscience Section, v. 65,
can Association of Petroleum Geolo- Society of Economic Paleontologists p.383-390.
o gists , Bulletin, v. 51, p. 2430-2440. and Mineralogists, Core Workshop No. Valyashko , M.G., 1972, Playa lakes - a

o Roedder, E., 1984a, Fluid Inclusions: Miner-


alog ical Society of America, Reviews in
Mineralogy, v. 12, 644 p.
3, Calgary, Canada 1982, p. 1-32.
Schreiber, B.C . and Schreiber, E., 1977, The
salt that was : Geology, v. 5, p. 527-528.
necessary stage in the development of a
salt-bearing basin, in Richter-Bernburg,
G., ed., Geology of Saline Deposits:
Roedder, E., 1984b, The fluids in salt: Amer- Schwerdtner, W.M., 1964, Genesis of pot- UNESCO , Earth Sciences Series, Paris,

o ican Mineralogist, v. 69, p. 413-439.


Roedder, E. and Belkin, H.E., 1979, Appli-
ash rocks in Middle Devonian Prairie
evaporite Formation of Saskatchewan:
v. 7, p. 41-51,
VolI, G., 1960, New work on petrofabrics:
o cation of studies of fluid inclusions in
Permian Salado salt, New Mexico, to
American Association of Petroleum
Geologists, Bulletin, v. 48 , p. 1108·1115.
Liverpool and Manchester Geological
Journal, v. 2(3), p. 503-56?
o problems of sit ing the Waste Isolation
Pilot Plant, in McCarthy, G.J., ed. , Scien-
Shearman , D.J., 1966,Origin ofmarineevap-
orites by diagenesis : Institute of Mining
VolI, G., 1976, Recrystallization of quartz-
biotite and feldspars from Eastfeld to the
o tific Basis for Nuclear Waste Manage-
ment: Plenum Press , New York, v. 1,
and Metallurgy (Newcastle-upon-Tyne),
Transactions , v. 75, p. 208-215.
Leventina Nappe, Swiss Alps and its
geological significance : Schweizer-
p.313-321. Shearman, D.J., 1970, Recent halite rock, ische Mineralogische und Petrograph-

r. Rubey, W.W., 1951, Geologic history of sea


water - an attempt to state the problem :
Baja, California, Mexico: Institute of Min-
ing and Metallurgy, Transactions, v. B79,
ische Mitteilungen, Bulletin, v.56,
p.641-647.
(; Geological Soc iety of America, Bulletin, p.155-162. Wardlaw, N.C., 1968,Carnallite-sylvite rela-
v. 62, p. 1111-1147. Sonnenfeld, P., 1984, Brines and Evapo- tionships in the Middle Devonian Prairie
o Schaller, W.T. and Henderson , E.P., 1932,
Mineralogy of drill cores from the potash
rites : Academic Press lnc., Orlando, FL,
613 p.
Evaporite Formation Saskatchewan:
Geological Society of America, Bulletin,
field of New Mexico and Texas: United Spencer, R.J., 1987, The or igin of Ca-CI v. 79, p. 1273-1294.
States Geological Survey, Bulletin , brines in Devonian formations, western Wardlaw, N.C., 1972,Unusual marine evap-
v. 833, 124 p. Canada sedimentary basin: Applied orites with salts of calcium and mag-
Schlager, W. and Bolz, H., 1977, Clastic Geochemistry, v. 2, p. 373-384. nesium chloride in Cretaceous basins
accumulation of sulfate evaporites in Stanton, R.L. and Gorman, H., 1968, A phe- of Sergipe, Brazil: Economic Geology,

o deep water: Journal of Sedimentary


Petrology, v. 47, p. 600-609.
nomenological study of grain boundary
migration in some common sulfides:
v. 67, p. 156-168.
Wardlaw, N.C . and Schwerdtner, W.M. ,
o Schlichta, P.J., 1968, Grow1h, deformation
and defect-structure of salt crystals, in
Economic Geology, v. 63, p. 907-923.
Stein , C.L. and Krumhansl, J.L. , 1988, A
1966, Halite -anhydrite seasonal layers
in the Middle Devonian Prairie Evapor ite
o Mattox, A.B., ed., Saline Deposits: Geo-
logical Society of America, Special
model for the evolution of brines in salt
from the lower Salado Formation, south-
Formation, Saskatchewan, Canada:
Geological Society of America, Bulletin,
o Paper88,p.59~617.
Schreiber, B.C., Catalano, R. and Schrei-
eastern New Mexico : Geochimica et
Cosmochimica Acta, v. 52, p. 1037-1046.
v. 77, p. 331-342.
Wardlaw, N.C. and Watson , D.W., 1966,
ber, E., 1977, An evaporit ic lithofacies Stewart, F.H., 1949, The petrology of the Middle Devonian salt formations and
continuum: Latest Miocene (Messinian) evaporites of the Eskdale No.2 bor ing, their brom ide content , Elk Point area,
G deposits of Salemi Basin (Sicily) and a east Yorkshire. Part I. The middle evapo- Alberta: Canadian Journal of Earth Sci-
5 modern analog, in Fisher, J.M., ed.,
Reefs and Evaporites - Concepts and
rite bed: Mineralogical Magazine. v. 29,
p.445-475.
ences, v. 3, p. 263-275.
Warren, J.K., 1982, The hydrolog ical set-
r. Depositional Models: American Asso-
ciation of Petroleum Geologists, Studies
Stewart, F.H., 1951, The petrology of the
Eskdate No. 2 boring east Yorkshire,
ting, occurrence and significance of
gypsum in late Quaternary salt lakes in
in Geology, v. 5, p. 169-180. Part II, The middle evaporite bed: Miner- South Australia: Sedimentology, v. 29,
,.- Schrieber, B.C., Friedman, G.M ., Decima, alogical Magazine, v. 29, p. 445-475 . p.609-639 .
A. and Schreiber, R., 1976, Depositional Stewart, F.H., 1953, Early gypsum in the Weiler, Y., Sass, E. and Zak, I., 1974, Halite
environments of Upper Miocene (Mes- Permian evaporites of north-eastern oolites and ripples in the Dead Sea,
sinian) evaporite deposits of the Sicil- England: Proceedings of Geological Israel: Sedimentology, v. 21,p. 623-632 .
ian Basin : Sedimentology, v.23, Assoc iation of London , v. 64, p. 33-39 .
p.729-760. Accepted 1988
c
164 Diagenesis Geoscience Canada Reprint Series 4 c
C
C
C
C
(
C
C
(
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
C
Pore cast of a sandstone. All mineral matter has been dissolved and pore spaces stand in relief. Pores C
are connected by throats which are sheet-like and represent spaces at grain contacts. Scanning electron
photomicrograph. Photograph courtesy of N. Wardlaw (University of Calgary). C
C

e
c
C
l
C
(
C
C
(
c Coarse-grained Siliciclastic Rocks 165

c
(
While it istemptingtodivide the subject arrive at some understanding of how all
r: of diagenesisinto those processeswhich these processes contribute to turning
are physical and those which are chemi- sand into sandstone. Finally, we will
(; cal, the interdependence of physical and briefly examine the practical applica-
( chemical processes makes this impos- tion of diagenesis to the exploitation of
sible. The reader also should be warned hydrocarbon reservoirs.
o that even sandstone diagenesis itself

c cannot be separated from the interplay


of differing sedimentary environments,
METHODS OF STUDY
The petrologist stUdying diagenesis
lithologic variation within basins, and set- relies on transmitted light microscopy,
ting and evolution of sedimentary basins. much like metamorphic or igneous
( Aspects of the All of these factors are ultimately gov- petrologists. However, because many
(
Diagenesis of erned by the tectonic setting. of the materials he is attempting to
Coarse-Grained observe are extremely fine-grained
o Siliciclastic Rocks
INTRODUCTION
Sandstone diagenesis is a subject
(1-20 ILm), he relies heavily on the scan-
ning electron microscope (SEM) and
o which has been investigated by many
different methods, and this reflects the
special X-ray diffraction techniques to
assist in mineral identification and
Ian Hutcheon
Geology and Geophysics nature of the processes governing dia- petrography. In many diagenetic stud-
o The University of Calgary
Calgary, Alberta T2N 1N4
genesis.ln this review paper, the chemi-
cal aspects of the diagenesis of coarse-
ies, extensive use is made of SEM
petrography. With an energy dispersive
grained siliciclastic rocks are empha- spectrometer, the SEM can provide
o SUMMARY
The process of diagenesis, by which
sized. In the broadest sense, .Q.iagene-
sis includes all the changes which affect
qualitative mineral analyses suitable,
when combined with X-ray diffraction
o sediments become rock, has many a sediment , from the time it is physically data and morphology, to assist in the

o physical and chemical aspects. Even a


cursory examination of the scientific lit-
aeposited, until all the constituent grains
come to chemical e uilibrium dirT
identification of clay minerals and other
authigenic phases. The scanning trans-
erature shows that mineral reactions, m-etamor Ism. Diagenesis lies be- mission electron microscope (STEM)
original depositional environment, dia- tween sedimentation and metamorphism, offers the possibility of determining the
genetic environment, the flow of fluid, both in the sequence of events in the exact nature of very fine intergrowths of
the evolution of organic matter, the com- rock cycle and in the methods used to authigenic minerals and the potential
( paction of sediment and the precipita- study diagenesis. Physical changes, for accurate chemical analyses of very
o tion , replacement and destruction of
cements all play a role in sandstone
such as compaction, fluid migration and
pressure SOlution, are accompanied by
small particles.
Many other methods may be applied
o diagenesis. The importance of sand- chemical changes caused by mineral during the study of clastic diagenesis.

o stone diagenesis is evidenced by the


rapid increase of pure and applied
reactions, mineral replacement, ce-
mentation and dissolution.
Resin pore casts and mercury injection
tests can provide detailed information
o research in this area. The oil and gas
industry has greatly accelerated re-
As rocks are buried, they evolve
water, hydrocarbons and various gases.
about the size and distribution of pores
and are especiallly useful in studies
o search into sandstone diagenesis, pri- As these fluids move through a sedi- relating to the recovery of hydrocar-

o marily because the nature and distribu-


tion of porosity and permeability
mentary sequence, they will gener-
ally follow fractures or the most perme-
bons. Fluid inclusion studies of clastic
rocks are not common (see Currie and
o ultimately governs the extent of oil and able units. In siliciclastic-dominated
sequences , the most permeable units
Nwachukwu, 1974), but the success of
fluid inclusion studies of carbonates
o gas recovery, and diagenes is is a con-
trolling factor in the formation and generally are the sandstones, which implies that theywill become more com-
o destruction of porosity. In addition , as
our demand for oil and gas grows,
become the conduit for the evolving
fluids. ~ndstone diagenesis is con-
mon. Stable isotopes and methods of
bulk chemical analysis (X-ray fluores-
o and the relatively easily extracted
oil is exploited, there is an increasing
trolled b a maze of interdependent
processes, including burial rate, sedi-
cence) have been applied to the study
of diagenesis, but separating authi-
emphasis on secondary and tertiary ment com osition and texture sedi- genic minerals from allogenic phases is
( recovery of conventional oil and re- mentaryandtectonicenvironment,chem- always difficult and may complicate
covery of heavy oil and tar sands. icatreactlon rates, degree of litho- interpretation of the results of such
f Enhanced recovery agents, whether ltlglc vana ion, hy ro na studies. Some very successful studies
physical (injected water or steam) or t erma gra ents and a host of comb ine organic geochemistry with
chemical (surfactants, acids , polymers, factors . We will enter this maze by start - detailed study of the diagenet ic events,
caustic and clay stabilizing agents), are 109 wnFi the observed effects of sand- either by characterizing the organic
in direct contact with the pore space of stone diagenesis, and continue by material (Foscolos and Powell, 1980), or
the rock. It is important to understand examining pressure solution, mineral by employing properties such as the
the present state of diagenesis of any authigenesis, cementation, and devel- vitrinite reflectance of coal (Hutcheon et
rock, and how that state will be affected opment of secondary porosity and fluid al., 1980), which is related to time and
by an agent used to stimulate recovery. movement. By this route, we hope to temperature of burial.
c
166 Diagenesis Geoscience Canada Reprint Series 4 c
c
DIAGENESIS AND POROSITY matrix all tend to lead to more rapidly attendant diagenetic processes) is c
The most obvious physical change in decreasing porosity. These conclusions
are reinforced by Selly's (1978) study of
strongly affected by geothermal gra- c
siliciclastic sediments during burial is
the loss of porosity, which was the sub- porosity evolution in the North Sea ~
dients . initial sediment composition.
tectonic setting. presence of secondary c
ject of an early study by Taylor (1950).
Figure 1 incorporates data from the
number of studies indicate that poros-
Ity evolution and the general path of dia-
porosity and presence of overpressure.
We shall see that other factors also are
c
Gulf Coast of Texas(Stuart, 1970), north- gen-esis-ate greatly affected by the ere:- important during diagenesis. Many of c
east Pacific (Galloway, 1974) and the
Mackenzie River Delta (Schmidt and
senceof hydrocarbons, earlyhydrocarbon
migration tending to reserve orosit
our ideas about diagenesis are based
on the Gulf Coast because of the large c
McDonald, 1979a). It is obvious that
porosit ~ tends to decrease with increas-
and immature lagenetic assemblages
(Lowry, 1956; Wilson, 1977).
amount of data from that area. It would
be incorrect to assume that all basins
c
ing dee!th but less obvious that tM,te- Galloway (1974) notes that, within will show the same diagenetic trends as c
may be zones in which RQLll§i.!,y -d.e-
crease is not as rqgjd, or iIJ.w.l;ticb.p.o.tOS;.
the Queen Charlotte Basin, sandstone
cementation is accelerated in areas W
the Gulf Coast.
c
ity actually increases. The porosity loss,
in general, results from compaction of
higher geothermal gradient (Figure 1),
which implies that the rate of diagenetic
PRESSURE SOLUTION AND
QUARTZ OVERGROWTHS
c
V0'12:::- Q.rains, pressure..soMiOf.\.of.grains..alld alteration is temperature dependent. Pressure solution is a subject worthy of c
~rowth of authigenic minerals(cements).
It can be seen in Figure 1 that there is n
Sandstones from the northeast Pacific
seem to lose porosity more rapidly than
an entire article, but since this process
contributes to sandstone cementation a c
single relationshipbetween porosity and their counterparts in more stable tec- very brief review is presented here. Two c
depth. Variations occur between basins
and between units within basins, reflect-
tonic regimes. such as the Gulf Coast of
the United States and the Mackenzie
types of petrographic phenomena are
attributed to pressure solution, stylo- c
ing many interacting processes which
contribute to diagenesis. Maxwell (1964
Delta. The sands in the northeast
Pacific basins, in addition to being in an
lites and dissolution of grains at grain-
to-grain contacts. Dissolytion at grain-
c
attempted to quantify by experime t area of higher heat flow, have higher to-grain contacts is more commonly c
the relationships between porosity an
other factors, and concluded that in-
contents of volcanic rock fragments,
feldspars and other immature or chemi-
observed in sandstones than are stylo-
lites, which are more common in car- c
creasing temRerature....!!ge. pressure .
amount of flu id flow and amount of
cally less stable constituents than
sands in the Gulf Coast or Mackenzie
c
Delta. It would seem that chemical c
/-
./ instability (or compositional "imma-
turity") of sandstones also pla)/s a rola c
c
/ ! during dia enesis.
he data from the Mackenzie Delta
are interpreted by Schmidt and McDon- c
/ I
I
I
ald (1979a)to show two different trends
c
2
/ - ,,
I
I
of porosity loss with depth. Poros-
c
/
I
ity which these authors refer to as
/ , I
"primary", or porosity represented by
...fo ,,
I
I
I

the original interstices in the sediment, c


3
- , ,, is lost more ra idly than " secondar "
porosit , which results from fractures c
i
" '---" , shrinkage and dissolutio c
s " \
\
I
in cements or rains. On Figure 1.the
porosity-depth curve for the Gulf Coast c
/
I
I
sands shows a rapid increase in po-
rosity with depth below 3500 m. The
c
10 20
POROSITY %
30
Gulf Coast basin contaiii'SSi9nificant c
Figure 1 Porosity versus depth curves for
sandstones can be generalized for a number
'(olumes of "overpressured" or " geo-
pressured" rocks. This means that
rather than the normal depth-pressure
c
of sedimentary basins . Data for the North- curve expected for an open column of Figure 2 An idealized interface between
east Pacific are from Galloway (1974), and
are shown by the long-dashed (geothermal
water, pore fluids in the Gulf Coast
sands are isolated from communication
two spherical quartz grains is shown with
the pressure distribution as postulated by
c
gradient = 39°C·km-')and dot-dash (geo- with the surface and can develop and Robin (1978). Thepressures p1 to p3, at the (
thermal gradient = 29°C ·km-') lines. Rela- grain contact, are not equal, nor are they
tionships also are shown for the Gulf Coast
sustain abnormally high water pres-
sures. These "overpressures" affect the
equal to the fluid pressure, pw. An over- C
(short-dash curve; Stuart, 1970) and the growth is shown on the grains (shadedarea).
Mackenzie Delta (solid curve ; Schmidt and evorution of diagenesisjo1be.GuJiCGast. The difference in pressures supplies the C
In summary, we see that porosity is
McDonald, 1979a) . The "P" and "S " on the
data from the Mackenzie Delta indicate pri- occluded with depth , but the rate of
chemical potential gradient, which leads to
the diffusion of silica from thegrain contact to
C
mary and secondary poros ity, respectively. porosity destruction (and presumably the pore space. (
(
C
r:
Coarse-grained Siliciclastic Rocks 167
c
r:
bonate rocks. In 1863, H.C. Sorby de- (1895) work on solids under homoge- along the interface between grains is
scribed convincing petrographic evi- neous stress in a fluid and continuing to not constant, nor is it equal to the pres-
( dence to support the concept of pres- the present-day experimental work of sure exerted by the fluid in the pore
sure solution, and since that time there Sprunt and Nur (1977) , DeBoer et al. space . The difference in thermody-
has been an abundance of petrograph- (1977) and Robin (1978). Robin (1978) namic chemical potential produced by
ic work to bolster Sorby 's original obser- gives a brief, but excellent, summary of this pressure difference is sufficient to
( vations . A satisfactory theoretical ex- the development of theories regarding put quartz into solution, allowing it to
( planation for pressure solution has been pressure solution . Figure 2 summarizes migrate along the grain boundary and
farmoreelusive, beginningwith Reicke's a theory proposed by Robin. Pressure to be precipitated in the pore space.
C Robin's analysis verifies the conclusion
that force across a grain contact is a
C function of burial depth, grain size,grain
shape and grain packing, and all these
C factors must playa role in the pressure
o solution process.
Figure 3 ~1!9..~S various petrographic
C features often attributed to pressure
o solution . In sandstones, interpenetrat-
ing grain-to-grain contacts , s~
o contacts, concavo-convexcontacts and

o quartz overgrowths, in many cases, are


'taken as eVidence of pressure solution.
o Spang et al. (1979) have demonstrated
that clay seams, stylolitic in part, may
o cause soiution .ot.adlacerrt .rock . The
o subsequent collapse will produce a tex-
ture very much like a pressure solution
o stylolite. In the strict sense, this tex-
ture actually results from chemical reac-
tions among minerals, which may pro-
c ceed in the complete absence of di-
rected stress, and thus is not truly
o " pressure" solution, Also, the work of

o Foscolos and Powell (1980) shows the


presence of considerable amounts of
c inorganic amorphous silica at depths up
to 2000 m in the Sverdrup and Beau-
o fort -Mackenzie basins. The solubility

o of amorphous silica, often in the form


of animal skeletons, is considerably
o higher than that of quartz, and dissolu-
tion of amorphous silica and reprecipita-
o tion as quartz can lead to the formation

o 9f quartz overgrowths, a feature often


?scribed to pressure solution but which,
o in this case, is not related to directed
pressure.
c /1
~rtz overgrowths are commonl~072
'~ost significant porosity-reducin
feature in the diagenesis of quartz-rich
8 ..,.--.... sandston~ Reactions -betweenoclay
mirJ..erals and reRlacement of silic a:
bear ing minerals by other minerals ,
s ucn as carlJOlfgteCl:Jffcpnurirle-_
'-...
sources of silica . The variability in the
development of quartz overgrowths
Figure 3 These photomicrographs show textures commonly associated with pressure
is governed by the nature of the host
solution .
(a) quartz grains show " dust rings" where the original grain boundary (gb) has been grain, with monocrystalline quartz
overgrown by euhedral quartz (og) . Theconcavo-convex contactbetween the two grains cuts grains producing different forms of
the dust rings and the overgrowths, indicating solution of material at the interface. (60 x) overgrowths when compared with poly-
(b) a highlysutured contact has developedbetween two grains in a quartz sandstone. (400 x ) crystallinequartz(Waugh, 1970). The"dust
c
168 Diagenesis Geoscience Canada Reprint Series 4 (
t:
lines " associated with quartz- over- tite and illite when found as authigenic The paths of cementation in sand- C
growths (Figure 3a) mark the interface minerals in sandstone. Most workers
acceptthe authigenicnatureofcarbonate
stones are extremely complex. For C
between the overgrowth and the host example, Galloway (1974) recognizes
grain and are often voids (Pittman, or other types of pore-filling cements relatively early calcite pore-fill formed C
1972). The voids seem to form because (Figure5). In manyinstances,there is not near the surface, and a phase of calcite
nucleation is initiated at a number of a sufficient local source within the sedi- cementation displaying replacment
C
sites on the surface of the host grain ment to produce all the observed textures which occurs only at depths C
and, as competitive crystal growth pro- cementing material, suggesting that greater than~ Numerous authors
ceeds, a small number of the original material for ceroa~~~ have documented paragenetic sequen- C
nuclei will grow to form the overgrowth. scavenged from the pore water The ces for authigenic minerals in sand-
The voids represent the interstices material in the pore water may be de- stones in which appearances and dis-
between these original nuclei. rived from connate saline water (sea- appearances of minerals overlap (see, c
/ AUTHIGENIC CEMENTATION
water), dissolution of soluble rocks
(i.e., evaporites) by percolating ground-
for example, Galloway, 1974; Surdam
and Boles, 1979; Mankiewicz and c
Wilson and Pittman (1977) emphasize
the necessity and textural criteria for
wateror expulsion fromshgilles and Otbet
rocks undergoing mineral or or anic
Steidtmann, 1979; Tillman and Almon,
1979). This im lies that, rather than the
c
distinguishing between allogenic (intro- reactions.CilFfiS-r1978, 0 es 1979) and appearance aod..dis.appearance eta. c
duced during deposition) and aut hi-
~rowth in situ during diagenesis)
Bo es and Franks (1979) have recog-
nized the probability that material for
single mineral, there are reactions tak-
ing place, via the ore water, amon .~ c
clay minerals. Figure 4 shows typical cementation may be transferred from minerals in a sandstone. c
morphologies of kaolinite, chlorite, smec- shales, via pore waters, to sandstones.
c
c
c
c
c
c
c
c
c
c
c
C
E
C
C
C
C
c
e
l
(
C
Figure 4 Scanning electron photomicrographs of (A) smectite honeycombs, (B) euhedral kaolinite booklets. (C) illite fibres (marked by black
arrows) growing on altered plagioclase feldspar and (D) rosettes of iron-rich chlorite. The bar scale on each photograph is in um. All
c
photomicrographs were taken by Alan Oldershaw. c
c
c
r:
Coarse-grained Siliciclastic Rocks 169

Boles (1982) has recognized active (in these same variables), Boles convin- demonstrate that if we consider the min-
albitization in Frio Sandstones from the cingly demonstrates that albitization is erals with in the pore space as a chemi-
Gulf Coast. Using scanning electron occurring, probably at the present time, cal system (Figure 6), we can treat many
microscopy, the reaction in the subsurface of the Gulf Coast. The of the chemical problems in sandstone
2Si0 2 + 'I2H 20 + H+ + Na- + CaAlzSizOe(1)
reaction shown provides a source of diagenesis using equilibrium thermo-

c quartz
= NaAISi30e + 'I2AI2Si205(OH)4
plagioclase
+ Ca 2 +
calcium for the production of carbonate
cements. Many diagenetic mineral re-
actions are interrelated in a similar way,
dynamics. We will see that chemical
kinetics, mass transfer and fluid move-
ment also may have a major impact on
( plagioclase kaolinite
and to obtain a complete picture of dia- sandstone diagenesis.
can be documented. By plotting the genetic evolution, a complex sequence In examining the published work on

r activity ratio of Ca2 + INa + versus pH,


contoured tor 1000,125° and 150°C, and
of textures, indicative of mineral reac-
tions, must be interpreted. The studies
chemical aspects of sandstone diagen-
esis, it would be easy to conclude that
also plotting the compositions of waters of Merino (1975) and Nesbitt (1980) minerals an d aqueous solutions are
the onl substa c e e 'ui"
in diagenesis. From fluid inclusion stud-
ies of sedrments, Burruss (1981) cites
( examples of hydrocarbon-, methane- or
carbon dioxide-bearing fluid inclusions
associated with diagenetic events. The
importance of carbon dioxide in control-
ling carbonate dissolution and re-
cipi ation has Ion been reco niz d
Many authors have noted the production
of methane and carbon dioxide during
diagenesis of organic matter, While this
may be the case, howmuchofthevapour
is carbon dioxide and how much is pre-
sent as other species is a moot point. In
1942,German n and Ayers noted the pro-
duction of carbon dioxide from lime-
stones with trace amounts of silica, alu-
minum, iron and magnesium at temper-
atures as low as 98°C. More recently,
Muffler and White(1969), in a study ofthe
Salton Sea geothermal field, postulated
a carbon dioxide-producin mineral
reaction between clay minerals and car-
bonates. Hutcheon eta/. (1980) havedoc-
umented the mineral reaction
5CaMg(C0 3 ), + AI2Si20s(OH). + Si02 + 2HzO(2)
dolom ite kaolinite quartz

= Mg sAI2S i30,o(OH)& + 5CaC0 3 + 5CO z


chlorite calcite

which is observed in the Kootenay For-


mation, at approximately 5000 m (strati-

Figure 5 Authigenic, pore-filling cements are shown in both photomicrographs. (a) calcite Figure 6 The minerals in the pore space,
is shown enclosing angular quartz grains in a sandstone. The calcite is well crystallized (cc) which are in contact with the pore fluids,
and shows some euhedral crystal faces. (160 x) often can be considered as a system which
(b) a pore in a sandstone with well-rounded quartz grains is filled by authigenic kaolinite. (160 x) may come to thermodynamic equilibrium.
(
170 Diagenesis Geoscience Canada Reprint Series 4 C
C
graphic plus structural) burial. Figure 7 The results of Muffler and White previously, Schmidt and McDonald
C
shows the topology of reaction (2) as a (1969) and Hutcheon et al. (1980) show ascribe dissolution of carbonates to car- C
function of temperature at constant that mineral reactions may produce bon dioxide produced by organic dia-
pressure in a mixture of carbon dioxide carbon dioxide. This is an alternate, genesis, whereas Curtis (1978) blames C
and water. As temperature increases, additional source to carbon dioxide the identical process for the carbonate
reaction (2) proceeds to the carbon produced by organic reactlons.Oarbon precipitation. Which interpretation is
dioxide-bearing side, and this carbon dioxide is an interest ing constituent of correct? As is usual in geological pro- c
dioxide is added to the vapour phase , in-
creasing the mole fraction of carbon
diagenelre-pTo'c~'Sse-g-in-thaCsol'Ti'e
authors have attri outed carbonate ce-
blems, both are, maybe!
Using calcium carbonate as an exam- c
dioxide in the vapour and making higher
temperatures necessary for the reac-
mentation to campn qj.o~ide. p-rod uc~
(Curtis, 1978), while other authors
ple, dissolution of carbonates is control- c
tion to proceed. The mineral reaction attribute dissolution of carbonate (and
led by a reaction similar to (3):
CaC0 3 + H + = HCO; + Ca2+ (3)
c
will follow along the curve in Figure 7
until the miscibility surface between
the formation of "secondary porosity")
to the effect of carbon dioxide (Schmidt
calc ite
c
carbon dioxide and water is reached
and carbon dioxide will no longer dis-
and McDonald, 1979a). Although these
authors are referring to processes
assuming, as is often the case, that the
pH range issuch that HCO; is the domi-
c
solve in an aqueous fluid. At that point, which take place at different burial nant aqueous carbonate species in c
carbon dioxide is produced as a va-
pour. Most fluids observed in sedi-
depths, the effects of carbon dioxide
production on carbonate stability re-
solution. If the pH (activity of hydrogen
ion) is controlled by mineral reactions c
mentary rocks are aqueous liquids; it is quire clarification . with an aqueous phase, or by organic
materials, such as acetic acid, the addi-
c
reasonable to expect that the intersec-
tion of the mineral reaction and the car- SECONDARY POROSITY tion of carbon dioxide will increase the c
bon dioxide - water miscibility surface
represents the maximum equilibrium
Many authors have examined the im-
portance of secondary porosity in the
amount of HCO; by dissociat ion of
H2C03 • This will cause an increase in c
temperature for the mineral reaction in development of sandstone reservoirs the solubility product for reaction (3) c
liquid water. Hutcheon et al. (1980)
describe this process in more detail,
(Hayes, 1979; Loucks et al., 1979). A
comprehensive account of the role and
and lead to carbonate precipitation .
However, if the pH is not fixed by some c
and show calculated phase diagrams
which indicate the maximum tempera-
recognition of secondary porosity is
given by Schmidt and McDonald
organic matter or minerals in the rock,
something different will happen. The
c
ture for reaction (2) in the Kootenay (1979a, b). They recognize porosity pro- addition of carbon dioxide will produce c
Formation is about 180°C, in agreement
with coal maturation data for the Koo-
duced by fracturing, shrinkage , dissolu-
tion of sedimentary material and dis-
H2C03 which, being a weak acid, will
dissociate, producing hydrogen ions c
tenay Formation. solution of auth igenic material, b~tk- and lowering the pH. This will decrease
consider the dissalutiOD-Of carbon ~1\ the solubility product for reaction (3),
c
A number of interesting observations
can be made as a result of chemical to be a m,.mor contributor:..to.secondar.y. leading to carbonate dissolution. Pre- c
studies of diagenesis. Boles and his co-
workers have shown that many diage-
porosity. in sJ~ndstones . The data of
-SChmidt and McDonald show a marked
sent knowledge of water-rock systems
does not allow unequivocal determina- c
netic processes appear to be active JlL
other w.Q.!:ds.,..we can obseeve.trorn drill
reductionintherateofporositylosswith
burial depth (Figure 1,line labelled "S")
tion of pH from mineral assemblage
data; therefore recourse lies in obtain-
c
core that ankerite cementation and albi- over depth ranges in which secondary ing reliable, accurate water chemistry C
tization are taking place as th estidiment porosity is being destroyed. As stated from subsurface waters.
is buried. By using mineral chemistryand
E
GEOLOGICAL CONTROLS OF
equilibrium thermodynamics , it has
DIAGENESIS
C.
been possible to show that material
has moved between shales and sand- 1 Siever (1979)has summarized plate tec- C
tonic controls on diagenesis. He notes
stones during diagenesis. This result is
directly comparable to the study by source area by rial rate heat flow and C
Hower et al. (1976) in which the smec- residence time as generally important
.tartars.While it is obvious that burial en-
C
tite-illite transformation in mudrocks is
interpreted as an active process. vironment and original sediment com- c
The research of many authors dem-
onstrates that, rather than single miner-
XCOz -
position and texture, which are deter-
mined by depositional environment, are e
als appearing and disappearing, there two important geological controls, there c
are complex mineral reactions with pore
fluid in the subsurface. JQ-.pro per.ly
Figure 7 Mineral reactions similar to the
one shown will attemptto control the carbon
dioxide content of a vapour phase during
is a paucity of studies which relate
these two important variables. A study
of Foscolos et al. (1982) marks the be-
c
~ d e [~an d diagenesis , it is necesary.to
.QPcumenLthe.se reactions.wlth.careful.
burial. As the carbon dioxide content in the ginning of a project devised to relate C
vapour increases, the reaction is stable at
~gmp-hY,J:_om b i n i ng X-ray.J.hin.s.ec:- higher temperatures. Once the miscibility
diagenetic alteration to burial and sedi- l
tion and electron microbeam_t.e.ch- mentary environment. Concentration of
!}iQu.~
surface (solid curve) between carbon diox-
ide and water is reached, carbon dioxide- effort in this area is badly needed. C
rich vapour is produced. C
C
C
c
( Coarse-grained Siliciclastic Rocks

FLUID FLOW AND DIAGENESIS Although convective flow is ~ booklets may become detached from
~ It is clear that as sediments are buried hypothesis which requires further ver- their substrate and lodge in the pore

o they lose water and other volatile con-


stituents. Many of our concepts of sand-
ification by careful study of diagenetic
mineral assemblages, there is little
throats, shutting off flow in that part of
the rock. The smectite group of cla¥
r stone diagenesis are founded on stud-
ies of the Gulf Coast , an area of low
doubt that fluid flow, whether by upward
moving compaction water, circulating
minerals tends to swell when in contact
Wiffi water due W~Sl1'ltltltswetlii'ig1rnCl­
C topograph ic relief and active burial. groundwater cells in hydrodynamically 1tle adsorptIon of water molecufes In tne
( . Movement of fluid in the Gulf Coast is complex basins or convective flow, is a interlayer eosltlon ~ This swelling can
upward and laterally outward along per- controlling process of mass transport in oe up to two orders of magnitude of the
meable units (Magara, 1976; Neglia, porous sandstones. Fluid flow probably solid volume occupied by smectite with
1979). In addition, the fluids are largely dominates over diffusion controlled a corresponding decrease in porosity
connate marine water and water from mass transfer for mass movement on and permeability: Further, all clay min-
() the dissolution of evaporites, modified
by diagenetic mineral reactions (Car-
the large scale . Nevertheless, diffusion
is an important process in pressure
erals have high surface area to volume
ratio~ and tend to have electrically
0, penter,1978; Hanor, 1979). Most ancient ~Iution (Robin, 1978) and may playa char ged surfaces, making them efreC-'

o sedimentary basins are not found in this


particular setting. For example, the
greater role in sandstone diagenesis 't1Veat binding water and causing bigh
than is presently recognized . Studies irreducible water saturations. The dif:.
o Alberta Basin is in close proximity to a
mountain range which provides suffi-
such as those by Aagaard and Helgeson
(1982) mark the beginning of the use of
f ering cation exchange capacities for
groups of clay minerals indicate dif-
o cient hydraulic potential that meteoric kinetics as a means of understanding ferent surface charge distributions.

c water circulates through permeable


units to depths on the order of 3000 m
sandstone diagenesis. Clays with higher cation exchange
capacities, such as smectite, tend to be
o below ground surface (Toth, 1980). This
origin for waters has strong influence on
DIAGENESIS AND HYDROCARBON
RESERVOIRS
more effective at binding water than
suc h clays as kaolinite, which has a low
o water composition and therefore influ- Intergranular, dissolution, fracture and c ation exchange capacity. Van Elsberg

o ences the nature of mineral react ions


taking place between pore fluids and
micro-porosity are important in sand-
stone reservoirs. The aythigenic c1a1P!
'(1978) has noted that many amorphous
hydroxides have similar properties to
n the enclosing rocks. Concentrations of
dissolved solids in formation waters in
content of sandstone reservoirs can
create mIcro-porosity, which is largely
clay minerals , and are very difficult to
detect. In addition, the role of arnor-
o Alberta are commonly 50,000 rnq- L-\ ineffec tive, and low permeabiljties by phous material in sandstone diagenesis
o but can range up to 200,000 mq- L-1
in Devonian rocks (Hitchon et a/., 1971 ;
decreasing the size of pore apertures- is poorly understood, with very few
The high surface area to volume ratio of workers (Foscolos and Powell (1980)
o Hitchon , 1980). Since some of these
waters can circulate to a great range of
most clay minerals and the tendency fOrJ.4-- being notable exceptions) recogn izing
expansion of the smectjtes or migratiod'1 the importance of amorphous material.
depths, fluid movement is a process ofkaolinitewhenexpQsedtofresbwa~er Almon and Davies (1981) and Thomas
r: which can transport large amounts of are limiting factors in oil recover y. Many (1981) outline possible problems cre-
material, even in the time scale of the of these factors are affected by dia- ated by the presence of clay minerals,
Holocene (Toth, 1980). genesis (Pittman, 1979). Consequently, and offer general methods for minimiz-
.J'< The presence of overpressured zones much effort is being expended to un- ing their effect on recovery. Almon
1'1 ~n many basins implies that porous and derstand the role of diagenesis in hydro- (1981) also outlines the necessity for
permeable units may be isolated from carbon recovery, encouraging an over- using diagenetic trends as a method for
communication with other permeable all increase of interest in sandstone porosity prediction in oil exploration . .
rocks by impermeable bodies. These diagenesis. Table 1 summarizes some of the more
permeable sands still show evidence of The recovery efficiency of sand- general ways in which clay minerals can
diagenetic features associated with stones has strong positive correlations affect recovery and common methods
other diagenetic settings, and it ap- ~ith high porosity, small pore-to-throat of treating these problems.
pears that fluid movement must have size ratiOS, small mean particle size and
c occurred. Also spatial patterns of min-
erai distribution may be developed, as,
low percentage of carbonate (Wardlaw
and Cassan, 1979).Ofthese properties,
HEAVY OIL AND TAR SANDS
(Artificial Diagenesis)
for example, in the alteration of volcanic pore-to-throat §!ze ratio and carbonate The tar sands and heavy oil deposits in
rocks (Surdam and Boles, 1979). Wood percentage can be markedly affected Alberta and Saskatchewan represent a
and Surdam (1979), Cassan eta/. (1981) by diagenesis. For example, in studies. huge resource, but oil viscosities are so
and Wood and Hewett (1982) all con- of reservoir sandstones it is c;mmon high in the tar sands that there is little or
r:
sider convective fluid movement to be see I Itebridging~J;!orethroats.(Figure8) no conventional production. Schemes
an important process. Cassan et a/. -and effectively doubling or tripling pore- to mobilize the vast amounts of oil that
(1981) surmised that convective fluid to-throat size ratios. Kaollmte (FigUr~* are too deep to be mined involve heat-
movement controls the dissolution of 4b) commonly forms aggregates and ing , either by steam injection or by in-
feldspar and cementation by quartz and pore":fUllngs which are larger than the situ combustion. Mineralogical altera-
calcite in the Gabon Basin by imposing pore throats . When interstitial flow tion , especially of pore space minerals,
temperature changes as a result of con- velocities become high, during recov- is to be expected and may be observed
vection cells. ery, these aggregates and individual both in laboratory tests (Perry and
c
172 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
c
c
(

c
(
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
(
c
c
Figure 8 During steam stimulation, (A) fine smectite and (B) illite are reacted to produce (C) coarse-grained corrensite (Cor, a smectite-
chlorite intergrowth which in this case is not identified by X-ray diffraction), and (0) coarse-grained, euhedral analcime. The scale on each c
photograph is in um. All photomicrographs were taken by Alan Oldershaw.
c
c
c
Table 1 Problems and treatments for authigenic minerals in reservoirs. (After Almon and Davies, 1981).
c
Mineral Problem Incompatible with: Compatible with : Remedy
c
Smectite
Mixed-layer Smectite-Illite
swelling
swelling
fresh water
fresh water
KCI, hydrocarbon
KCI, hydrocarbon
HCI, HF
HCI, HF c:
Illite microporosity fresh water KCI, hydrocarbon HCI, HF (
Kaolinite mobile fines high flow rate low flow rate clay stabilizers
Chlorite iron precipitate 02-rich, pH 3.5 + HCI, organic acid HCI, organic acid
Calcite, dolomite CaF2 precipitate HF HCI
c
c
c
(
(
C
c
c Coarse-grained Siliciclastic Rocks 173

c
(. Gillott, 1979, 1982) and in actual field observations that smectite isa hightem-
( results(Sedimentology ResearchGroup, perature phase compared with kaolin-
1981). The impact of steam on volcan- ite. The diagram also explains the tex-
G iclastic tar sands from Cold Lake is seen tural observation that analcime is the
c in Figure 9. When compared with the
well-lithified, oil-free portion of a core
last-formed phase in these rocks. When
injection stops, more saline formation
( cut after two years of steam injection, water will invade the rocks and the
a pre-steam injection core is a pasty, phase diagram predicts that analcime
( unconsolidated mixture of mineral will be stable at higher salinities than
( grains and tar. Detailed petrographic kaolinite and smectite at the same tem-
work demonstrates that an early, fine- perature. All the studies mentioned
( grained diagenetic assemblage (less demonstrate that "artificial" diagenesis
than 4 ILm) of illite, smectite, zeolites does occur during steam injection or in-
( Ond chlorite is replaced by coarse (4-10 situ combustion. The studies also indi-
ILm) smectite and large euhedral ana- cate that artificial diagenesis affects
lcime crystals (20 ILm, see Figure 8). the petrophysical parameters of the
Figure 10 shows that decreases in rock and, presumably, the efficiency

o porosity correspond to decreased kao-


linite and increased smectite content in
of oil recovery.

o the less than 2 ILm size fraction. The


reaction postulated for these mineral
SUMMARY AND CONCLUSIONS
The most obvious feature of sandstone
( alterations is diagenesis is the modification and gen-

c 7AI2Si 20s(OH)4 + 8Si0 2 + 2Na+


kaolinite quartz
(4)
eral reduction of porosity. Compaction,
pressure solution and authigenic ce-
o = 2NaAl~i11030(OH)6 + 7H 20 + 2H +
mentation by mineral reactions are the
p rinciple processes contributing to this
o smectite
porosity modification. The rate and

o Figure 9 A pre-steam core from the Cold


(Sedimentology Research Group, 1981)
and in conjunction with albite- and
pathway of sandstone diagenesis is
strongly influenced by sediment com-
Lake tar sand is a pasty mixture of bitumen analcime-bearing reactions can be position, which IS In turn dependent

c and mineral grains. Two years of cyclic


steam injection and steam flooding have
used to construct a phase diagram to
outline the stability fields for analcime,
on sedimentary and tectonic environ-
ments. Temperature also is a regulating
o removed most of the oil and lithified the
sand. The minerals in Figures 8c and 8d ce-
kaolinite, smectite and albite. The
phase diagram constructed (Figure 11)
factor, most easily recognized by the
different paths of diagenesis in areas of
CJ ment the individual grains together. verifies the mineralogical and textural varying geothermal gradients. Upon
r......
Ka Sm II Ch
C ;:-_-T-_...;;1? -;0 ~ 4? -~o 9 4? -4;.:,0:.....,.-.:;~:......;2? -1~0
- 410

o 1350 -
300

o 1360 - - 415
u
0

w
albite

-
smectite
'"
0, Q)
I/O
Q;
~
-c
:Ii
200

...
o
Q)
~ 1370 - Q;
I
~

\ ...\ , E ~
l-
,, I
I
,
I I
I
- 470 I kaolinite
C c, 1380 -
W
Cl
I ,I
I
I
\
\
l-
n,
w
100

,,
\
... \
l 1390 - I
I I
\
Cl 6 10
Ln aNa+ -
12
Ln aH+
14 16

,I \

8
(f
I \
- 425
,I ... I
",\ I
Figure 11 Phase relations at constant
C 1400 -
""...... ,- I
\
pressure and silica acivity for kaolinite,
smectite, albite and analcime show that, for
a given fluid composition, smectite is a
Figure 10 This figure shows changes in porosity (tb), kaolinite (Ka), smectite (8m), illite (II) higher temperature phase than is kaolinite.
and chlorite (Ch) contents in the tar sand samples examined. Whengoing from the pre-steam to In addition, at constant temperature, anal-
post-steam samples, a negative change means a decrease, and a positive change means an cime requires higher values of the equilib-
increase. The antipathetic relationship between smectite content and kaolinite content is the rium constant (at constant pH, this could be
basis for the mineral reactions postulated. Note that increases in smectite content correspond interpreted as increased salinity) than do
to decreases in porosity. kaolinite or smectite.
c
174 Diagenesis Geoscience Canada Reprint Series 4 c
C
burial , sandstones display evidence of Boles, J.R. and Franks, S.G., 1979, Clay Surdam, R.C. and Boles, J.R., 1979, Dia-
C
"active" diagenesis which can be mod- diagenesis in Wilcox sandstones of genesis of volcanic sandstones, in (
elled by mineral-solution equilibria. southwest Texas: Journal of Sedlmen- Scholle, PA and Schluger, P.R., eds.,
Much of the material required for sand- tary Petrology, v. 49, p. 55-70. Aspects of Diagenesis: Society of Eco- C
Currie, J.B. and Nwachukwu, S.O., 1974, nomic Paleontologists and Mineral-
stone diagenesis (especially in very
quartz-rich sands) is transferred from
Evidence on incipient fracture porosity ogists, Special Publication 26, p. 227- C
in reservo ir rocks at depth : Bulletin of 242.
other rock by fluid movement. Fluid Canad ian Petroleum Geology, v. 22 , C
movementmay. result from upward and
oytward flow of compaction wate r,-
p.42-58.
Curtis, C.D., 1978, Possible links between
Porosity Variation with Depth (
circulation of grollndwater in hydro-
dynamically complex basins or by con-
sandstone diagenesis and depth-re-
lated geochemical reactions in enclos-
Hayes, J.B., 1979, Sandstone diagenesis -
the hole truth, in Scholle, P.A. and
C
vective tJo.w...wi1hin basinal units. ~ ing mudstones: Geological Society of
London, Journal, v. 135, p. 107-117.
Schluger. P.R., eds., Aspects of Diagen-
esis: Society of Economic Paleontolo-
C
The propert ies of hydrocarbon reser-
voirs are affected by diagenesis, and Foscolos, A.E., Reinson, G.E. and Powell, gists and Mineralogists, Special Pub- C
T.G., .1982, Controls on clay-mineral lication 26, p. 127-139.
IV 07J.
can be dramatically altered by drilling
fluids or enhanced recover y tech -
authigenesis in the Viking sandstone, Galloway,WE., 1974, Deposition and diage- C
::.---- niques. Very detailed understanding of
central Alberta . I. Shallow depths: Cana-
dian Mineralogist, v. 20, p. 141·150.
netic alteration of sandstone in North-
east Pacific arc-related basins: Implica-
C
~ interaction between minerals ,
aqueous fluids, hydrocarbons and
Foscolos, A.E. and Powell, T.G., 1980, Min-
eralogical and geochem ical trans-
tions for greywacke genesis: Geological
Society of Amer ica, Bulletin , v. 85,
C
gases is required in order to maximize
hydrocarbon recovery.
formation of clays during catagenesis
and their relation to oil generation, in
p.379-390.
Loucks, R.G., Dodge, M.M. and Galloway,
C
The emphasis on more sophisticated Miall, A.D., ed., Facts and Principles of WE., 1979, Importance of secondary C
ways of modelling fluid and mass trans- World Petroleum Occurrence: Cana- leached porosity in Lower Tertiary sand-
fer (Wood and Hewett, 1982) and deal- dian Society of Petroleum Geologists , stone reservo irs along the Texas Gulf C
Memoir 6, p. 153-172. Coast: Gulf Coast Association of Geo-
ing with the overall kinetics of processes
Hower, J., Eslinger, E.V., Hower, M.E. and logical Societ ies, Transactions,v. XXIX, C
which are governed by reactions at
the mineral-solution interface (Aagaard
Perry, E.A., 1976, Mechanism of burial
metamorphism of argillaceous sedi-
p.164-171.
Lowry, WD ., 1956, Factors in the loss of
C
and Heldeson, 1982)indicate the direc-
tion of physical and chemical research
ments: I. Mineralogical and chemical
evidence : Geological Society of Amer-
porosity by quartzose sandstones
of Virginia: Amer ican Association of
C
on sandstone diagenesis . The applica- ica, Bullet in, v. 87, p. 725-737. Petroleum Geologists, Bulletin , v. 40, C
tion of scanning transmission electron Hutcheon, I., Oldershaw, A. and Ghent , p.489-500.
microscopy (STEM)offers the hope that E.D., 1980, Diagenesis of Cretaceous Maxwell , J.C ., 1964, Influence of depth, C
our ability to deal with the composition
and structure of very small mineral
sandstones of the Kootenay Formation
at Elk Valley (Southeastern Br itish
temperature and geologic age on the
porosity of quartzose sandstones: c
Columbia) and Mt. Allan (Southwestern American Association of Petroleum
grains will keep pace with the theoreti-
cal data. The chemistry of mineral sur-
faces, the kinetics of mineral reactions
and the thermod ynamic prOperties of'
Alberta) : Geoch imica et Cosmochimica
Acta , v. 44, p. 1425-1435.
Merino, E., 1975, Diagenesis in Tertiary
sandstones from Kettleman North
Geologists , Bulletin, v. 48, p. 697-709.
Selly, R.C ., 1978, Porosity gradients in
North Sea oil-bearing sandstones: Geo-
logical Society of London , Journal,
?
c
clay minerals and com elex .!.9 ueous
SOiutions at el~vated temReratur~
Dome, California - II. Interstitial solu-
tions: distribution of aqueous species at
v. 135, p. 119-132.
Taylor, J.M., 1950, Pore-space reduction in c
pressures are not well enough under-
stood to solve the scientific and practi- -
100°C and chemical relation to dia-
genetic mineralogy: Geochim ica et
sandstones: American Association of
Petroleum Geologists, Bulletin, v. 34, c
cal problems of diagenesis. Cosmoch imica Acta, v. 39, p. 1629-
1645.
p.701-716.
Schmidt, V.and McDonald D.A., 1979a,The
c
REFERENCES Muffler, L.J.P.and White , D.E., 1969,Active role of secondary porosity in the course c
metamorphism of Upper Cenozoic sedi-
ments in the Salton Sea geothermallield
of sandstone diagenesis , in Scholle, P.A.
and Schluger, P.R., eds., Aspects of Dia- c
Minerals Reactions in Sediments and the Salton Trough, Southeastern
California: Geological Society of Amer-
genesis: Society of Economic Paleon-
tologists and Mineralogists, Special c
Aagaard , P. and Helgeson , H.C., 1982,Ther-
modynamic and kinetic constraint on
ica, Bulletin, v. 80, p. 157·182.
Nesbitt, H.W., 1980, Characterization of
Publication 26, p. 175-208.
Schmidt, V., and McDonald, D.A., 1979b, c
reaction rates among minerals and
aqueous solut ions. I. Theoretical con-
mineral-formation water interactions in
Carbon iferous sandstones and shales
Texture and recognition of secondary
porosity in sandstones, in Scholle, P.A.
e
siderations: American Journal of Sci- of the Illinois Sedimenta ry Basin: Amer- and Schluger. P.R., eds., AspectsofDia- (
ence, v. 282, p. 237-285. icanJournaJofScience,v. 280,p. 607-630. genesis: Society of Economic Paleon-
Boles, J.R., 1979, Active ankerite cementa- Schmidt, G.W , 1973, Interstitial water com- tologists and Mineralogists, Special (
tion in the subsurface Eocene of south- position and geochemistry of deep Gulf Publication 26, p. 209-226.
west Texas: Contributions to Mineralogy Coast shales and sandstones : American Stuart, C.A., 1970, Geopressures: Second C
Association of Petroleum Geologists, Symposium on Abnormal SUbsurface
and Petrology, v. 68, p. 13-22.
Boles, J.R., 1982, Active albitization of pla- Bullet in, v. 57, p. 321-337. Pressures, Baton Rouge , Louisiana , C
gioclase , Gulf Coast Tertiary: American
Journal of Science, v. 282, p. 165-180.
121 p.
C
C
C
C
c
c Coarse-grained Siliciclastic Rocks 175

c
r, Van Elsberg, J.N., 1978,A new approach to Diagenesis and Sedimentary Magara, K., 1976, Water expulsion from
c sediment diagenesis: Bulletin of Cana- Environments clastic sediments during compaction -

c) dian Petroleum Geology, v. 26, p. 57-86.


Wilson, H.H., 1977, "Frozen-in" hydrocar-
bon accumulations or diagenetic traps
Mankiewicz, D. and Steidtmann, J.R., 1979,
Depositional environments and dia-
Directions and Volumes: American
Association of Petroleum Geologists,
Bulletin, v. 60, p. 543-553.
( - exploration targets: American Associ- genesis of the Tensleep sandstone, Neglia, S., 1979, Migration of fluids in sedi-
ation of Petroleum Geologists, Bulletin, Eastern Bighorn Basin, Wyoming, in mentary basins: American Association
C v. 40, p. 483-491. Scholle, PA and Schluger, P.R., eds., of Petroleum Geologists, Bulletin, v. 63,
Aspects of Diagenesis: Society of p.573-579.
( Pressure Solution and Quartz Economic Paleontologists and Min- Toth, J., 1980, Cross-formational flow of
(' Overgrowths eralogists, Special Publication 26, groundwater: A mechanism for trans-
p.319-336. port and accumulation of petroleum
c DeBoer, R.B., 1977, On the thermodynam- Siever, R., 1979, Plate tectonic controls on
diagenesis: Journal of Geology, v. 87,
(The generalized hydraulic theory of
petroleum migration), in Roberts, WH.,
c ics of pressure solution-interaction be-
tween chemical and mechanical forces: p.127-155. III and Cordell, R.J., eds., Problems in

o Geochimicaet Cosmochimica Acta, v. 41,


p.249-256.
Tillman, R.W and Almon, W.R., 1979, Dia-
genesis of Frontier Formation offshore
Petroleum Migration: American Associ-
ation of Petroleum Geologists, Studies

o DeBoer, R.B., Nagtegaal, P.J.C. and


Duyvis, E.M., 1977, Pressure solution
bar sandstones, Spearhead Ranch
Field, Wyoming, in Scholle, P.A. and
in Geology 10, p. 121-167.
Wood, J.R. and Surdam, R.C., 1979,
o experiments on quartz sand: Geo-
chimica et Cosmochimica Acta, v. 41,
Schluger, P.R.,eds. Aspects of Diagene-
sis: Society of Economic Paleontolo-
Application of convective-diffusion
models to diagenetic processes, in
o p.257-264.
Pittman, E.D., 1972, Diagenesis of quartz
gists and Mineralogists, Special Pub-
lication 26, p. 337-378.
Scholle, P.A. and Schluger, P.R., eds.,
Aspects of Diagenesis: Society of Eco-
as revealed by scanning electron nomic Paleontologists and Mineral-
microscopy: Journal of Sedimentary Fluids in Basins ogists, Special Publication 26,
Petrology, v. 42, p. 507-519. p.243-250.

o Reicke, E., 1895, Ober das Gleichgewicht


zwischen einem festen, homogen defor-
Burruss, R.C., 1981, Hydrocarbon fluid in-
clusions in studies of sedimentary dia-
Wood, J.R. and Hewett, TA, 1982, Fluid
convection and mass transfer in porous
( mierten Kerper and einer flussigen genesis, in Hollister, L.S. and Crawford, sandstones - a theoretical model: Geo-
Phase, insbesondere uber die Depres- M.L., eds., Fluid Inclusions: Applica- chimica et Cosmochimica Acta, v. 46,
o sion des Schmelzpunktes durch einseit-
ige Spannung: Anals Physik, v. 54,
tions to Petrology: Mineralogical Asso-
ciation of Canada, Short Course Hand-
p. 1707-1713.

( p.731-738. book, v. 6, p. 138-156. Diagenesis and Hydrocarbon Reservoirs

c Robin, P.-Y.F., 1978, Pressure solution at


grain-to-grain contacts: Geochimica et
Carpenter, A.B., 1978,Origin and chemical
evolution of brines in sedimentary Almon, WR., 1981, Depositional environ-

o Cosmochimica Acta, v. 42, p. 1383-1389.


Sorby, H.C., 1863, On the direct correlation
basins: Oklahoma Geological Survey,
Circular, v. 79, p. 60-77.
ment and diagenesis of Permian
Rotliegendes sandstones in the Dutch
o of mechanical and chemical forces:
Royal Society of London, Proceedings,
Cassan, J.-P., Garcia Palacios, M. delC.,
Fritz, B. and Tardy, Y., 1981, Diagenesis
sector of the southeastern North Sea,
in Longstaffe, F.J., ed., Clays and
v. 12, p. 538-550. of sandstone 'reservoirs as shown by the Resource Geologist: Mineralogical
Spang, J.H., Oldershaw, A.E. and Stout, petrographical and geochemical analy- Association of Canada, Short Course
o M.Z., 1979, Development of cleavage in sisofoil bearing formations in the Gabon Handbook, v. 7, p. 119-147.

c the Banff Formation at Pigeon Moun-


tain, Front Ranges, Canadian Rocky
Basin: Bulletin Centres de Recherche
Exploration et Production Elf Aquitaine,
Almon, WR. and Davies, D.K., 1981, Forma-
tion damage and the crystal chemistry of

o Mountains: Canadian Journal of Earth


Sciences, v. 16, p. 1108-1115.
v. 5, p. 113-135.
Germann, F.E.E., and Ayers, w., 1942, The
clays, in Longstaffe, F.J., ed., Clays and
the Resource Geologist: Mineralogical
o
, .
Sprunt, E.S. and Nur, A., 1977, Destruction
of porosity through pressure solution:
origin of underground carbon dioxide:
Journal of Physical Chemistry, v. 46,
Association of Canada, Short Course
Handbook, v. 7, p. 81-103.
Geophysics, v. 42, p. 726-741. p.61-68. Perry, C. and Gillott, J.E., 1979,The forma-
Waugh, B., 1970, Formation of quartz over- Haner, J.S., 1979,Thesedimentary genesis tion and behaviour of montmorillonite
o growths in the Penrith sandstone (Lower
Permian) of Northwestern England as
of hydrothermal fluids, in Barnes, H.L.,
ed., Geochemistry of Hydrothermal Ore
during the use of wet forward combus-
tion in the Alberta oil sands deposits:
C revealed by scanning electron micro- Deposits, Second Edition: Wiley-Inter- Bulletin of Canadian Petroleum Geol-
scopy: Sedimentology, v. 14, p. 309-320. science, New York, 789 p. ogy, v. 27, p. 314-325.
(:. Weyl, P.K., 1959, Pressure solution and the Hitchon, B., 1980, Some economic aspects Perry, C. and Gillott, J.E., 1982,Mineralogi-
force of crystallization - a phenomeno- of water-rock interaction, in Roberts, cal transformations as indicators of
8 logical theory: Journal of Geophysical W.H., III and Cordell, R.J., eds., Pro- combustion zone temperatures during
C Research, v. 64, p. 2001-2025. blems in Petroleum Migration: American
Association of Petroleum Geologists,
in situ combustion: Bulletin of Canadian
Petroleum Geology, v. 30, p. 34-42.
( Studies in Geology 10, p. 109-119. Pittman, E.D., 1979, Porosity, diagenesis
Hitchon, B., Billings, G.K. and Klovan, J.E., and productive capability of sandstone
1971, Geochemistry and origin of for- reservoirs, in Scholle, P.A. and Schluger,
mation waters in the western Can- P.R., eds., Aspects of Diagenesis:
ada sedimentary basin, III. Factors con- Society of Economic Paleontologists
trolling chemical composition: Geo- and Mineralogists, Special Publication
chimica et Cosmochimica Acta, v. 35, 26, p. 159-173.
p.567-598.
,-
'--.
r:
c
176 Diagenesis Geoscience Canada Reprint Series 4 (
C
Sedimentology Research Group , 1981, The C
effects of in situ steam injection on
Cold Lake oil sands: I. Mineralogical
C
and petrographic considerations (Older-
shaw, A., Hutcheon, I. and Nahnybida,
C
C.); II. Petrophysical and petrological C
considerations (Hutcheon, I., Older-
shaw, A..and Nahnyb ida , C.): Bulletin C
of Canadian Petroleum Geology, v. 29,
p.447-478.
(
Thomas , J.B., 1981, Classification and dia-
genesis of clay minerals in tight gas
C
sandstones : Case stud ies in which clay
mineral properties are crucial to dril -
C
ling fluid selection, formation evaluation C
and completion techniques, in Long-
staffe, F.J., ed., Clays and the Resource C
Geologist: Mineralogical Association
of Canada, Short Course Handbook, C
v. 7, p. 104-118.
Wardlaw, N.C. and Cassan , J.-P., 1979, Oil
C
recovery efficiency and the rock-pore
properties of some sandstone reser -
C
voirs: Bulletin of Canadian Petroleum
Geology, v. 27, p. 117-138.
C
Wilson , M.D. and Pittman, E.D., 1977, Auth i- C
genic clays in sandstones: Recognition
and influence on reservoir properties
(
and paleoenvironmental analysis: Jour-
nal of Sedimentary Petrology, v. 47,
C
p.3-31. C
C
Originally published in C
Geoscience Canada v. 10 Number 1
(March 1983)
C
C
C
C
C
C
C
C
C
C
c
e
(
(
C
C
C
(
(
(
CJ
C Catagenesis of Argillaceous Sedimentary Rocks 177

C
C sediments ranged from 4,000 to 10,000 quartz. Thus, the rnlneraloqical compo-
o feet, the hydrocarbon production depths
were distributed about a mean of 1,500
nents in pelitic sediments adjust to the
prevailing physicochemical condit ions.
c feet above the theoretical first clay In 1974, Foscolos and Kodama stud-

c dehydration level. Finally, the same


investigator correlated his three stages
ied the transformation of smectite to
illite in the Cretaceous shales of north-
c of sediment dehydration with the flush- eastern British Columbia and showed

c ing of hydrocarbons from the source


rocks, which he called the "Gulf Coast
Fluid Redistr ibution Model " (Figure 2).
that in order to promote the dehydrat ion
of expandable layer silicates , the tem-
perature must first reach a critical value
(
Catagenesis of Thus, gravitational displacement and then alum inum must enter and
c Argillaceous
squeezes out water from the pore
throats by the rearrangement of sedi-
substitute for silicon in the structure of
the expandable clay. This isomorphic
Sedimentary Rocks mentary grains while alteration of the substitution upsets the crystal electro-
o 2:1 layer silicate promotes the slough-
ing of water layers from their surfaces.
neutrality because an ion with 3 val-
ence, aluminum, substitutes for an ion
o A. E. Foscolos The latter was thought to be instrumen- with a 4 valence, silicon, thus increas-

o Geological Survey of Canada


Institute of Sedimentary and
tal in the dissolution of hydrocarbons,
thereby aiding primary oil migration.
ing the negative charge which origi-
nates from the oxygens and hydroxyls
o Petroleum Geology
3303 - 33rd Street N.W
Dunnoyer de Seconzac (1970) re-
viewed the mineral transformation that
of the lattice. To counterbalance this
negative charge, potassium must be
Calgary, Alberta T2L 2A 7 takes place during the stepwise burial of absorbed on the clay surface . This pro-
and shales and concurred that smectite cess triggers the expulsion of calcium
Schoolof~ineralResources undergoes conversion to interstratified from the clay surface and the sloughing
o Engineering
Technical University of Crete
illite-smectite and finally to illite. Perry
and Hower (1972) proposed a two-step
off of the absorbed water. Further iso-
morphic substitution of silicon by alumi-
Chania 73132 dehydration model, instead of the one- num releases magnesium and iron into
Crete, Greece step model suggested by Burst. In the the solution. The same authors recog-
first step, there is water expulsion nized also that the transformation of
INTRODUCTION engendered by the relatively rapid col- smectite to illite involves an intermedi-
Argillaceous sediments undergo pro- lapse of the smectite layers, while the ate state . Smectite is transformed to
gressive transformation upon burial second step is marked by the transition vermiculite and then to illite.
beneath succeeding sediments. These from random to ordered interlayering. SUbsequent work by Foscolos et al.
transformations affect the water con- This promotes a second dehydration (1976) and Powell et al. (1978) in north-
tent and the mineralogical , inorganic from the layered illites. The conversion eastern British Columbia, the Canadian
and organic components of the pelitic of smectite to illite through the inter- Arctic Islands and the Beaufort-Mac-
rocks. The combined changes in or- mediary step of a binary mixed-layered kenzie Basin of the Canadian North-
ganic or mineral matter resulting from silicate is discussed further by Hower west Territories has shown that though
pressure and temperature conditions in et al. (1976) and Aronson and Hower clay dehydration coincides with the on-
the subsurface that are much different (1976).They have suggested that smec- set of hydrocarbon generation at 0.5%
from those at deposition are attributed tite reacts with K-feldspar and some- Ro vitrinite reflectance , the main phase
to catagenesis. times with mica , in absence of K-feld- of hydrocarbon generation occurs
Compaction and gravitational dis- spar, to produce illite, chlorite and at greater levels of burial. Quantitative
placement of water was the first de-
watering mechanism recognized (Hed- POWERS BURST PERRY AND HOWER
berg, 1936). Power (1967) recognized (1967) (1969) H.GEO.GRAD. L.GEO .GRAD.
-2.7S"C/10om -2.1S"C/100m
that dewatering also occurred during
( the conversion of smectite to illite. He
designated these two processes of :I: I
C dewatering as States I and II, respec-
l-
Q,
w
I I

tively (Figure 1). c


6 In 1969, Burst used statistics to corre- w
o II
Cl:
late clay dehydration with petroleum II. II
a: m
occurrences by plotting the difference :)
CIl
between the depth of the first clay III
m Ii:
dehydration, which occurs when 25% of
:)
CIl m
smectite is converted to illite, and the I[

production depth from 5,368 locations


STAGE I, rr, ETC.
in the Gulf Coast area of the United
States. He found it significant that
although dehydration depths of the Figure 1 Dewatering process of argillaceous sedimentary rocks upon burial .
c
178 Diagenesis Geoscience Canada Reprint Series 4 (
C
mineralogical and geochemical studies accomplished by removing the other growth (Longstaffe , 1983).Oxygen iso- C
showed systematic decreases in amor- cations either by forming new minerals tope work can verify this process. 51 8 0
phous inorganic components and in the in situ which are less rich in silica, or by valuesfor Si0 2, derivedfrom igneousand
C
quantity of layer silicateswith increasing transporting the products to adjacent metamorphic rocks, must be lower than C
depth (Foscolos and Powell, 1982). sandstones, leaving silica gel behind. that derivedfrom the conversion of amor-
Recent work in diagenesis of pelitic For example, K-feldspar can be trans- phous silica gel to crystalline quartz. C
sediments "indicates that diagenesis
is a multifaceted process consisting
formed to a 2:1 layer silicate by reacting
with carbon ic acid. The latter can be
Thus, silica gel absorbed on pre-existing
quartz grains should have higher 5180
C
of mineral alterations along with the released from the thermal and bacterial values, or if one peels off the successive C
dewatering processes. The latter com- decarboxylation of the concomitant layers of Si02 by HF,then &1 8 0 valuesof
prises at least four mechanisms: organic matter (Tissot and Welte, 1978). the remaining quartz crystal should de- C
(1) gravitational displacement; (2) wa-
ter expulsion from the inorganic gels; (3)
This reaction yields amorphous silica
as follows:
crease progressively.
Feldspars.
C
the sloughing of water from the hydrous
3KAISi 308 + H2C0 3 + 12H20 =
The most common feldspar encoun- C
layer silicates; and (4) the release of tered in pelitic sediments is K-feldspar.
water from the destruction of clay miner- KAI2(AISi3 08 ) + 6H4Si04 + K2C0 3 (1) Albite and anorthite are very seldom en- C
als along with cations which migrate
individually or in chelating form to the
Another reaction which also pro- countered because they are easily
weathered (Birkeland, 1973). In the
C
duces amorphous silica is the trans-
adjacent sandstones forming authi- formation of smectite to illite which in early stages of diagenesis K-feldspar C
genic cements. The primary objective of also disappears when attacked by car-
this review is to discuss the alterations
diagenesis usually follows the first
equation. The reaction can be written in boxylic acids (Surdam et al., 1984; Sur-
C
and genesis of minerals in shales during general terms : dam and Crossey, 1985) or from car- C
diagenesis along with the generation of bonic acid derived from the thermal
water from the last three processes and
K+ + smectite = illite/smect ite +
silica + other products (2)
and bacterial < 80°C, decarboxylation C
the ir relat ion various auth igenic ce-
ments encountered in sandstones . Indeed, equation 2 yields Ca2-; Mg2-;
of organic matter. The organic origin of
CO2has been reported byCurtis (1978),
C
Finally the relationship between clay Fe2+ and H20 (Foscolos and Kodama, Schmidt and McDonald (1979), Car- C
catagenesis, the organic matter dia- 1974; Hoffman and Hower, 1979; Boles others and Kharaka (1980), and Lun-
genesis and cementation of adjacent and Franks, 1979). Amorphous silica, degard et al. (1984). The attack by C
sandstones is discussed. generated from either or both reactions
1 and 2, can be re-adsorbed on existing
organic acids on silicates should be
considered as a significant factor be-
C
MINERAL TRANSFORMATION IN quartz grains, inducing crystal over- cause of its dual effect as an acid and C
PELITIC SEDIMENTS DURING
BURIAL C
The most abundant minerals in shales
are the silicates, where carbonates are
C
minor components. Mineral identifica- C
tion in pelitic sediments reveals more or
less the same components. However,
6.6
C
quantitative estimation of individual
minerals with burial depth indicates that
C
some key components, such as smec-
NON-LIQUID
HYDROCARBONS C
tite, kaolinite and chlorite , disappear or 5 .1

appear at certain depths, while others


0
0
C
0
transform gradually.
.e
M
C
The nature of the most commonly en-
countered constituents with burial depth
;
E
3 .4
C
E
is, therefore discussed individually.
Quartz.
s:
~
C
Quartz is ubiquitous in shales and,
GO

"
~
c
apparently, its absolute amount in-
creases with burial depth (unpublished
"
lD
e
c
1.7
data from the Beaufort-Mackenzie and
Sverdrup Basins) . This implies that
either the remaining minerals are c
removed from the system, thus increas-
ing its relative abundance, or that quartz c
is added to the system during the
destruction of other minerals. This is
23.3 37.7 66.5 93.2
Temperature in CO
121 .0 14 6 . 7

c
Figure 2 Correlation between burial depth, geothermal gradients in °C per 100metres and
(
occurrence of hydrocarbons. (Modified after Burst, 1969).
c
c
c
(
c Catagenesis of Argillaceous Sedimentary Rocks 179
C.
r:
a chelat ing agent capable of removing relates mineral assemblages in shales , from within the unit cell as well as cal-
r: the products of dissolution such as alu- sandstones and volcanic rocks from cium and magnesium from the surface

c minum (Surdam etal., 1984). Finally, the


products of feldspar dissolution are
ambient temperture to 350°C.
Smectite.
are expelled into the solution . In addi-
tion , absorbed H2 0 sloughs off from
C. used to enhance quartz overgrowth or
to activate the transformation of smec-
Smectites are stable at temperatures
much higher than those encountered
smectites . These changes are recog-
nized by the reduction of the doo, spac-
C tite to illite through the intermediary
step of mixed layer silicates.
during diagenesis. However, the chemi-
cal composition of the interstitial solu-
ing of a Ca-saturate smect ite from
1.56 nm to 1.20 nm in the mixed layer
( Layer Silicates. tions is the most important factor in (Figure 3). One should notice the per-
Layer silicates are the second most transforming smectites to illite via the manent imprint that these chemical
C abundant component of pelitic sedi- mixed-layer path . Discrete smect ites changes impart on the smectite lattice
('. ments after quartz and feldspars. They are usually abundant in the middle or in order to be identified by x-rays. Had

o include smectite, illite, interstratified


2:1 layer kaolinite, and chlorite. Step-
wise burial of shales and sandstones
late stages of diagenesis (telodiagene-
sis). Any occurrence of discrete smec-
tite in deep zones of diagenesis should
the isomorphic substitution of Si4+ by
A13+ in the crystal lattice of smectite not
taken place, the doo, spacing of the clay
show changes in composition of hyd- be considered as due to hydrothermal mineral should have stayed the same,
( rous layer silicates as a function of depth phenomena. that is, 1.56nm. As a result, the amount

o reflecting mainly the increase of tem-


perature. Recent sediments are en-
Mixed-Layered Silicates.
Mixed-layered silicates appear in the
of water loss by dehydration for one
gram of smectite converted to one gram
riched in discrete minerals such as illite, early stages of diagenesis. Once potas- of 50% illite - 50% smectite is calcu-
kaolinite, smect ite or vermiculite while sium and aluminum are present in the lated as follows:
older sediments contain mixed -layered interstitial pore water and the tempera- Two facing areas of a unit cell = 2ab =

o silicates and even older sediments,


discrete chlorite and 1 Md illites (Grim,
ture is between 90° -100°C, smectite is
converted to illite (Foscolos et al., 1976;
2 x 5 .25~ x 9 .20~ = 96 .6~2
where a and b are the unit cell dimens ions
o 1968; Weaver and Beck, 1971; Foscolos
and Kodama, 1974; Foscolosetal. , 1976;
Powell et al., 1978). Aluminum, derived
probably from the breakdown of feld-
for smectite.
The specific planarsurfacein m2 • g-' is
o Hower et al., 1976).Due to this systema- spars , substitutes for silica in the tetra- 96.M2x 10-20 m2 .Jl.2
tic variation in composition with depth, hedral positions, thus promoting a Molecular weight of smectite/6.02 x 1023 mole "
that is temperature, hydrous layer sili- charge deficit within the crystal cell
cates have been used as paleotempe- unit. To counterbalance the negative 96 .6 m 2 x 6.02 x 1023 mole "
_ _ _ _ _ _ _ _ = 808 m2 ' g"
rature indicators between 80°- 300°C charge, a potassium ion is preferentially 720 g ' mete-i x 10.20
(Steiner, 1968;Sumi, 1969; Eslinger and absorbed on the smectite surface by
where 720g is the atomicweight of smec-
Savin, 1973; McDowell and Elders, displacing absorbed calcium andlor
tite in grams, 10-2 0 is a conversion factor
1980). A review art icle by Eberl (1984) magnesium . This implies that silicon
from 'A2 to m2 and 6.02 x 1023 mole-t is
Avogadro's number.
d-spac1ng in nm Since there is a reduction of the doo,
~ ! i ~:m ~ II ~ ~ spacing from 1.54nm to 1.18 nm, that is
- --
II 0.36 nm, then the water loss per m2'g-'
VJ nanometres
of smectite when convertedto 50% illite-
50% smectite is

rvV
V 1.0 1.6
808 x 104 cm2 • go' x 0.36 X 10-7 cm =
r-
VJ .426.7

~731.5
290.88 x 10-3 cm 3 • g" .
r
....
_ 1 1271
II rv ..".. I Assuming a density of 1 g ' cm-3, this
.-
l-
V ~ .11 27.7
water loss converts to 290.99 mg per
I
."
-
S !1493.5
- lilltJI
V gram of clay. This result is comparable
.s:: r- ::
C
.-
.'"
..." ... 'V
~ I .-
"
:E 2 /.-<:Z8.8 to the experimental result of Mooney et
al. (1952) who reported a loss of 270 mg
r- ~ I ~ j2133.6
~
. .s::
.- ,2438 .4 of H2 0 per gram of Ca smectite when
IQ
"
"-- ,......
'v I
"
C- .2758.4 the doo , spacing is reduced from 1.56
6
I-
1/\ r 3 I
13093.7 nm to 1.20 nm, that is, by 0.36 nm.
.... ,
I
j3352.8
r By the thermodynamic manipulation
i'--- f-I \.... V
.... / of water vapour absorption and desorp-
k
r-:
'-
'"''
:, T
I
VI tion isotherms of the clay and simul-
taneous layer distance measurements
'-' J5 25 10
by x-ray diffraction of the doo, spacings
r- Degrees, 28 CoKa of smectites, Keenan et al. (1951) and
'-" Mooney et al. (1952) have calculated
Figure 3 d oo1 spacings of calcium saturated 0.2 ~m specimen at 50% relative humidity the required pressure to remove a
versus burial depth from a North Sabine H-49 well sample (Foscolos and Powell. 1980). monolayer of water of 0.36 nm (3.6'A)
(
180 Diagenesis Geoscience Canada Reprint Series 4 c
c
thickness, as follows: From this calculation, it is obvious that passing research in northeastern Brit- C
-AT
the second clay dewatering process
requires much more energy, especially
ish Columbia, the Beaufort-Mackenzie
and the Sverdrup Basins in Canada , has
C
II = - - In PIPo
v,.M if the mineral is vermiculite. shown that the transformation of smec- C
To remove the last monolayers of tite to 2:1 mixed-layer silicates passes
where II = gas constant in atmospheres water which is absorbed on the clay through the vermiculitic step. Thus, the C
R = gas constant in litre-atmospheresl surface, different free energies and
pressures will be required, depending
mixed-layered system cons ists of iIIite-
smectite-vermiculite rather than the
C
mole degree
T = absolutetemperature(25°C = 2981<) on the type of expandable 2: 1 layer sili- binary system observed by Perry and C
cate and the ion adsorbed on its clay Hower (1972). The implication of having
v,.M = Molar volume of water =
0.01802 litre ' molet surface. If it is smectite, the required a ternary system with vermiculite as an
C
PIPo = relative humidity at which the free energy to release the last mono-
layer of water is much less than that of
intermediary in the transformation of
smectite to illite is that the last layer
C
doo , spacing is observed.
At 50% relative humidity, or at PIPo = vermiculite. The explanation lies in two absorbed water on the clay surface is C
factors: first, the amount of charge defi- very difficult to expel within the range of
0.5, the d oo , spacing of Ca-smectite is
15.6'- or 1.56 nm (Brown, 1961). There- cit originating from the clay mineral is oil generation and therefore it should
C
fore, at PIPo = 0.5 d oo , spacing of Ca- larger in vermiculites than smectites, not be considered in the oil migration C
smectite is and secondly, the seat ofthe charge is in mechanism, at least for the wells stud-
both octahedral and tetrahedral posi- ied in Canada. Perry and Hower (1972) C
0.0821 x 298
II = 0.01802 x 2.303 log 0.5
tions, the latter being very close to the
clay surface. This renders very strong
reported a second clay dehydration
from the pelitic sediments of the Gulf
C
= 941.02 atm . or 941 atm x 1.013 bar/atm.
attractive forces on the last monolayer Coast at temperatures around 140°C, C
of water. The magnitude of the force can while in the Sverdrup and Beaufort-
= 953.25 bars. be calculated from Coulomb's law: Mackenzie Basins the second dehy- C
At 4% relative humidity, PIPo = 0.04,
dration step was not encountered at
temperatures close to 150°C. The
C
the doc, spacing of Ca vermiculite is
12.0'- or 1.2 nm, therefore:
author believes that the difference is C
probably due to the type of smectites
0.0821 x 298 where F is the attractive force, Q is the encountered in the different basins. C
n = 0.0802 x 2.3031090.04 = 4066.92alm. charge of the particles in d-J,DKI.utn m C
esu, D is the dielectric con- ~ ~ § ~
As a result, to remove the second layer
stant of water, and r is the C
of water 4066.92 atm . or 4119.79 bars
(4066.92 atm x 1.013 bar/atm) of pres-
distance between the origin C
of charges and the centre of .::;:::~::..
sure is required. For 0.25 nm thickness,
van Olphen (1977) has calculated the
water molecules. C
It is obvious that in vermic-
pressure of removal of the second layer
ulites the a value is large W:~:t=':'H . C
of water at 4000 bars.
Using the partial free energy dif-
and the r value is small. As a C
result, even at extremely low Ca <2j11rtlOl'tented
ference, .tof, we can measure the work in
ergs -go' of H 2 0 , wh ich is required to
PIPo relative humidity val- _ ,",",,,"""•.H C
ues water is still adsorbed on (
free the second layer of water from the
the vermiculite surfaces, C. '2~,""""'''
clay surface. This is given by making the desorption of __ .t ........ c..
~ =
-AT
M x 2.303 log PIPo
the last monolayer of water
very difficult. The exact free C. '2~,"orie"," c
c
specunenat 5!5O'C
energy or work requires a
very precise knowledge of
where R = the gas constant(8.316 x 10
erg ' mole-i . degree K or
7
the PIPo value at which the ~~::.::,e:..
d oo, spacing of vermiculites
c
8.316 joules) becomes 9.6'-, or 0.96 nm.
T = the temperature in Kelvin (273°C)
M = the molecular weight of water
So far this value has not ":'~""~;'H
been determined, but it is in
e
(18.02 gm· mote-t) the order of tens of thou- (
PIPo = the relative humidity. sands of atmospheres. A ..:::.:::.;:'~'.':..
Thus, the respective free energy good discussion on this sub - l
between free water and the second ject is presented by van
water layer which is absorbed on the Olphen (1954, 1965) and Kit-
clay surface is -412.05 x 107 ergs · g-' trick (1969a, b). Work by Fos-
(-412.05 joules). Since one calorie is colos and Kodama (1974), Figure 4 d oo1 spacings of calcium and potassium satu-
4.184x 107 ergs, the partial free energy Foscolos et al. (1976) and rated < O.2p.m oriented specimen under various x-ray
can be calculated as -98.48 cal, go'. Powell et al. (1978), encom- conditions from a North Sabine H-49 well sample.
c
c
c
(
( Catagenesis of Argillaceous Sedimentary Rocks 181
(
c' It is possible that trioctahedral smec- The crystallinity of illite, that is, the Chlorite.
tites behave differently than diocta- morphology of the 1 nm peak, has been Diagenetic chlorite is not detected in
hedral smectites, the latter being closer used by Weaver (1960, 1961) and by pelitic sediments in the early or middle
C' to a vermiculitic structure (Kishk, 1967). Kubler (1964) as a diagenetic indicator. stages of diagenesis in either the Sver-
( . Todate, dioctahedral expandable clays This indicator, which is quantified by drup or the Beaufort-Mackenzie Basins
have been encountered in all samples measuring the ratio of heights at 1.0nm or in northeastern British Columbia
C· from the Sverdrup and Beaufort-Mac- and 1.5nm orthe width ofthe 1 nm peak (Foscolos and Stott, 1975; Foscolos et

r kenzie Basins. IlIite-vermiculite-chlo-


rite-smectite mixed layers are very
at half height, is valid only at the late
stages of diagenesis or early metamor-
al., 1976; Foscolos and Powell, 1980).
The possible explanation lies in the pre-
c often encountered at deeper burial
depths (Powell et al., 1978).
phism. In the early stages of diagenesis
the rearrangement of ions in the inter-
sence of CO2 derived from thermal, and
bacterial decarboxylation of organ ic
To identify a ternary or quaternary layering spacing ofthe 2:1 layer silicates matter or carboxylic acids generated

o system of mixed-layer silicates the clay


fraction must be subjected to a series
and the experimental condition under
which the sample is x-rayed renders its
from the thermocatalytic degradation
of kerogen (Tissot and Welte, 1978;
( of treatments with two different ca- value questionable. A comparative Carothers and Kharaka, 1978, 1980).
tions absorbed on the clay surfaces. By scheme using all these indiators for dia- These render the pore fluids acidic. Un-
C knowing the adsorbed cation on the clay genesis is presented by Foscolos and der low pH values, the chelating action

o
r
surface and the physicochemical condi-
tions under which the sample is sub-
Stott (1975) and Foscolos et al. (1976).
Incipient metamorphism (anchizone)
of monofunctional and difunctional
carboxylic acids complex Ala+ and Fea+
jected during x-ray analysis , the doo1 and low greenschist facies from the mar- and at the temperature of 80°C chlorite
spacing can define the kind of expand- ginal zones of the Swedish Caledonides, can not be formed and therefore de-
( able layer silicates, the components and Swiss Alps and VenezuelanAndes were tected at the early stages of shale dia-
their weighted percentages (Brown , determined on the basis of illite "crystal- genesis. The instablity of chlorite in acid
C 1961). Under given physical conditions, linity" (Kisch, 1980;Frey, 1970;Kubler et media and temperatures around 80°-
a binary mixture of illite-smectite with al., 1974; Shaga, 1977), while the lattic 100°C is used as a technique for re-
r Ca2+ absorbed on its surface will show parameter b, of dioctahedral iIIite/mus- moving it from samples where kaolinite
specific d oo1 spacings. K+ -saturated covite has been used for the characteri- and chlorite are present. This facilitates
r: illite-smectite will achieve similar doo1 zation of PIT gradients in incipient meta- mineral identification by x-ray diffrac-
spacings under the same physical con- morphism (Padan et et., 1982). tion (Brown, 1960).
r:
ditions. However, a ternary system of Kaolinite. In late diagenesis, where amorphous
clays consisting of illite-smectite-ver- Kaolinite is abundant in the early and silica , aluminum, iron and magnesium
miculite with Ca2+ absorbed on its sur- middle stages of diagenesis, while usu- are available, chlorite an be formed
face will show d oo1 spacings (Figure 4). ally absent in the last stages (Dunnoyer from the aluminum , silica, iron and mag-
Chemical analysis of the calc ium-satu- de Seconzac, 1970; Foscolos and Pow- nesium, as proposed by Almon and
rated clays can be used to confirm the ell, 1980; Hower, 1981; Boles, 1981). It Davies (1979), where
results of the x-ray analysis . The CaO seems that once the chloride salt solu-
contents are used as a measure of tions have been expelled from pelitic 2AI(OH)
the cation exchange capacity (C.E.C.) sediments, the pH value of the system 4Mg2+(aq) + Fe2+(aq) =
which is the charge of the clay surface, becomes more alkaline. With tempera-
r while the K20 contents measure the tures rising above 100°C, kaolinite is Fe2+ M9 4AI2SiaO,o(OH)s(solid)
illitic component of the mixed layers. dissolved ortransformed to other miner- + 2H 20(I) + 8H+
From these two results, an estimation of als. As the ratio of [K+ JI [H+] in the
the expandable component can be pore solution increase, kaolinite is iIIit- or as proposed by Hutcheon et al.
made . Consequently, the chemical ized (Hemley, 1959). For a [K + JI [W ] (1980), where
analysis can check the information ob- equal to 106, kaolinite is transformed
5CaMg(CO a)2 + AI2Si20s + Si02
tained from the x-ray patterns concern- to illite at 100°C while , at a ratio of
+ 2H20 =
ing the composition of the mixed layers. [K+ J/[H+ J equal to 10a, a temperature
Illite. of 200°C is needed to achieve the same dolomite kaolinite quartz
Illite is not a particular mineral. The term conversion . Dunnoyer de Seconzac
is used to designate a group of clay (1969) demonstrated the instability of M9sAI2Sia01o(OH)s + 5CaCOa
minerals having a mica-type structure. kaolinite in seawater above 200°C. An- + 5C02
Illites exist in 1M, 1Md, 2M and 3Tforms. other reaction where kaolinite is trans- chlorite calcite
The latter is a rare type . 1 Md illite, the formed at elevated temperatures is re- or, as proposed by Boles and Franks
disordered form , is the most common ported by Hutcheon et al. (1980). At high (1979), where
type in sedimentary basins , and as the temperatures, kaolinite reacts with do-
temperature rises during catagenesis lomite and silica to produce a magne- 3.5Fe 2++ 3.5Mg2+ + 92H20
the reaction goes from 1Md to 2M. The sium chlorite, calcite and CO2, How- + 3AI2Si20s(OH)4 =
methods for studyi ng these transforma- ever, if Fe(OHb is present, an iron- kaolinite
tions by x-ray techniques and their sig- magnesium chlorite can be produced,
nificance in sedimentary rocks are re- a product very often encountered in Fe a.sMga.sAI6.oSi6.1 02o(OH)16
ported by Maxwell and Hower (1967) diagenesis. chlorite.
and Velde and Hower (1963).
r:
182 Diagenesis Geoscience Canada Reprint Series 4 r
r
However, in most cases, chlorite in the water released between ambient tem- formation. Under acid or neutral pH C
late stages of diagenes is of pelitic sedi-
ments seems to derive from amorphous
perature and 100°C is approximately
15%, while the water given between
values amorphous silica probably is
retained in shale, while amorphous alu-
C
aluminum , iron and magnesium ions 100°C and 150°C is 7% (Jackson, minum being complexed by organic C
which are incorporated into the ternary 1956). This implies that prior to first clay acids, probablydiffunctional carboxylic
systemof2:1Iayersilicates. Theconver- dehydration, 1.5 g of H20 will be re- acids as suggested by Surdam et a/. C
sion of chloritic integrades to discrete
chlorites with depth was documented in
leased from 10g of amorphous material
to the pore space, while 0.7 g will be re-
(1984) or as hydroxyaluminum ion,
migrates to form a monomer with amor-
C
samples from Drake Point 0-68 and leased after the first clay dehydration. phous silica. The latter is available in C
Cape Norem A-80 wells in the Sverdrup This amount of water is roughly equal to sandstones during this diagenesis.
Basin and in samples from Cretaceous that given off from 10g of smectite clay These monomers, as proposed by Sif-
C
shales of northeastern British Columbia when it transformed to 50% illite and fert(1967), can be considered as precur- C
(Figure 5). Based upon the presence of 50% smectite. On the basis of the pre- sors of authigenic booklets of kaolin-
carbonic acid, derived from the matura- viouscalculat ions, this amountsto 1.35g ite and hairy illites encountered in the C
of H20. Thus, the amount of pure or salt- sandstones (Figures 6 and 7). Such
tion of the organic matter at the early
stages, the overall reaction can be sum- free water released in the pore system monomers can then link to similar
C
marized as follows: prior to, and during, the first dehydration monomers to form tetrahedral and octa- C
of clays from both the amorphous ma- hedral sheets. The formation of an octa-
interchange terial and the smectite transforma- hedral sheet involves the rearrange - C
H+ + expandable clays reaction .... tion process creates an over-pressure
zone. Statistical data indicate that there
ment of OH ions and AI ions, while a
tetrahedral sheet requires the removal
C
is a good correlation between the over- of water from the OH group linked to C
pressured zone and the sonic transit- silica ions. From Figures 6 and 7, it is
time time in shales (van Elsberg, 1978). obvious that the ratio of silica/aluminum C
expandable clays heat .... Amorphous inorganic gels, besides
supplying water to the system, also pro-
determines the kind of amorphous
monomer gel to be formed and, there-
C
time
.... chloritized (2:1 layer silicates) heat....
vide cementing agents to either the peli- fore, the kind of layer silicate. However, C
tic sediments or the adjacent sand- to precipitate clay minerals from solu-
stones through the process of mineral tion, aluminum must be present in six-
C
.... chlorites .
C
A B
The absorption of protons by clays d-spacing in nm d-spacing in DID C
and their interchange with octahedral ~ ~ i ~ a~ii e l! ss § U
...... ~ ~ ~ ~ ~~ l!a e ss § §...
§ ..10
aluminum, iron and magnesium have
..,; .,.;

C
been discussed by Foscolos (1964) and
Foscolos and Barshad (1969).
731.5 -A. ./
- I-'
t-.
I\. f C
C
AMORPHOUS INORGANIC GELS
Amorphous material, or gels, occur
either by initial deposition or during the
destruction of silicates such as feld- _
1127.7

14".5
-.
1\
I...... r.- wi

)\"'"" J
-
-
v\ -
\
J

~ ! C
C
..... )\. )
co ~-
spars, through the action of carbon ic
.. C
acid and organic acids generated from
kerogen degradation, or the transfor-
~ 112&1 I\. I
_. I--' \
mation of smectite to illite. The colloidal
I\. I\.. / \ I\.
~ ) c
portion of silica, aluminum and iron can
be extracted and measured following
)
,.....f-

_J c
the techniques of Aquillera and Jackson I...... ) ..... C
(1953) and that of Jackson (1965). Fos- l-
I\.
- f-'"
colos and Powell (1980) have deter-
mined free iron, silicon and aluminum ...... I\, ./ \ ) L
I\.
- -- e
\ )
in six wells and one formation in the
Sverdrup and Beaufort-Mackenzie
Basins of the Northwest Territories. The ...... Il / f- \~ - ' I\.,. (
results indicate that amorphous mater-
ial, which in some cases amounts to '" " . . I I
20 15 10
I I II c
over 35% , decreases with burial depth.
_Zltol<a
C
If one accepts that the amorphous
inorganic gels have a composition simi- Figure 5 X-ray diffraction patterns of oriented clay specimens from North Sabine H-49 well l
after heating at 550°C for 30 minutes (Fosc%s and Powell, 1979).
lar to allophane, as proposed by Ross
(A) 0.2-2.0 Itm fraction.
(
and Kerr (1934), then the amount of (8) <0.2Itm fraction.
C
C
C
l Catagenesis of Argillaceous Sedimentary Rocks 183
l
r:
fold co-ordination in orderto form a gibb- Carbonates. Kodama , 1974). The exchanged cal-
r
sitic layer. Linares and Huertas (1970) Calcite is very seldom encountered in cium moves with HCO; , derived in the

r and Surdam et al. (1984) have shown


that organic acids complex aluminum
pelitic sediments as a product of diagen-
esis. In the early stages of diagenesis,
early stages of diagenesis from the
thermal and bacterial decarboxylation
in six-fold co-ordination , and that CO2 favours the dissolution of calcite of organic matter, to the adjacent sand-
with pH change, aluminum hydroxide is through the reaction stone, precipitating authigenic calcite.
c formed and oriented into a gibbsitic CaC0 3 + H20 + CO2 = Ca(HC03)2 Carbonate cements , dissolved total

o layer. The latter absorbs silica tetra-


hedra to form kaolinite. Therefore , or-
Once Ca(HC0:J2 has encountered a
neutral pH, authigenic calcite is formed.
carbonates and c5 13 C values of CO2 in
natural gas yield evidence for the or-
c ganic compounds derived from the dia- This usually occurs in sandstones adja- ganic origin of CO 2 (Boles , 1978 ;

c
r:
genesis of organic matter in source
rocks act similarly to induce synthesis
and authigenesis of many different clay
cent to shales. Calcite cement is also
formed when K~ derived from feldspar
dissolution substitutes absorbed Ca2+
Carothers and Kharaka, 1980 ; Lun-
degard et et., 1984). Therefore, calcite
cement is encountered in sandstones
minerals in either shales or sandstones. or Mg2+ on the smectite surfaces, thus during the early stages of diagenesis
o Finally,iron should migrate from shale indicating the transformation of smectite (eodiagenesis). As transformation of

c to sandstone in a similar way as alumi-


num that is, chelated by organic acids.
to interstratified smectite-illite along
with the expelled water (Foscolos and
smectite to illite proceeds with burial
depth, pore fluids are enriched mainly
o
o
,.c

~><--
I- • I Octahedral
- - I
r Tetrahedral
sheet sheet
Figure 6 Formation of authigenic kaolinite (Siffert, 1967).

HO
10 HO 'Si-OH +5 [Al(OH)]2+-+
HO/
r

Tetrahedra
sheet sheet
Octahedral
sheet

Figure 7 Formation of authigenic 2:1 layer silicate (Siffert, 1967).


(
184 Diagenesis Geoscience Canada Reprint Series 4 (
(

with magnesium, and to a lesser extent, RELATIONSHIP BETWEEN CLAY An important aspect of diagenesis, C
with iron. These enriched pore fluids mi-
grate to sandstones along with carbonic
CATAGENESIS, ORGANIC MATTER
DIAGENESIS AND CEMENTATION
however, is the destruction of 2: 1 layer
silicates, as reported by Foscolos and
C
acid to form dolomite cement or to react The relationship between clay cata- Powell (1980). Although smectite is C
with calcite and form dolomite as follows: genesis and organic matter diagenesis transformed to illite via vermiculitiza-
2CaC03 + Mg2+ = CaMg(C03 k + Ql2+ . has been put forward by Powell et al. tion, the absolute amount of 2:1 layer C
When the concentration of iron in the
expelled pore fluids increases, ferroan
(1978) and Foscolos and Powell (1979)
in their study of the Sverdrup Basin.
silicates decreases with burial depth.
The destruction of silicates might have
C
dolomite and finally ankerite The results are illustrated in Figure 8 implications because absorption sites, C
(CaMgo.5Feo.5(C03)2) and show that amorphous inorganic where organic matter can be absorbed,
is generated as an authigenic cement. matter loses water and decreases in are destroyed. Therefore, hydrocar- C
Ankerite is very seldom encountered in
shales. It seems that as diagenesis pro-
concentration at a burial depth about
600 m above the first dehydration step
bons might be moving away from pelitic
sediments because the seats of absorp-
C
ceeds the pH of the pelitic sediment of smectite. The first clay dehydration tion are destroyed. There is also a dis- C
becomes alkaline because K-clays, in step coincides with 0.5% Ro vitrinite tinct possibility that once the absorbed
the absence of buffering salts in the reflectance and occurs at about 1500 m sites are reduced, that is, once the cat- C
pore fluids, raise the pH of the rock. This above the main phase of oil generation.
The second dehydration takes place
ion exchange capacity is lowered, the
absorptive sites are reduced and polar
C
induces iron to precipitate as Fe(OHb
probably on the 2:1 clay mineral sur- below the depth of the oil-generating organic liquids are released to the pore C
faces. This process eventually leads to
chloritization of the 2:1 layer silicates
zone, since vermiculite is a major com-
ponent in the mixed layers (Powell et
systems. The effects, if any, of the
destruction of the 2: 1 layer silicate with
C
and the formation of iron-rich sedimen- al., 1978). These results suggest that burial depth to the migration of hydro- C
tary chlorites. If authigenic kaolinite and the depths of clay dehydration and the carbons and to cementation of adjacent
quartz are present, then iron, magne- loss of water from the amorphous alu- sandstone is a new area of research C
sium and lor ankerite may react to pro-
duce iron-rich chlorite, calcite and CO 2,
minosilicate gels are not coincident
with the depths of oil generation, and it
worth probing.
Crystal-lattice-water derived from
C
as documented by Muffler and White is difficult to envisage a role for water the breakdown of the layer silicates en- C
(1969) and Hutcheon et al. (1980). derived by this process in oil migration. sures an ongoing sediment dehydra-
C
ORGANIC MATTER
VITRINITE HYDROCARBON MINERALOGY
SHALES
INORGANIC
SANDSTONES
AUTHIGENIC MINERALS
C
GENERATION GEOCHEMISTRY
SILICATES ,CARBONATES
C
Reflectance
percent Intensity <0.2 p.m fraction 0.2 -2 p m fraction
C
R o max.
C
Intera.ratlfted clays Samacllte
C
> 30~ emactlte

...,25" vermiculite
Kaolinite

Chlorite In,.grad••
C
< 50'" Illite IIl1to
Lon of amorphous
Inorganic matter
C
C
-8 -----
0.5
C
..51 . 2
Intera'ratlfled clays
FIRST CLAY DEHYDRATION

Inters'ratlfled clay.
Isomorphous substhutlon

.
" 51
< 20'4 smactho ~
zw lncr•••ing IlIItlaotlon
of A1 3+for 814+ In

Interstratlfl.d clays
C
iE Ii~"
II ~
-.. 20'" vermiculite

> 55'4 IUlto incr••• lng


8>- Disapp••renee
Lo•• of ad.orbed .at.r C
z:
aII
... 3
IIIltle.tlon ~
o
of kaoUnite
I
Incr•••• In K20
C
:lc Decr•••• In c.tlon
:i
!;
a:
w
Form.tlon of chlorlt. (
.a >

e
o from chlorlt. Intagrade=
E Incorporation of
::0 ill
.Ii
." amorphoua matt.r e
~
4 In mixed lay.r to form
chlorlt. component.
z
;;;
c
w
a:
c
15
o
w
o c
: :: !
.:.•..: ::.. -:..,..: v, :••: • • '. ".
..•...:...-.~-,..•::.• ....•..\.'
5
SECOND CLAY DEHYDRATION
C
18
l
Figure 8 Relation between diagenesis (catagenesis) ofshales andthe occurrence ofauthigenic minerals in sandstones (Fosco/os and Powell,
C
1979). C
C
C
c
( Catagenesis of Argillaceous Sedimentary Rocks 185
o
(
tion. For example, in the North Sabine (2) The firstclay dehydration isattributed REFERENCES
( H-49 well, it was calculated that water to the conversion of smectite to mixed
derived prior to first clay dehydration layer silicates and occurs prior to the Diagenesis
( from all reactions involving clay miner- onset of hydrocarbon generation from
Almon, W.R. and Davies, D.K., 1979,
( als (absorbed water, cavity water and the organic matter. Dehydration is
Regional diagenetic trends in the Lower
crystal-lattice-water) amounts to 3.8%, attributed to isomorphic substitution of
Cretaceous Muddy Sandstone, Powder
while the water loss between two de- silicon ions in the clay structure and the
River Basin, in Scholle, PA and Schluger,
c hydration steps, that is, within the
hydrocarbon generating zone, amounts
ensuing absorption of potassium ions
and displacement of calcium and mag-
P.R., eds., Aspects of Diagenesis: So-
ciety of Economic Paleontologists and
o to 3.7% (Foscolos and Powell, 1980).
In addition to water, the dissolution of
nesium ions from the clay surface.
(3) The first dewatering of the clays
Mineralogists, Special Publication 26,
p.379-400.
c the amorphous inorganic matter and the marks the onset of the destruction of the Aronson, J.L. and Hower, J., 1976, Mecha-

o destruction of the layer silicates releases


silica, aluminum, iron, calcium, magne-
2:1 layer silicates, as well as kaolinite.
Thus, there is a net decrease in con-
nism of burial metamorphism of argilla-
ceous sediments: 2. Radiogenic argon

o sium and potassium to the pore water. If


these elements remain in place, they
centrations as the clays undergo struc-
tural transformations.
evidence: Geological Society of America,
Bulletin, v. 87, p. 738-744.
Boles, J.R., 1978, Active ankerite cementa-
may precipitate to form part of the exist- (4) The mixed layer clays comprise a ter-
tion in the subsurface Eocene of South-
( ing mineral, such as quartz, or form nary system of smectite-vermiculite- west Texas: Contributions to Mineralogy
authigenic clays, such as chlorites. How- illite. Vermiculite appears to be an inter- and Petrology, v. 68, p. 13-22.
J ever, the net decrease of the layer sili-
cates with depth suggests that some of
mediary mineral in the conversion of
smectite to illite.
Boles, J.R., 1981, Clay diagenesis and effects
on sandstone cementation (case histo-
) the cations may migrate with compaction (5) The second dewatering of the clays ries from Gulf Coast Tertiary), in Long-
water into more porous and permeable occurs after oil has become cracked to staffe, F.J., ed., Clays and the Resource
horizons, forming authigenic clays in gas. The high temperature requirement Geologist: Mineralogical Association of
sandstone reservoirs (Curtis, 1978;Fos- is attributed to the presence of a Ca- Canada, Short Course Handbook, v. 7,
J
p. 148-168.
r colos and Powell, 1979). In such cases,
both permeability and porosity of shales
vermiculite component inthe mixed layer
clays.
Boles, J.R. and Franks, S.G., 1979, Clay
diagenesis in Wilcox sandstones of
and adjacent sandstones are affected by (6) After the first dewatering of the clays, southwest Texas: Journal of Sedimen-
formation of authigenic cements both iron hydroxide precipitates on 2:1 layer tary Petrology, v. 49, p. 55-70.
before and during hydrocarbon genera- silicates to form in the less than 0.2JA, Burst, J.F., 1969, Diagenesis of Gulf Coast
r tion and migration. fraction iron-rich chlorite integrades and clayey sediments and its possible relation
The importance of organic acids re- in the 2-0.2JA, fraction iron-rich chlorites. to petroleum migration: American Asso-
leased during diagenesis from various (7) With burial, pelitic sediments release ciation of Petroleum Geologists, Bulletin,
types of kerogen in relation to ion migra- water not only upon compaction but also v. 53, p. 73-93.
tion from shales to sandstones and to from the crystallization of amorphous Carothers, W.W. and Kharaka, Y.K., 1978,
Aliphatic acid anions in oil field waters -
the development of secondary porosity material, the dehydration of the expand-
implications for origin of natural gas:
in reservoir rock is discussed in detail able layer silicates and the destruction of
American Association of Petroleum Geo-
by Gautier et al. (1985) and Eglinton et the layer silicates. logists, BUlletin, v. 62, p. 2441-2453.
al. (in press). (8) The destruction of feldspars, the Carothers, WW. and Kharaka, Y.K., 1980,
The economic significance of apply- transformation of the layer silicates and Stable carbon isotopes of HC03 - in oil
r: ing the diagenetic modelling techniques the production of organic acids during field waters - implication for the origin of
with regard to the search for hydro- the diagenesis of organic matter provide CO 2 : Geochimicaet CosmochimicaActa,
carbons and in evaluating reservoir inorganic material and chelating agents v. 44, p. 323-332.
properties (porosity and permeability) of for the transportation of cations in ad- Curtis, C.D., 1978, Possible links between
targeted sandstone intervals prior to jacent sandstones. These cations, de- sandstone diagenesis and depth-re-
pending on their concentration, pH, tem- lated geochemical reactions occurring in
drilling is discussed in detail by Surdam
enclosing sandstones: Journal of the
and Crossey (1985) and Surdam et al. perature and other physicochemical
:; (1986)and summarized by Surdam and conditions, form carbonates or authi-
Geological Society of London, v. 135,
p. 107-118.
Crossey (1987). genic silicates thus cementing the pore
l' throats of sandstone reservoir rocks.
Dunnoyerde Seconzac, G., 1969, Les Miner-
aux argileux dans la diagenese: Passage
( CONCLUSIONS au Metamorphisme, These Universite du
The following conclusions concerning Strasburg, Memoire, Service Carte Geo-
the catagenesis of shales can be made: logique d'Alsace-Lorraine, No. 29,
(1) The first stage in catagenesis is 3200 p.
marked by the accumulation of amor- Dunnoyer de Seconzac, G., 1970, The trans-
phous inorganic components which formation of clay minerals during diagen-
esis and low grade metamorphism. A
occur either by initial deposition andlor
review: Sedimentology, v. 15, p. 281-340.
during the destruction of silicates. This
stage takes place prior to the onset of
the first clay dehydration of the 2:1 layer
silicates.
(
186 Diagenesis Geoscience Canada Reprint Series 4 (
(

Eberl, D., 1989, Clay mineral formation and Hoffman, J. and Hower, J., 1979,Clay min- Power, M.C., 1967, Fluid release mecha-
C
transformation in rocks and soils, in
Fowden, L., et al. , ed., Clay Minerals:
erai assemblages as low grade geother-
mometers . Application to the thrust
nism in compact ing mar ine and
mudrocks and their importance in oil
C
their st ructure, behaviour and use:
Royal Society of London, Philosophical
faulted disturbed belt of Montana,
U.S.A., in Scholle, PA and Schluger,
exploration : American Association of C
Petroleum Geologists, Bulletin, v. 51,
Transactions, v. 311A, p. 241-257. P.R., eds., Aspects of Diagenesis: p. 1240-1253. C
Eglinton, T.I., Curtis, C.D. and Rowland, Society of Economic Paleontologists Schmidt, Y. and McDonald, DA, 1979,Tex-
S.J., 1987, Generation of water-soluble and Mineralogists, Special Publication ture and recognition of secondary C
organic acids from kerogen during 26, p. 55-80.
hydrous pyrolysis; implications for Hower, J., 1981, Shale diagenesis, in Long-
porosity in sandstones, in Scholle, P.A.
and Schluger, P.R.,eds., AspectsofDia-
C
porosity development: Mineralogical
Magazine, v. 51, p. 495-503.
staffe, F.J., ed., Clays and the Resource
Geologist: Mineralogical Association of
genesis: Society of Economic Paleon-
tologists and Mineralogists, Special
C
Foscolos, A.E. and Kodama, H., 1974, Dia-
genesis of clay minerals from Lower
Canada, Short Course Handbook, v. 7,
p.60-80.
Publication No. 26, p. 209-225. C
Surdam, R.C. and Crossey, L.J., 1985,
Cretaceous shales of northeastern Hower, J., Eslinger, E.V., Hower, M.E. and Organic-inorganic reactions during pro- C
British Columbia: Clay and Clay Miner- Perry, E.A., 1976, Mechanism of burial gressive burial: Key to porosity/per-
als, v. 22, p. 319-335. metamorphism of argillaceous sedi- meability enhancement and/or preser- C
Foscolos, A.E. and Stott, D.F., 1975,Degree ments: I. Mineralogical and chemical
of diagenesis, stratigraphic correlations evidence: Geological Society of Amer-
vation: Royal Society of London,
Philosophical Transactions, v. 315A,
C
and potential sediment sources of Lower
Cretaceous shale of northeastern Brit-
ica, Bulletin, v. 87, p. 725-737.
Hutcheon, I., Oldershaw, A. and Ghent,
p.135-156.
Surdam, R.C., Crossey, L.J., Hagen, E.S.
C
ish Columbia: GeologicalSurveyofCan-
ada, Bulletin 250, p. 1-46.
E.D., 1980, Diagenesis of Cretaceous
sandstones of the Kootenay Formation
and Heasler, H.P., 1986, Application of
Basin Analysis to Diagenetic Modeling:
C
Foscolos, A.E. and Powell, T.G., 1979,Cata- at Elk Valley (southern British Columbia) American Association of Petroleum C
genesis in shales and occurrence of and Mt. Allen (southwestern Alberta): Geologists, Bulletin, v. 70, p. 653.
authigenic clays in sandstones, North Geochimica et Cosmochimica Acta, Surdam, R.C. and Crossey, L.J., 1987, Inte- C
Sabine H-49 well , Canadian Arctic
Islands : Canadian Journal of Earth Sci-
v. 44, p. 1425-1435.
Kubler, B., 1964, Lesargiles, indicateursde
grated diagenetic modeling: A process-
oriented approach for clastic systems:
C
ence, v. 16, p. 1309-1314.
Foscolos, A.E. and Powell, T.G., 1980, Min-
metamorphism: Revue de I'lnstitut
Francals du Petrole, v. 19, p. 1093-1112.
Annual Review of Earth and Planetary
Sciences, v. 15, p. 141-170.
C
eralogical and geochemical transfor-
mation of clays during catagenesis and
Longstaffe, F.J., 1983, Stable isotope stud-
ies of diagenesis in clastic rocks: Geo-
Tissot, B. and Welte, D.H., 1978,Petroleum
Formation and Occurrence : Springer-
C
their relation to oil generation, in Miall, science Canada, v. 10, p. 43-58. Verlag, 538 p. C
A.D., ed., Facts and Principles of World Lundegard, P.D., Land, L.S. and Galloway, van Elsberg, J., 1978, A new approach to
Petroleum Occurrence: Canadian W.E., 1984, Problem of secondary sediment diagenesis . Part 1. An C
Society of Petroleum Geologists, porosity: Frio Formation (Oligocene) ,
Memoir 6, p. 153-171. Texas Gulf Coast: Geology, v. 12,
observed relation between sonic transit-
time and depth in the Tertiary sediment C
Foscolos, A.E., Powell, T.G. and Gunther,
P.R., 1976, The use of clay minerals,
p.299-402.
Maxwell, D.T. and Hower, J., 1967, High-
of the Mackenzie Delta : A potential
petroleum exploratory tool. Part II. A
C
inorganic and organic geochemical indi-
cators for evaluating the degree of dia-
grade diagenesis and low-grade meta-
morphism of illite in the Precambrian
revised concept of sediment diagenesis:
Bulletin of Canadian Petroleum Geol-
C
genesis and oil generating potential of belt series : American Mineralogist, ogy, v. 28, p. 57-86. C
shales: Geochimica et Cosmochimica v. 52, p. 843·857. Velde, B. and Hower, J., 1963, Petrological
Acta, v. 40, p. 953-960 . Muffler, L.J.P.and White, D.E., 1969, Active significance of illite polymorphism in C
Foscolos, A.E., Reinson, G.E. and Powell, metamorphism of Upper Cenozoic sedi- Paleozoic sediment rocks : American
T.G., 1982, Controls of clay mineral ment in the Salton Sea geothermal field Mineralogist, v. 48, p. 1239-1254. C
authigenesis in the Viking sandstones,
Central Alberta: I. Shallow depths:
and Salton trough, southeastern Califor-
nia: Geological Society of America, Bul- Mineral Chemistry and Physical
C
Canadian Mineralogist, v. 20, p. 141-150.
Frey, M., 1970, The step from diagenesis to
letin, v. 80, p. 157-182.
Padan, A., Kisch, H.J. and Shagam, R.,
Chemistry C
metamophism in pelitic rocks during 1982, Use of lattice paramter b, of dioc- Aquillera, N.H. and Jackson , M.L., 1953, C
Alpine orogenesis : Sedimentology, tahedral illite/muscovite for the charac- Iron oxide removal from soils and clays:
v. 15, p. 261-279. terization of PIT gradients of incipient Soil Science Society of America, Pro- C
Gautier, D.L., Kharaka, Y.K. and Surdam,
R.C., 1985,Relationship of Organic Mat-
metamorphism: Contributions to Miner-
alogy and Petrology, v. 79, p. 85-95.
ceedings, v. 17, p. 359-364.
Eslinger, E.V. and S. Savin, 1973, Miner- c
ter and Mineral Diagenesis: Society of
Economic Paleontologists and Mineral-
Perry, E. and Hower, J., 1972, Late stage
dehydration in deeply buried pelitic sedi-
alogy and oxygen isotope geochemistry
of hydrothermally altered rocks of the
e
ogists, Short Course No. 17, 279 p.
Hedberg, H.D., 1936, Gravitational com-
ments: American Association of Petro-
leum Geologists, Bulletin , v.56,
Chake-Broadlands, New Zealand geo-
thermal area: American Journal of Sci-
c
paction of clays and shales: American p. 2013-1021, ence, v. 273, p. 240-267. (
Journal of Science, 5th series, v.31,
p.241·287.
Powell, T.G., Foscotos, A.E., Gunther, P.R.
and Snowdon, L.R., 1978, Diagenesis of
organic matter and fine clay minerals:
Foscolos, A.E ., 1964, Factors affecting
the replaceability of octahedral Mg ion
of various soil minerals with H ions,
c
a comparative study: Geochimica et M.Sc. Thesis, University of California,
Cosmochimica Acta, v. 42, p. 1181-1197. Berkeley, California.
l

(
(
c
c
r:
Catagenesis of Argillaceous Sedimentary Rocks 187

r
Fosolos, A.E. and Barshad, I., 1969, Equilib- van Olphen, H., 1954, Interlayer forces in McDowell, S.D. and Elders, W.A., 1980,
rium constants between both freshly bentonite: Clays and Clay Minerals, v. 2, Authigenic layer silicate minerals in

o prepared and aged H-montmorillonites


and chloride salt solutions: Soil Science
p.418-438.
van Olphen, H., 1965, Thermodynamics of
borehole Elmore 1, Salton Sea geo-
thermal field, California, U.S.A.: Contri-

c Society of America, Proceedings, v. 33,


p.242-247.
interlayer absorption of water in clays.
I. - sodium vermiculites: Journal of Col-
butions to Mineralogy and Petrology,
v. 74, p. 293-310.
( Hemely, J.J., 1959, Some mineralogical loid Science, v. 20, p. 822-9837. Ross, C.S. and Kerr, P.F., 1934, Halloysite
equilibria in the system (K 20-AI 20 3 - van Olphen, H., 1977, An Introduction to and allophane: United States Geologi-
c Si0 2-H 2 ) : American Journal of Science,
v. 257, p. 241-270.
Clay Colloid Chemistry: John Wiley and
Sons, A Wiley-Interscience publica-
cal Survey, Professional Paper 185,
p. 135-148.
( Jackson, M.L., 1956, Soil chemical ana- tion, 317 p. Shagan, R., 1977, Stratigraphic models for

o lyses: Advanced course: Mimeograph


published by the author, Department of
Soil Science, University of Wisconisn,
Mineralogy
the northern Venezuelan Andes, in
Espejo, C.A., et a/., eds., Tema II,
Petrologia y Geochronologia; Tema III,
CJ Madison, Wisconsin. Birkeland, P.W., 1973, Pedology, Weather- Geodinamica (Sismologia, Tectonica y
o Jackson, M.L., 1965, Free oxides, hydrox-
ides and amorphous aluminosilicates, in
ing and Geomorphological Research:
Oxford University Press, 285 p.
Geologia Estructural): Congreso Geo-
logico Venezolana, Memoir 5,
o Black, C.A., ed., Methods of Soil Analy-
sis, Part I: American Society of Agricul-
Brown, G., 1961, X-ray Identification and
Crystalline Structure of Clay Minerals,
p.855-877.
Steiner, A., 1968, Clay minerals in hydro-
c ture, p. 478-603. Second Edition: Mineralogical Society thermally altered rocks at Wairakei,

o Keenan, A.G., Mooney, R.w. and Wood,


L.A., 1951, The relation between ex-
of London, 544 p.
Grim, R.E., 1968, Clay Mineralogy:
New Zealand: Clays and Clay Minerals,
v. 16, p. 193-213.

o changeable ions and water adsorption


on kaolinite: Journal of Physics and Col-
McGraw-Hili Book Co., New York, 596 p.
Kisch, H.J., 1980, Incipient metamorphism
Sumi, D., 1969, Zonal distribution of clay
minerals in the Matsukawa geother-

o loid Chemistry, v. 55, p. 1462-1474.


Kittrick, J.A., 1969a, Interlayer forces in
of Cambro-Silurian clastic rocks from
.the Jantland Supergroup, central Scan-
mal area, Japan: International Clay
Conference, Japan, Proceedings,
montmorillonite and vermiculite: Soil dinavian Caledonides, western Swe- p.501-512.
Science Society of America, Proceed- den: illite crystallinity and vitrinite re- Weaver, C.E., 1960, Possible uses of clay
o ings, v. 33, p. 217-222. flectance: Geological Society of Lon- minerals in search for oil: American

o Kittrick, J.A., 1969b, Quantitative evalua-


tion of the strong-force model for expan-
don, Journal, v. 137, p. 271-288.
Kishk, F.M., 1967, Chemical and physical
Association of Petroleum Geologists,
BUlletin, v. 44, p. 1505-1578.

o sion and contraction of vermiculite: Soil


Science Society of America, Proceed-
properties of soil vermiculite clays as
related to their origin, Ph.D. Thesis, Uni-
versity of California, Berkeley, Califor-
Weaver, C.E.,1961, Clay minerals ofOuach-
ita structural belt and adjacent fore-
land, in The Ouachita System: Bureau of
( ings, v. 33, p. 223-225.
nia, 175 p. Economic Geology, Austin, Texas,
Mooney, R.W., Keenan, A.G. and Wood,
0: L.A., 1952, Adsorption of water vapour
by montmorillonite. I. heat of desorption
Kubler, N., Martini, J. and Vuagnat, M.,
1974, Very low grade metamorphism in
p.144-160.

o and application of BET theory: Journal the Western Alps: Schweizerische

o of the American Chemical Society, v. 74,


p. 1367-1371.
Mineralogische und Petrographische
Mitteilungen, v. 54, p. 461-469.
Originally published in
o Siftert, B., 1967, Some reactions of silica
in solutions: Formation of clay: Israel
Linares, J. and Huertas, F., 1970, Kaolinite,
synthesis at room temperature: Sci- Geoscience Canada v. 11 Number 2

o Program for Scientific Translations,


Jerusalem, 100 p.
ence, v. 171, p. 896-897. (June 1984)
Revised 1988
o
o
o
o

Cd
C
~.

'-- r
c
188 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
(
c
c
c
c
c
c
c
c
c
C
E
Scalenohedral calcite crystal coated by pyrobitumen (arrows 1 and 2). Note further that pyrobitumen bridges
intercr ystalline spaces (arrow 3) and is segmented by hairline cracks. Oil-wet rather than water-wet conditions appear
to have been present in this porous system as is indicated by the low contact angles between the pyrobitumen and the c
calcite crystal faces . Beaverhill Lake reservoir sample. Photograph courtesy of F. Krause and S. Sayegh (University of
Calgary and Petroleum Recovery Institute, respectively). c
c
c
e
c
(
c
c
C
l
l
c Chemistry and Diagenesis of Organic Matter 189

c
c In this chapter, we describe organic are thus "pre-diagenetic " by traditional
c diagenesis from both petrographic and
geochemical perspectives. The petro-
definitions. For example, it is commonly
estimated that, under normal oceanic
o graphic study of organic matter evolved conditions, no more than one percent of

c from coal petrology, which has strongly


influenced the terminology used. In a
the phytoplanktic organic matter pro-
duced in the marine euphotic zone
o similar way, petroleum geochemistry
has provided much of the terminology
survives microbial decomposition and
zooplankton grazing to reach the sea
and techn iques of organic geochemis- floor unaltered (Wakeham et al., 1980;
c Chemistry and
try. The nomenclature of these fields is
complex, sometimes inconsistent and,
Knauer and Martin, 1981). Diagenetic
changes that take place in organic mat-
o Diagenesis of Organic
to most geologists, unfamiliar. In this ter at shallow depths below the sedi-

o Matter in Sediments
paper, we have attempted to simplify the
terminology, hopefully without a major
ment-water interface are largely bio-
chemical , and occur as a result of the
o and Fossil Fuels
loss of information. Also, we provide a
background to the geochemistry and
metabolism of fungi, bacteria and other
micro-organisms. At greater sediment
o petrography of organic matter and trace depths, microbial activity is much

o M.A. Barnes
W.C. Barnes
its progressive diagenesis, which gen-
erally accompanies increasing depth of
slower, and geochemical parameters
more familiar to geologists (tempera-
o A.M. Bustin burial. Our companion paper (this vol-
ume, p. 205-226) delineates some of
ture , time) become dominant.
The diagenesis of organic material is
o Department of Geological Sciences
University of British Columbia the methods of quantifying diagenesis progressive and irreversible with few

o 6339 Stores Road


Vancouver, British Columbia V6T 2B4
and evaluates predict ive models. Be-
cause of the breadth of organic diagene-
exceptions . The progress ive dia-
genesis of organic matter has been con-
o sis we can only present an overview of
the subject here, and thus have avoided
sidered in terms of different stages.
Tissot and Welte (1984) and many
o INTRODUCTION
Organic matter occurs in almost all sedi- both controversial topics and those we others (see Durand, 1980)refer to three

o mentary rocks. In some rocks , such as


coal and oil shale, organic matter is a
consider less important. The reference
list is essential for those readers who
stages of organic diagenesis: dia -
genesis, catagenesis and metagenesis.
o major component, but, in most sedimen-
tary rocks, it occurs in minor or trace
wish to pursue the subject in greater
detail.
For the purpose of this chapter,
eogenesis (Choquette and Pray,1970) is
o amounts (Figure 1). The economic im- General Considerations. used to refer to those biological , physi-
o portance of organic matter, however,
far outweighs its relative abundance.
Diagenesis of organic matter begins
early and proceeds rapidly under surfi-
cal and chemical changes in organic
matter that occur at temperatures less
[ Organic matter, in one form or another, cial conditions. As a result, the terminol- than those required for significant
comprises the fossil fuel resources. The ogy of diagenesis , which was largely cracking of hydrocarbons (Figure 2). As
o diagenesis of organic matter is thus of developed for more slowly changing such, our eogenetic stage is equivalent
o particular importance in understanding
the generation and migration of oil and
inorganic materials, requires some
modification. Some of the changes take
to the diagenetic stage of Tissot at al.
(1974) and we introduce the term solelyto
o gas, in evaluating source rocks, and in
estimating levels of maturation of oil
place even during sedimentation, and prevent confusion between diagenesis

o shales and coals. Organic matter plays coal. oil shales, oil. gas,
o an important role in the transport of metal
complexes (J.F. Barker, 1982),the forma-
/ living organic matter

o tion of strata-bound and stratiform ore bituminous rocks

o deposits (Anderson and Macqueen,


1982,1988; Macqueen and Powell, 1983)
o and has a significant influence on the
diagenesis of other minerals (Powell et
mudrocks

al., 1978;Schmidt and McDonald, 1979;


Foscolos and Powell, 1980). While the
8 diagenesis of organic matter is less
and

C understood and more complicated than


that of the common minerals, significant s iltstones
progress has been made. It is now possi-
ble to predict the diagenetic state of
organic matter if the burial and thermal
history ofthe strata is known. The degree
of diagenesis of organic matter has also
become an accepted geothermometerto Figure 1 Occurrence of organic matter in sediments as a percentage of mass of organic
which other diagenetic reactions can be carbon. Hydrocarbons dissolved in water are not included. (Modified from Vassoyevich (1973)
compared (Bostick, 1979). and Vassoyevich at al. (1976) in Bostick (1979)).
c
190 Diagenesis Geoscience Canada Reprint Series 4 c
c
- ---
c
(
Sea Water c
Bacterial
Oxidation c
Bacterial
Sulphate
Te/ogene.'.
c
Reduction
Fermentation CH4
c
cO 2 c
Catagene.'.
c
c
c
c
c
c
c
lliopolyme rs
c
Figure 2 (above) Schematic representa-
tion of the terminology commonly used in
describ ing the stages of diagenesis of
c
organic matter (Tissot and Welte, 19 78 and c
others). The terms " eogenetlc ': " meso-
genetic " and "telogenetic" were originally c
usedby Choquette and Pray(1970) to refer to
the stages of diagenesis of carbonate rocks . Monomers
Unalter ed
molecules c
The eogenetic zone includes reactions that
are, mainly, biochem ica l. The eogenetic c
stages shown are modified from Curt is
(1977). Catagenetic and metagenetic reac-
rn Prese rved
c
tions are chem ica l, in response to the
Ci5
w
z \t:\
\\)~
c
thermal history of the strata . Telogenesis
results from contact with meteoric waters
w
(!)
o Random po lyme rizatio n c
contain ing aerobic micro-organisms and
atmospheric oxygen.
w and cond ensat ion
c
(
Random ,
het ero g_ous
geopo lYmef s c
c
c
Ro- O.5 - - -- -- - - c
Figure 3 (right) Diagenetic fate of organic rn c
matter in sediments. (After Tissot and Welte,
1984).
Ci5
w
z e
w
(!)
-e c
I-
<
o Gas + c
Ro - 2 """""'Wf-=~===:....j -- -- -
Condensa tes
c
METAGENESIS c
c
c
c
(
c Chemistry and Diagenesis of Organic Matter 191

C'
c as a stage of diagenesis and diagene- as discrete sedimented organics or pre- EOGENESIS
c sis as conventionally used by geolo- cipitates. Although it is a minor compo- The term eogenesis covers all low tem-

o gists. Diagenetic changes occurring at


greater depths (and thus higher temper-
nent of rocks, it forms the major part of
the organic matter present. With the
perature diagenesis of organic matter ;
eogenetic reactions are partly bio-
c atures) in the lithosphere are referred to
sequentially as catagenesis and meta-
exception of coals, it requires con-
centration before petrographic analysis
chemical, arising from metabolic pro-
cesses occurring within organisms, and
( genesis (Figure2). Diagenetic reactions by treatment with acids, bases and partly abiotic chemical reactions which
resulting from organic material coming organic solvents to remove silicates and incorporate metabolic products re-
into contact wi th meteoric water or carbonates, or extractable organics in leased to the sediments. The effects of
( atmospheric oxygen following burial the case of pollen preparations (Karr temperature and pressure are subord i-
are referred to as telogenesis (Cho- 1978a,b, 1979). nate , and eogenetic reactions cannot
C' quette and Pray, 1970). The different Sources of Organic Matter. be simulated by simple pyrolysis (Tissot
diagenetic stages do not have well- Precursor organic material varies con- and Welte, 1984).
C defined boundaries, but rather are gra- siderably in its chemistry, depending on Preservation of organic matter is a
o dational, which, to some extent, results
from the heterogeneous composition of
its source and depositional environ-
ment. Unlike simple minerals or even
function of the oxygen content of the
environment. Estimates of the preser-
organic matter. Eogenetic, catagenetic solid solution series, organic matter vation of primary organic matter in the
and metagenetic stages are summar- consists of a complex array of com- surficial sediments of marine environ-
ized in Figure 3. The processes and pounds. These compounds mainly fall ments average about 0.1 % (Menzel and
c products of the diagenesis of organic
matter can be described in kinetic
into four or five general classes that
react differently, particularly during
Ryther, 1970). Preservation in subaerial

c terms. Because the compounds formed eogenesis (Figure 4).


env ironments is even less, as chemical
oxidation and aerobic microbial decom-

o are metastable, and because the sys-


tem is open, enabling migration of gen-
Prior to the Devonian, photosynthetic
phytoplankton and bacteria were the
position are favoured by the high oxy-
gen content of air as compared to only a
o erated hydrocarbons, equilibrium, if
ever established, is continually dis-
principal sources of organic matter. At
present, marine organisms contribute
few mL· L-' dissolved in water. Regions
of rapid terrestrial sediment deposition,
placed (Durand, 1980). If diagenesis approximately 60% of the total organic such as deltas and continental slopes
c proceeds into what is generally consid-
ered the metamorphic realm , the or-
productivity, with terrestrial plants mak-
ing up most of the rest. Aquatic orga-
and rises (Dow, 1978), may have rela-
tively low organic contents because of
ganic residue may ultimately be trans- nisms contribute mainly proteins, lipids dilution by inorganic sediments; how-
formed into graphite (Wedeking and and , in the phytoplankton , carbohy- ever, the preservation of th is organ ic
Hayes, 1983). drates; in addition, higher plants con- matter is high because of limited diffu-
The results of diagenetic studies of tribute resins, waxes, Iignins and car- sion of oxygen into the sediments
organic matter are significantly affected bohydrates in the form of cellulose (Ibach, 1982). Terrigenous organic com-
by the methods of sample preparation, (Figure 4). Lipids, which are major con- ponents are better preserved than
analytical procedures and equipment tributors to petroleum, contain fewer those from aquatic sources (Meyers et
( used. As a result data must be inter- heteroatoms (nitrogen, oxygen and sul- al., 1984). The maximum preservation
preted in terms of what fraction of the phur) than do proteins and carbohy- of primary organic matter, about 4%,
total organic matter present in the sam- drates. Thus, petroleum tends to be rich occurs in anoxic environments such
ple was "seen" by the method selected. in carbon and hydrogen, and poor in as the Black Sea (Deuser, 1971), as
Organic matter in rocks occurs as heteroatoms. Rates of primary produc- anaerobic microbial processes provide
gases, liquids and solid particles; they tion in aquat ic environments are less energy, are slower and result in
differ in their physical and chemical affected by the amounts of light and less complete decomposition of initial
properties, and in their accessibility to nutrients presen t. Most photosynthesis organic compounds . Although dis-
extraction by organic solvents, or to takes place in the upper 60-80 m of the solved oxygen is lacking, other oxidiz-
stripping by mechanical processes in water column , with rates being highest ing agents such as sulphate are abun-
the case of gases. Extractable organics where abundant nutrients are present, dant in marine sediment pore waters
are analyzed by a broad array of chemi- such as in areas of upwelling and near and are utilized during bacterial sul-
( cal and spectrometric methods. The river mouths. Open marine waters have phate reduction.
analytical data obtained are used (1) in estimated organic productivities that As noted, rapid sedimentation limits
modern environments to monitor the average 50g C ' m-2a-' (grams carbon exposure to oxygen and thus favours
l fate of organic matter from natural bio- per square metre per year); coastal the preservation of organic matter.
genic sources and industrial pollutants; waters average about twice that value, Areas where organic matter tends to be
(2) to " fingerprint" oils and source rocks except on the western margins of conti- preserved and concentrated include
for oil-source rock correlations; (3) to nents, where values as great as 300g cont inental marginal environments
assess maturation in coals; and (4) to C'm- 2a- ! occur (Krey, 1970). Preserva- such as shelves, slopes and rises,
assess the effects of maturation, migra- tion is more important than productivity, marine landlocked basins, and lakes.
tion and biodegradation which occur however, in determining the organic Peats accumulate in regions of slow
during the diagenetic conversion of bio- content of sediments. continuous subsidence with water
logical lipids to petroleum. Solid organic tables at or near the surface, low pH
matter tends to be finely disseminated (3 to 5) and low Eh. Most paralic coals
(
192 Diagenesis Geoscience Canada Reprint Series 4 (
(

were formed in swamps developed on through the elimination of water; the a primary cycle that occurs in both the
C
deltas, interdeltaic plains , coastal resulting biopolymers are sensitive to water column and the sediment, and a C
plains and in back barrier regions . Pro- hydrolytic cleavage with the re-incor- secondary cycle that occurs in sedi-
teins, carbohydrates (sugars, cellulose poration of water by either chemical or ments and sedimentary rocks (Figure3). C
and chitin), lipids (fats, waxes and steryl
esters) and lignins are the principal bio-
microbial processes (Figure 4).
Eogenetic changes , arising from
The primary cycle, which is by far the
more rapid, is the biochemical cycle ope-
C
polymers contributed by organisms to microbial and chemical processes, pro- rated mainly by microbial metabolism, C
sediments (Figure 4). However, these foundly affect (1) the physical structure which hydrolyzes the various bio-
original biopolymers are rapidly de- and chemical stability oforganic matter, polymers (Trudinger and Swaine, 1979; C
polymerized to their monomers by
microbial processes occurring during
which can subsequently become fossil
fuel after burial and catagenesis; (2)the
Bolin, 1983;Krumbein and Swart, 1983).
The primary cycle operates on a total
C
and shortly after sedimentation. As a fate of organic pollutants arising from pool estimated at 2.7-3.0 x 101 6 g organic C
result, the dominant organic com- humankind's activit ies; (3) the forma- carbon, with a turnover half-life ranging
pounds found in sediments are geo- tion of humic compounds which form from days to tens of years. The second- C
polymers (humic compounds and ker-
ogen) which arise from random
metalcomplexes and act as metal trans-
port agents in groundwater systems;
ary, geochemical, cycle affects a pool of
organic carbon which is about 2000
C
chemical recombination of monomers and (4) Eh, pH, the precipitation of times larger,but hasa tumover half-lifeof C
released by these micro-organisms. carbonates and the formation of sul- several million years (Welte, 1970).
During biosynthesis of the orig inal bio- phides in sedimentary environments As a result of the primary cycle, the
C
polymers by organisms, their mono- (Gautier, 1985). Two carbon cycles af- major constituents of organisms - pro- C
mers are linked together in bonds fect the constitution of organic matter: teins, carbohydrates, lipids and lignins -
C
PROTEINS

o H H
U I I
-0

"'C-C-N-C-C-N'"
I
H
I
H
I h......".
- C H -C-C-OO
--
NH,
I
LIPIDS
Pot.,,,*,

CH,-ICH,).C-O-cH,
o
I
C
C
C
_
I, I ' I II HO-CH,
R RHO I
.'
CH,-ICH,l,,-~-O-r I 3 CH -(CH ) - COOH+ HO- CH
, 'n I
II I I j' ...... HO-CH, C
--- HO-C-C-C-C-C-QH acid CH,-ICH,ln- C-O - CH,
I HI HI 0II
H
(Glutamic ~
Fa«" acid. GJycerol C
I I I I N,' o
Ii
o
II
C
--- NH -C-C-C-C-C-C-oo
, I I I I I II
H H H H H 0
CH,- {CH' )n- C- O- ICH' )n- CH,
Wax (.at.,)
CH,-ICH, ln-C -00
Fatty acid
C
+
HO-ICH')n-CH,
C
CARBOHYDRATES
C
o
Monom...
hydrol."" U
• CH,-ICH')n- C-OH
C
"'oAL-(
EovO~ -' C
H-C=O
Fatty ac id
I
hydrolytit H-C-OH +
o
~oAo·
I
HO-C-H
I CH,-ICH,'n-C-O
II C
OH CH,OO H-C-OO
I
H-C-OH
Slaryl ••'., C
lHIIuco.. I
C
H,-C-OH
HO
C
"'oAL-(
H-C=O

Eovo~OCH~.
I
H-C-N-C-CH,
I
#0
C
~c/"O' HO-C-H
I
H LIGNIN
CH,OH
I
CH,OO
I
-eH,OH
I
c
e
H,COC+IH CH,OO H-C-OO
I CH CH CH
H-C-OH c..... age 01 II II II
I .tMrbDNla CH CH CH
(
~~, ","4~. ¢
H,-C-OH

OH OH
SIn.",1
00
c
alcohol

c
Figure 4 (above) Variation in huminite-vitrinite reflectance in oil (Ro %), level of diagenesis (coal rank) and typical molecular structures at
different diagenetic levels. The aromatic clusters are shown in plan view and show increases in ordering and cluster size with increases in coal
c
rank. (Modified, in part, from TeichmOl/er and TeichmOl/er, 1982). c
c
c
c
r Chemistry and Diagenesis of Organic Matter 193

c
(. comprise less than 20% of the organic formation occurs through loss of func- a poor fit for templating by the microbial
r:
matter present in sediments and are tional groups and cross linkage forma- enzymes which catalyze their hydro-
much less significant in older sedi- tion early in the diagenetic history of lysis and decomposition.
r mentary rocks. Primary cycle hydro- organic matter (Philp and Calvin,1976), These diagenetic processes not only
r lysis produces monomeric amino acids
and sugars that (1) provide energy for
mostforms later,reaching a peak during
thermal maturation at the catagenetic
produce energy for the microbial popu-
lations, but also release large quantities
r bacteria, leading to the formation of
CO2 , H2 0 , CH4 , NH3 and other simple
stage. Kerogen can also arise directly
from monomers without an intervening
of new compounds which significantly
alter the Eh, pH and ionic composition
( inorganic products; (2)are incorporated humic stage, especially under anoxic of pore waters in the sediments. Eh
into new biopolymers in microbial cell conditions (Huc and Durand, 1977; decreases abruptly from the oxic to the
walls ; and (3)are chemically condensed Debyser et al., 1977). anoxic zone. The pH increases slightly,
o and randomly recombined to form the Microbial metabolism in the water col- with the reduction of sulphate, ferric iron

o irregularly organized geopolymers


known as humic compounds (Figure 3).
umn and the upper few centimetres of
the sediment is commonly aerobic and
and manganic manganese, production
of ammonia and sulphide, and increas-
o The term humic compounds includes
the humic and fulvic acids, the humins
produces carbon dioxide and water as
end products (Sundby et a/., 1983). In
ing alkalinity, leading to the precipita-
tion of carbonates and to the dissolution
and kerogen, all of which are defined areas of high productivity, aerobic pro- of amorphous silica and, to a lesser

c simply on the basis of their solubility


and molecular weight. Because they
cesses can deplete the oxygen content
of the water, leading to the development
extent, of quartz (Suess, 1979). Iron
(and copper, lead and zinc if present)
o form by random recombination, their
structures are variable, depending on
of anoxic conditions. Anaerobic metab-
olism, on the other hand, allows more of
may be precipitated as sulphides. The
complex role organic matter plays in the
o the monomers available and the diage- the initial biological compounds to sur- sulphur cycle and the formation of sul-

o netic conditions at the time of their for-


mation. Humic compounds increase in
vive; it also leads to the reduction of
sulphate to sulphide, the reduction of
phide minerals has been reviewed by
Jtlrgensen (1983). Those amino acids
molecular weight and decrease in sol- ferric iron, and the production of meth- and sugars which were released by
ubility in progressing from fulvic acids ane and ammonia. In the water column, hydrolysis of proteins and carbohy-
o through humic acids and humins to these processes are favoured by re- drates, but not utilized in the energy
o kerogen.
The humic and fulvic acids are de-
stricted water circulation arising from
salinity or temperature stratification
cycles of micro-organisms, can recom-
bine through abiotic chemical pro-
o fined on the basis of their solubility in
bases and acids (Schnitzer and Khan,
(Powell, 1984). Anaerobic processes
are themselves limited by a lack of
cesses to form the geopolymers found
in sediments and sedimentary rocks.
o 1972; Schnitzer, 1975; Aiken et a/., nutrients and the toxicity of their end The boundary between eogenesis
o 1985). Fulvic acids are soluble in both
acids and bases and range in molecular
products .
Relative tothevery labile proteins and
and catagenesis is gradational, al-
though it is generally considered to be
o weight from 700 to 10,000 (Rashid and carbohydrates, lipids and Iignins are coincident with the boundary between

o King, 1969). Humic acids are base sol-


uble polymers which range in molecular
more resistant to primary cycle metabo-
lism. Depolymerization of Iignins re-
sub-bituminous and high volatile bi-
tuminous coals, which corresponds to a
o weight from 10,000 to 100,000 and can
beupto 10nm in size. Theyaresolublein
quires cleavage of chemically stable
ether bonds. Many of the lipids are pre-
vitrinite reflectance of about 0.5% (Fig-
ure 5). Base-soluble humic compounds
o acids above pH 2; at pH 2 or less, they
are insoluble and precipitate.
served in stable cell wall residues of
micro-organisms or are associated with
are usually negligible, although they are
found in some sub-bituminous coals.
With increasing cross linkage and water-insoluble waxes and cutin from Thermal history, a combination of time
loss of acidic functional groups (car- higher plants. As a result, lignins and and temperature, plays a significant
boxyl and phenolic hydroxyl groups), lipids tend to survive and are concen- role in the formation of high-volatile
the humic and fulvic acids lose their base trated along with spores, pollen, cutin, bituminous coals. Otherwise coal would
solubility and form an insoluble humin! chitin and plant resins in the humin! remain at a peat or lignite level of dia-
kerogen fraction. The term humin is kerogen fraction. This is especially genesis, as is the case for the Lower
used for the base-insoluble fraction of true in anoxic environments, which Carboniferous lignites of the Moscow
soils and young sediments. Humins are lack oxygen-requiring Iignolytic fungi Basin (TeichmQller and TeichmQller,
partly hydrolyzable; they can re-incor- (Debyser et al., 1978). In peat bogs, 1982, p. 58). Similar processes con-
porate water and release 15-40% of the concentration of humic acids also trol the eogenesis of organic matter
their weight as monomers or lower tends to decrease the activity of decom- whether it is disseminated in sediments
molecular weight polymers during de- posers. This is partly the result of the or concentrated in peats, which can
mineralization with hydrofluoric acid, low pH (3 to 5) and partly because the become coals, or in algal muds, which
the standard method used in sample humic compounds are themselves rela- can become oil shales.
preparation to remove silicates. In con- tively immune to decomposition be- Hydrocarbon generation during eo-
trast to the humin fraction , kerogens are cause of the presence of phenolic genesis is restricted to biogenic gas
high molecular weight geopolymers groups, which inhibit microbial activity. which originates from anaerobic decay
which are stable to hydrolysis with HF The irregularity of the linking bonds of organic matter (Oremland and Kven-
and are insoluble in organic solvents, in humic compounds and their bulky volden, 1981). Relative to gas genera-
acids and bases. While some kerogen three-dimensional structures make them ted during catagenesis, biogenic gas
c
194 Diagenesis Geoscience Canada Reprint Series 4 c
c
% Ro COAL RANK (,,oil c
0.15 Peat
(H
II
("tt
Ol/OH

~o~ ...
OIl
c
c
~"'
-.
1 o 0 0

0.25 Lignite
0" OllOH

c
!
OIl

c
Figure 5 (right) Chemical structures of
proteins , carbohydrates, lipids and lignins.
0.38

0.50
1.10
Sub-b ituminous

,
~
High-volat ile bituminous
+
Medium-vo lat ile bituminous
m
05.90'W
c
c
c
$~ll
1.45 Low-volatile b ituminous

~ c
1.90 Semi-anthracite

~
c
2.50

~ 10
Anthracite

!
Graph ite
Ii c
c
c
'H'rich ' C' r i c h
c
OrIgIn Lipid rich Lignin, Char c
components carbohydrates c
Maceral groups
+
Liptinite
+
Huminite
~
Inertinite
c
c
~ ~ ~
(Eogenesis)
c
Maceral groups Liptinite V itrinite Inertinite c
(Catagenesis,
Metagenesis) c
c
c
c
C
E
(
C
C
C
c
e
c
40 ).1m (
c
Figure 6 Terminology of organic petrography and representative photomicrographs of the main maceral groups at different diagenetic levels. (
Photomicrographs are oil immersion, reflected light images. Liptin ite group : (a) alginite I Ro 0.3%) ;(b) cutinite (blue light excitation) I Ro
0.50%) ; (c) bituminite-sporinite IRo 1.0% ). Huminite-vitrinite group: (d) huminite I Ro 0.30%]; (e) vitrinite IRo 1.2%] ; (f) vitrinite IR o4.0%).
(
Inertinite group : (g) inertinite and semi-inertinite I Ro O. 60% ) ; (h) inertinite I e; 1.2%] ; (i) inertin ite I Ro4. 0%) . Thecorrelation between vitrinite
reflectance (Ro %) and diagenetic level is shown in Figures 3 and 7. C
C
C
r:
\.

c Chemistry and Diagenesis of Organic Matter 195

c
is primarily methane (up to 99%) and 560 and 580 nm. Carbon-rich compo- commonly characterized by the use of
carbon dioxide (0-8%), with minor nents, such as semi-inertinite and iner- bulk parameters, such as the HIC and
amountsof heavier gases (Claypool and tinite, which originate from fires (char- OIC atomic ratios, obtained from ele-
G Kvenvolden, 1983). Locally, biogenic coal) or fungal attack, show no visible mental analyses and expressed as a
gas may form significant accumula- change. All organic components be- "van Krevelen diagram" (Figure 7). On
C tions, especially as gas hydrates (Bily come physically compacted with in- the basis of these ratios, three or four
(J and Dick, 1974; Hitchon, 1974; Kven- creased burial, and previously visible types of kerogen have been defined
volden and McMenamin, 1980;Kvenvol- cells and tissues become progressively which appear to follow distinct diage-
C den et a/., 1983). Other hydrocarbons less distinct. netic pathways. This type of diagram
present at the eogenetic stage of dia- was originally used to characterize
genesis are inherited from organic mat- CATAGENESIS coals and their coalification path-
ter. Those changes in organic matter With increased burial organic matter ways (van Krevelen, 1961), but was later
r occurring during eogenesis which are undergoes progressive diagenesis in applied to kerogens (Mciver, 1967;
evident in optical microscopy are most response to increased temperature and Durand et al., 1972). A similar plot of
o
r:
noticeable in the huminite fraction (Fig-
ure 6). This fraction originates from
time. Increased pressure has little dia-
genetic effect on organic matter, other
hydrocarbon index versus oxygen in-
dex is obtained from measurements of
humic acids and forms vitrinite during than compaction; it may actually retard the volumes of hydrocarbon gases and

c catagenesis. The huminite passes


through a stage referred to as gelifica-
diagenesis, as suggested in some ex-
perimental studies (TeichmOlier and
carbon dioxide released during the
pyrolysis of rock samples containing
o tion (TeichmOller, in Stach et el; 1982,
p. 228) in which it swells and its reflec-
TeichmOller, 1982; Sajg6 et al., 1986).
Kerogen makes up the great bulk of
kerogen (Espitalie et a/., 1977). Type 1
kerogen has high initial HIC and low
o tivity increases (from 0.15%to 0.50% - organic matter present at the catagene- OIC ratios. The small amount of oxygen

o oil immersion); it becomes slightly


darker and increasingly opaque in
tic stage. Kerogen is an irregular geo-
polymer formed by randomchemical re-
present occurs mainly in ester bonds
(Robineta/., 1977).Upt080%byweight
transmitted light. The lipid-rich fraction combination of organic compounds re- of immature type 1 kerogens can be
(Iiptinite) shows little or no change in leased by microbial decomposition of volatilized during pyrolysis (Tissot and
o incident light and becomes progressive- proteins, carbohydrates and lipids. As Welte, 1984). The source material is
o ly darker in transmitted light, changing
from nearly colourless to light brown.
such, its structure isvariable and cannot
be predicted in the same way that the
mainly algal, or a combination of algal
lipids and waxes from higher plants,
Under ultraviolet irradation the peak flu- structures of biopolymers such as pro- which have been selectively concen-
r: orescence intensity shifts from 500 nm teins or carbohydrates can be predicted trated by microbial reworking and en-
v wavelength (at deposition) to between from their constituents. Kerogens are riched by bacterial lipids. It forms part
o Type 1
of the Iiptinite macerals in coal, and is
found in Scottish torbanites and algal
bog-head coals (Claret et a/., 1981;
Liptinite macerals
Powell and Snowdon, 1983; Tissot and
1.5
Welte, 1984). Examples of type 1 ker-
o
o -o
...as
CJ 1.0
ogens in fresh to brackish water lacus-
trine source rocks include the Eocene
Green River "oil shales", the Early Cre-
taceous of the Songliao and Jinquan
Basins of China and the Late Triassic

-E
o
as
o..... 0.5
Ordos Basin, also in China (Powell,
1986). Type 1 enriched source rocks
produce oils with> 20% wax at matura-
tion levels above 0.7% Ro '

_C
f;.:;.. \: } A Type 2 kerogen has intermediate ini-
::L
Inertinite 1"i,i,i,II B tial HIC and OIC ratios, and larger con-
r, tributions by aromatic and carboxylic
o acid groups than the type 1 kerogens.
O+-----,------r-----r------r-----' Ester bonds are abundant, as are
o 0.1 0.2 0.3 0.4 0.5 medium-length aliphatic hydrocarbon
chains and naphthenic rings. Both algal
O/C atomic ratio and higher plant sources appear to con-
tribute to type 2 kerogens (Iiptinite coal
macerals).Organic sulphur is present in
Figure 7 "van Krevelen plot" of diagenesis of kerogen types and coal macerals: A, immature
- field ofhumic acid occurrence overlaps region of immature Types 1 and 2 kerogens; S, mature
heterocyclic groups and in sulphide
- boundary represents region of maximum oil generation; C, overmature; Rm , iso-evolution as bonds. Up to 60% of immature kerogen
measured by vitrinite reflectance; ., sites where coal macerals coincide with kerogen types; as can be volatilized during pyrolysis
diagenesis increases in the mature kerogen, coalmaceralsplotat slightly10werOlC values. (After (Tissot and Welte, 1984). Type 2 ker-
Durand, 1980; van Krevelen, 1961; Tissot and Welte, 1984). ogens commonly are found in reduced
c
196 Diagenesis Geoscience Canada Reprint Series 4 (
C
marine strata and have been the source kerogen types are common. For exam- unaltered higher plant compounds can C
for major oil and gas deposits. Exam- ple, marine sourced organic matter with also accumulate, as they are protected
ples of type 2 kerogens formed in mod- some contribution by terrestrial higher by rapid sedimentation from aerobic
C
erately reducing clastic sediments are plants produces a kerogen that falls degradation. The proportions of res- C
found in the Sverdrup Basin, in Upper between types 1 and 2 because of the inite, liptinite and vitrinite in terrestrially
Devonian, Lower Carboniferous and increased OIC ratio, as in the shales of
(
derived kerogen, however, strongly
Upper Cretaceous strata of Alberta, in
the Jeanne d'Arc sub-basin east of
the Viking Formation (Mciver, 1967).
Type3 kerogen has an initial HIC ratio
control both the level of thermal altera-
tion necessary for petroleum genera-
C
Newfoundland (Powell and Snowdon, less than 1,an initial OIC ratio of 0.2 to tion and the relative proportions of oil, C
1983) and in some parts of the North 0.3, and is derived dominantly from ter- wet gas and dry gas produced (Snow-
Sea region (Thomas et al., 1985).Exam- restrial plants. It consists mainly of aro- don and Powell, 1982;Powelland Snow- C
ples of type 2 kerogens formed in highly
reducing marine evaporites or carbon-
matic groups formed from lignins and
humic compounds, and represents the
don, 1983). Liptinite- and resinite-rich
kerogens can be sources of both oil
C
ates are found in the Permian Phos- huminitelvitrinite fractions of coal and gas, whereas vitrinite-rich kerogens C
phoria Formation ofthe northern United petrography. Aerobically oxidized semi- are mainly gas sources. Examples of
States and in Middle Devonian reefs of inertinite and inertinite macerals may type 3 kerogens include those of the C
northern Alberta and northeastern Brit-
ish Columbia. Sulphur-rich type 2 ker-
also be present. Oxygen is present as
carboxylic acids, ketones and ethers
Lower Mannville shales of Alberta, the
Mahakam Delta of Indonesia (Durand
C
ogens also develop in saline lacustrine rather than in ester bonds (Robin et al., and Oudin, 1980) and the Niger Delta. C
sedimentary sequences which had a 1977). Lesser amounts of aliphatic Resinite-rich type 3 kerogens are found
high initial sulphate content. Heavy oils groups may be present in liptinite and in the Beaufort-Mackenzie Basin; lip-
C
with a high asphaltene and sulphur con- resinite macerals, depending on the
preservation of resins and lipids from
tinite-rich but resinite-poor type 3 ker- C
tent (up to 12%) are generated at some- ogens occur on the Labrador Shelf
what lower levels of maturity (Ro = higher plant and algal sources. Deposi- (Powell and Snowdon, 1983). C
0.5%); an example occurs in the Eo-
cene to Oligocene of the Jianghan
tion is mainly in deltaic and other thick,
rapidly accumulating continental mar-
Catagenesis takes place at moderate
temperatures (50°-150°C) and pres-
C
Basin of China (Powell, 1986). Mixed gin sediments; as a result, relatively sures (30 to 100 or 150 MPa), corre- C
n-Alkanes Cyclo-
alkanes Aromatics C
C
C

~Ro Hydrocarbons generated


co 00 .C
C
C
-•....
c:
•at
r- ,,~~: (Biogenic)
~

.
CD
ZCD
_C.J ~
15 25 35 0 6
U
13 33
t
CD
C
C
ale

-
Q,

-~ ~
GEOCHEMICAL eO >-

i:J
eN
0
lU FOSSILS - s: ~
U
-O.5~
15 25 35 0 6 13 33
III
CD C
e

-•.. •e #
C

-~~LJ
0
N C
c: 0 I
..•..
at
II 15 25 35 0 6 13 33
C
c
CJ
-1.35~
....
_.e
~CI:3
Number of
Carbon atoms
Number of
Rings
Number of
Carbon atoms
e
- 2.0~ (
..•
cil
II >0.-e
...
OCl:3
~
-4-5~
c
Figure 8 Hydrocarbon generation: changes in chemical structure and quantity with increased burial depth (after Tissot and Welte, 1984). c
Ro 0/0, reflectance of vitrinite in oil. Upper profile: biogenic fingerprint (eogenesis); middle profile: dilution of biogenic fingerprint by
hydrocarbons generated in the oil zone; lower profile: loss of biogenic fingerprint and chain shortening of hydrocarbons with cracking of oil to c
form wet gas at lower end of oil zone.
c
c
c
r
( Chemistry and Diagenesis of Organic Matter 197
r
C sponding to the zone of bituminous and aromatic compounds formed during eo- and the gas potential increases with
C anthracite coal, and of oil and wet gas genesis are relatively small, and are increasing vitrinite content. Type 4, a
generation. At the end of catagenesis, extensively diluted in petroleum by vitrinite-rich terrigenous kerogen with
G aliphatic chains have been cleaved from those aromatic compounds generated HIC < 0.8, is primarily a gas source.
r kerogens, and the size of aromatic units
has increased through chemical con-
during catagenesis .
The oil death line is the level of dia-
Throughout catagenesis, kerogen
undergoes noticeable changes in
( densation, with the development of sig- genesis at which both kerogen and petrographic appearance (Figure 6).
nificant ordering (Figure 5). Coals pro- previously formed liquid hydrocarbons With increasing levels of catagenesis,
gressively increase in rank from sub- are cracked to create low molecular the vitrinite component (huminite of the
( bituminous to anthracite during cata- weight hydrocarbons (Figure 8, lower eogenetic stage) changes relatively uni-
genesis. profile). It corresponds to a vitrinite formly (Figure 6d,e,f) . In incident light,
C Changes in chemical structure of reflectance of about 1.35% (Dow, 1977). reflectance increases (from 0.5% to
o hydrocarbons and the quantities gener-
ated with increasing burial depth are
Significant amounts of gas are gener-
ated from kerogen throughout the oil
about2.0% - oil immersion); in transmit-
ted light vitrinite becomes darker and
o summarized in Figure 8. Hydrocarbons
contributed to the sediment by precur-
window and continue to be produced to
much higher levels of diagenesis. At
increasingly opaque. Cell structure and
plant tissues which are readily visible in
sor organisms are called biogenic; geo- low levels of catagenesis wet gas is the early stages of eogenesis (Figure
c chemical fossils, on the other hand, are
compounds, unknown in living orga-
generated; as the level of catagene-
sis increases the proportion of meth-
6d) become progressively more difficult
to recognize without etching with acids.
o nisms, which are generated during ane increases, through further cracking. Liptinite undergoes a rapid change in

o diagenesis but which still retain a


"fingerprint" characteristic of biogenic
By the onset of metagenesis, only meth -
ane (dry gas) remains .
appearance (Figure sa.b.c) and physi-
cal properties. The trend of these
sources. Biogenic hydrocarbons can The amount, timing and composition changes is discontinuous. A discrete
include methane and small amounts of of hydrocarbons generated depend on "jump" marks the transition from eo-
ethane and ethylene from bacteria the kerogen type as well as on the level genesis to catagenesis. Bitumen,

o (Oremland and Kvenvolden, 1981),C 1 6 -


C 1 8 alkanes from plankton, and long
of diagenesis (Rogers, 1980; Mon nier et
a/., 1983). The hydrocarbon generation
which includes both hydrocarbons and
compounds with functional groups con-
o chain hydrocarbons (C 1 2-C3 S ) from
higher plant waxes . Biogenic hydrocar-
model shown in Figure 8 applies mainly
to type 2 kerogens formed in moder-
taining N, 0 and S, is generated . The
kerogen residue which remains after
o bons in the immature zone are charac- ately reducing sediments. The ex- bitumen generation shows an abrupt,

o terized by normal alkanes with a signifi-


cant odd-carbon preference, by acyclic
panded hydrocarbon generation model
in Figure 9, proposed by Powell and
noticeable decrease in volatiles and a
corresponding relative increase in car-
(open chain) branched hydrocarbons, Snowdon (1983), shows how kerogen bon content. A second "jump" occurs

o by cycloalkanes with 2 to 5 rings, and


by terpenes, some of which are partly
to fully aromatized during early eo-
types 2, 3 and 4 generate different pro-
portions of oil and gas at different levels
of diagenesis. The oil birth line occurs at
with the formation of low volatile bi-
tuminous coal. In sediments with the
potential for oil generation, this level of
genesis and form geochemical fossils a somewhat lower level of maturation catagenesis corresponds to the oil
o (Wakeham et et., 1980; Barnes and
Barnes, 1983). The characteristic fin-
(Ro = 0.4%) for both resinite-rich type 3
kerogen and type 2 kerogen formed in
death line; at this second jump, lipitinite
macerals undergo another abrupt re-
o gerprints for biogenic hydrocarbons highly reducing carbonate or evaporite duction in hydrogen and volatiles. In
o and those generated during eogenesis
are shown in Figure 8 (upper profile).
environments. In carbonate environ-
ments, low iron contents inhibit the for-
reflected light the liptinite becomes pro-
gressively "lighter" grey; by the second
o As burial increases, hydrocarbons mation of pyrite , leading to the develop- jump it is indistinguishable in reflected

o generated by catagenetic processes


dilute precursor compounds and there
ment of S-rich type 2 kerogens; as a
result, heavy S-rich and asphaltic oils
light from vitrinite without etching.
With ultraviolet light excitation the Iip-
o is a gradual loss of the biogenic fin-
gerprint as oil generation progresses
are generated from lacustrine or marine
sources at somewhat lower levels of
tinites show a progressive increase in
maximum spectral fluorescence wave-
r (Figure 8, middle profile). The level of maturation. Non-marine oils generated length with increasing diagenetic level,

o catagenesis and its relation to hydro-


carbon generation is of particular im-
from liptinite-rich type 1 and type 3 ker-
ogens, however, are formed at some-
and total fluorescence intensity pro-
gressively declines. In transmitted light
8 portance in defining petroleum poten-
tial. The levels of catagenesis corres-
what higher levels of thermal matura-
tion (Ro = 0.6-0.7%). The maximum gas
the liptinite, initially pale yellow, be-
comes progressively darker and even-
ponding to the oil birth line and the generation for type 2 kerogen occurs tually black and opaque. The semi-iner-
oil death line have been used to define with the cracking of liquid hydrocar tinite and inertinite components are ini-
an "oil window" (Figure 8). The oil birth bons at levels of thermal maturation tially rich in carbon and strongly aro-
line is the level of catagenesis which greater than Ro = 1.35%. Significant matized (Telchmuller, in Stach et aI.,
initiates generation of medium to low amounts of gas are generated, however, 1982)at the time of deposition and thus
molecular weight (liquid) hydrocarbons at lower levels of maturation in liptin- undergo little additional alteration. The
from kerogen and corresponds to a ite- and resinite-rich type 3 kerogen degree of later alteration depends on
vitrinite reflectance of approximately (Ro > 0.55%)(Monnier eta/. , 1983). The the initial degree of charring. The reflec-
0.5% (Dow, 1977).The amounts of poly- liquid hydrocarbon potential decreases tivity of semi-inertinite and inertinite in
c
198 Diagenesis Geoscience Canada Reprint Series 4 (

C
Vitrinite reflectance. %Ro C
0.4 0.6. 0.8 1.0 1.2 1.4 C
C
--- Gas-naphthenic condensate
RESINITE-RICH /. c
H/C 0.8-0.95
light naptii'hen'lC ? c
------ ~
oil
.......
.
c
..._-
en

-------Cl:-----:::=========:;;====Ii;IE:=--
ca
.~ ---
Q)
_
Gas dry gas
c
c
L1PTIN1TE-RICH .~
RESINITE-POOR rn c
H/C 0.8-0.95
waxy on c
c
c
VITRINITE-RICH
H/C <0.8 --=:::::
HYDROCARBON GENERATION MODEL - TERRESTRIAL ORGANIC MATTER
Gas / drygas
c
c
c
c
Vitrinite reflectance, %Ro c
0.4 0.6 0.8 1.0 1.2 1.4 c
c
HIGHLYEUXINIC
ENVIR.: H/C >1.1
(Carbonate? Fe-poo:
;< c
c
c
heavy S-rich &
asphaltic oil intermediate
c
C\I Cl c
w
n,
.2
c: c
~ MOD. EUXIN1C
i" .......- - -
c
c
ENVIR.: H/C >1.1 c
(Clastic Fe-rich)
c
e
(

- . Dissolution in gas phase ..... Cracking


c
(
HYDROCARBON GENERATION MODEL - MARINE ORGANIC MATTER c
c
Figure 9 Hydrocarbon generation for kerogen types 2, 3 and 4. (After Powell and Snowdon , 1983). C
l
C
(
c Chemistry and Diagenesis of Organic Matter 199

(
incident light is initially high ; only at solution of hydrocarbons in ground oils. Significant differences in the CPI,
( advanced levels of diagenesis does waters, leading to a depletion of the the amount of oil,the hydrocarbon chain
any increase in reflectivity occur (Fig- lighter compounds, as the solubility of length and the relative distribut ion of
( ure 6g,h,i). In transmitted light semi- normal hydrocarbons in water is in- isoprenoids and triterpanes are appar-
o inertinite and inertinite are opaque
throughout diagenesis.
versely proportional to their chain
length. The second process, bacterial
ent in gas chromatograms of a solvent
extract of immature Kimmeridgian oil
degradation, is more important and can shale, Kimmeridgian crude oil, the

c METAGENESIS
Metagenesis refers to the stage of
lead to the total loss of normal alkanes
and isoprenoids, leaving a heavy oil
crude oil microbially degraded in the
laboratory and oils of different maturity
( organic diagenesis at which crystalline residue composed of cycloalkanes and generated from the immature shale by
ordering of the organic matter begins aromatics (Deroo and Powell, 1978). hydrous pyrolysis. While the immature
( (Tissot and Welte, 1984) . Aromatic The heavy oil belt of Alberta is estimated extract looks like a mildly degraded oil,
( nuclei increase in size, forming clusters, to contain 142billion m3 of oil in a 1000 the crude oil and oils generated by
and C-C bonds are broken , generating km arc from the Peace River in west- hydrous pyrolysis ofthe immature shale
o methane. Aliphatic molecules that sur- central Alberta to Lloydrninstsr in west- show a closer match in distributions of

o vived catagenesis and previously gen-


erated hydrocarbons are cracked to dry
ern Saskatchewan. Similarities in the
distribution of cycloalkanes, aromatics
normal hydrocarbons, triterpanes and
isoprenoids.
o gas. At the onset of metagenesis the
vitrinite component of the coal has a
and benzothiophenes were used as evi-
dence for the relationship of oil sands
Microbial degradation of petroleum
has long been recognized in the gene-
o reflectance of about 2%, which pro-
gressively increases with diagenesis to
and heavy oils (L1oydminster) with con-
ventional oils (Lower Cretaceous Mann-
ration of sulphur in the cap rocks of salt
domes (Thode et al., 1954; Krouse and
( about 4% or 5%, where the strata are ville reservoirs) (Deroo et al. , 1974; McCready, 1979) where sulphate from
generally considered to be in the realm Deroo and Powell, 1978). Selective re- anhydrite is used by anaerobes such as
of metamorphism. The liptin ite compo- moval of normal alkanes and isopre- Desulfovibrio to oxidize petroleum frac-
nent of the organics (type 1 kerogen) noids on going from non-degraded oils tions, leading to the formation of sul-
and, at later stages, the inertinite com- to biodegraded heavy oils is consistent phide , part of which is subsequently
ponent become visually and chemically with patterns observed in incubation oxidized to elemental sulphur. Such
indistinct from vitrinite. studies on the microbial degradation processes have been implicated in the
of a range of undegraded oil and oil degradation of oils in many areas, such
c TELOGENESIS sand samples (RUbinstein et al., 1977; as the Bell .Greek field, Montana (Win-

o Organic compounds in rocks can be


altered by late stage processes result-
Rubinstein and Strausz, 1978;Crawford
et al., 1978). Winters et al. (1983) pro-
ters and Williams , 1969)and the north-
ern Williston Basin of Saskatchewan
c ing from contact with meteoric waters of posed hydrous pyrolysis , where source (Bailey et al., 1973a,b, 1974). In shallow-

o low salinity and with atmospheric oxy-


gen (Figure 2). Two distinct processes
appear to be active (Bailey and others,
rocks are heated in liquid water for 1 to 5
days at temperatures below the critical
point [<374°Cj,asatechniquefordis-
depth groundwaters , where sufficient
dissolved oxygen may be present, aero-
bic bacteria can also degrade petro-
l 1973b).Water washing results from the tinguishing immature from biodegraded leum. In a study of biodegradation with
o aerobic cultures, Bailey et al. (1973a)
found that isoprenoids were attacked
( atter the removal of n-alkanes; lower
o ring napthenes and low molecular
weight aromatics were attacked at the
o same time as lighter normal paraffins,

o prior to the removal of heavier paraffins.


Similar processes affect kerogen that is
exposed to the atmosphere or to oxy-
genated groundwaters. Non-aromatic
( groups are preferentially removed,
leading to an increase in the aromatic
fraction of the kerogen (van Krevelen
and Schuyer, 1957). Acidic functional
groups such as carboxyl, carbonyl and
c phenolic hydroxyl are formed , even-
tually leading to the production of humic
acids. Such processes are analogous to
retrograde metamorphism in metamor-
phic rocks. If oxidation is intense it may
be distinguished petrographically by
the development of darker or lighter oxi-
Figure 10 Photomicrograph of oxidized vitrinite in a low-volatile bituminous coal. Oxidation dation haloes on the margins of kerogen
halos occur on periphery of vitrinite particle. part icles (Figure 10;Bustin et al., 1985).

'-
r"
c
200 Diagenesis Geoscience Canada Reprint Series 4 c
c
In coals oxidation results in a marked and about 4% or 5% at the end of meta- Brooks, J., 1980, ed., Organic Maturation c
decrease in coal quality. Coals exposed
to atmospheric oxygen or meteoric
genesis and onset of metamorphism.
During catagenesis and metagenesis,
Studies and Fossil Fuel Exploration: Ac-
ademic Press, New York, 441 p.
c
water have lower than normal caloric
values, form poor cokes or are non-
the liptinite component becomes pro-
gressively darker and opaque in trans-
(Includes 25 papers covering diagenesis
of organic matter, classification, chemis-
c
try and techniques). (
coking, and have reduced flotation mitted light. Inertinite, which originates
properties (hydrophobicity). from charcoal, undergoes little change
Bustin, M., Cameron, A.R., Grieve, D.A. and
Kalkreuth, W.D., 1985, Coal Petrology: its c
CONCLUSION
during the early stages of diagenesis
and only at advanced stages of meta-
principles, methods, and applications,
Second Edition: Geological Association of c
Organic diagenesis is progressive and
irreversible with few exceptions. It
genesis does its reflectivity in incident
light increase. Semi-inertinite macer-
Canada, Short Course Notes Volume 3.
Durand, B., 1980, ed., Kerogen: Editions
c
begins early and proceeds rapidly als, which are transitional in composi- Technip, Paris, 519 p.
(15papers on the petrography, chemistry
c
under surficial conditions so that even
in the most favourable environments,
tion between vitrinite and intertinite,
increase in reflectivity with diagene- and diagenesis of kerogen). c
only a small fraction of the organic mat-
ter is incorporated into the sediment.
sis. The increase in reflectivity depends
on the amount of carbonization that
Eglinton, G. and Murphy, M.T.J., 1969, eds.,
Organic Geochemistry: methods and re- c
During eogenesis, micro-organisms occurred prior to deposition.
sults: Springer, New York, 828 p.
Hunt, J.M., 1979, Petroleum Geochemistry c
metabolize most ofthe organic matterto
CO2 and H20 in oxygenated sediments
Hydrocarbons are generated from
organic matter throughout diagenesis.
and Geology: W.H. Freeman, San Fran-
cisco, 617 p.
c
and to CH4 , CO2 , H2 and H20 under
anoxic conditions. The remaining
During eogenesis biogenic methane
forms as a result of anaerobic decay of
Ibach, L.E.J., 1982, Relationship between
sedimentation rate and total organic car-
c
organic matter forms humic and fulvic organic matter. During catagenesis wet bon content in ancient marine sediments: c
acids. With increasing cross-linkage
and loss of functional groups, these
gas and/or oil is generated, depending
on the type of kerogen, in response to
American Association of Petroleum Geo-
logists Bulletin, v. 66, p. 177-188. c
acids decrease in solubility and form
part of the kerogen fraction. Similar
increased temperature and time ac-
companying burial. By the metagenetic
Karr, C., 1978a, ed., Analytical Methods for
Coal and Coal Products, v. 1: Academic c
processes control eogenetic reactions stage of diagenesis only dry gas is
Press, Toronto, 580 p.
(19 papers on the physical and chemical
c
whether the organic matter is dissemi-
nated in sediments or concentrated in
generated by cracking of kerogen and
earlier formed hydrocarbons. Coal
properties of coal and coal products and
c
peat. progressively increases in rank during
methods for their analysis).
Karr, C., 1978b, ed., Analytical Methods for c
The catagenetic and metagenetic
stages of diagenesis result from in-
diagenesis from peat through anthra-
cite. The most noticeable changes in
Coal and Coal Products, v. 2: Academic
Press, Toronto, 669 p. c
creased temperature and time accom-
panying burial ofthe sediment. All types
coal accompanying increased rank are
the loss of moisture, oxygen and hydro-
(17 papers covering the structures of coal,
coke, their combustion products and min- c
of kerogen progressively evolve toward gen and the corresponding increase in eraI matter).
Karr, C., 1979, ed., Analytical Methods for
c
pure carbon with a decrease in hydro-
gen and oxygen in response to the
fixed carbon. Telogenesis can affect
both organic matter and generated
Coal and Coal Products, v. 3: Academic
Press, Toronto, 641 p.
c
breakage of aliphatic chains and some
cyclic compounds and the accompany-
hydrocarbons. Contact with meteoric
water of low salinity results in leaching
(18 papers on coal gases and waste pro-
ducts, including analytical procedures).
c
ing generation of bitumen, including of the lighter molecules and promotes Larsen, G. and Chilingar, G.V.,1979,Diagen- C
hydrocarbons. By the metagenetic bacterial degradation of petroleum. esis of Sediments and Rocks, in Larsen,
stage of diagenesis, crystalline order- Oxidation of kerogen mayalso occur, re- G. and Chilingar, G.V., eds., Diagenesis G
in Sediments and Sedimentary Rocks:
ing of aromatic compounds occurs and
any aliphatic molecules that survived
sulting in preferential removal of the
non-aromatic fractions and formation of Elsevier, Amsterdam, p. 1-29. C
catagenesis, as well as previously gen- humic acids. Petrographically, oxida- Robert, P., 1981, Classification of organic
matter by means of fluorescence: ap-
C
erated wet gas and oil, are cracked to tion is marked by the occurrence of
dry gas. With diagenesis the petro- oxidation haloes and micro-fissures in
plication to hydrocarbon source rocks:
Coal Geology, v. 1, p. 101-137.
C
graphic constituents of the organic mat-
ter (macerals), originally distinct chemi-
the kerogen particles. Robert, P., 1985, Histoire geothermique et C
diagenese organique: Bulletin des Cen-
cally and morphologically, become REFERENCES tres de Recherches Exploration-Produc- C
progressively similar. During eogenesis tion Elf-Aquitaine, Memoire 8, 345 p.
the lipid-rich components (Iiptinite) alter General Reviews on Organic Compounds Stach, E., Mackowsky, M.-Th., Teichmuller, E
little except during extreme oxidation.
The huminite components swell with
in Sediments and Rocks M., Taylor, G.H., Chandra, D. and Teich-
muller, R., 1982, Stach's Textbook of Coal
C.
gelification and their reflectivity in inci- Barker, C., 1982, Organic Geochemistry in Petrology: Borntrager, Berlin, 535 p. (
Petroleum Exploration: American Asso- Tissot, B.P.and Welte, D.H., 1984,Petroleum
dent light increases from 0.15% to about (
ciation of Petroleum Geologists, Educa- Formation and Occurrence: a new ap-
0.5%. Duringthecatagenetic and meta-
genetic stages the vitrinite (huminite of
tion course notes 10.
Barnes, M.A. and Barnes, W.C., 1978,Organic
proach to oil and gas exploration, Second
Edition: Springer, Berlin, 538 p. c.
eogenesis) macerals progressively in-
crease in reflectivity in incident light,
compounds in lake sediments, in Lerman,
A., ed., Lakes: Chemistry, Geology,
Trudinger, P.A. and Swaine, D.J., 1979, eds.,
Biogeochemical Cycling of Minerai-form- c
reaching 2.0% atthe end of catagenesis Physics: Springer, New York, p. 127-152. ing Elements: Elsevier, Amsterdam, 612 p.
c
c
c
c
( Chemistry and Diagenesis of Organic Matter 201

c.
c. Sources of Organic Matter in Sediments Barker, J.F., 1982,The potential importance Knauer, G.A. and Mart in, J.G., 1981, Phos-
c Cohen, A.D . and Spackman , W., 1980,
of radionuclide or metal complexation
and transport by organic matter in
phorus-cadmium cycling in northeast
Pacific waters: Journal of Marine Re-
c~ Phytogenic organic sediments and sedi- groundwaters , in Geotechnical Re- search, v. 39, p. 65-76.

c mentary environments in the Ever-


glades-mangrove complex of Florida:
Part 3. The alteration of plant material in
search: Proceedings of the 7th Nuclear
Fuel Waste Management information
meeting, p. 66-110.
Krouse , H.R. and McCready, R.G.L., 1979,
Reductive reactions in the sulfur cycle,
in Trudinger, P.A. and Swaine, D.J., eds.,
( Barnes, MA and Barnes, W.C., 1983, Oxic Biogeochemical Cycling of Mineral-
peats and the origin of coal macerals :
( Palaeontographica , v. 172, ser . B., and anoxic diagenesis of diterpenes in Forming Elements : Elsevier, Amster-
p.125-149. lacustrine sediments, in Bjor~y, M., Al- dam, p. 315-368.
( Demaison, G.J. andMoore, G.T., 1980, Anoxic brecht,P.,Cornford,C.,deGroot,K., Eglin- Krumbein, W.E. and Swart, P.K., 1983, The
environmentsand oil source bed genesis: ton , G., Galimov, E., Leythaeuser, D., microbial carbon cycle , in Krumbe in,
AmericanAssociationof PetroleumGeolo- Pelet, A., RullkCitter, J. and Speers, G., W.E ., ed., Microb ial Geochem istry:

c gists, Bulletin, v. 64, p. 1174·1209.


Dow, w.G., 1978,Petroleum source beds on
eds., Advancesin Organic Geochemistry
1981: Wiley, Chichester, p, 289-298.
Blackwell , Oxford, p. 5-62.
Kvenvolden, K.A. and McMenamin, M.A.,

o continental slopes and rises : American


Association of Petroleum Geologists,
Bolin, B., 1983,The Carbon Cycle, in Bolin,
B. and Cook, R.B., eds., 1983,The Major
1980, Natural Gas Hydrates: a review
of their geologic occurrence : United
o Bulletin, v. 62, p. 1584-1606.
Krey,J., 1970,Die Urproduction des Meeres,
Biogeochemical Cycles and Their Inter-
actions: Scientific Committee on Pro-
States Geological Survey Circular 825.
Kvenvolden, K.A., Barnard, L.A., Brooks,
o in Dietrich, G., ed., Erforschung des
Meeres:Umschau, Frankfurt, p. 183-195.
blems of the Environment [SCOPE]:
Wiley, New York, p. 41-46.
J.M. and Wiesenburg, D.A., 1983, Geo-
chemistry of natural gas hydrates in
o Meyers, PA, Leenheer, M.J., Eadie, B.J. Bustin , A.M., Hills, L.V. and Gunther, P.R., oceanic sediment, in Bjor~y, M., Al-

o and Maule , S.J., 1984, Organic geo-


chemistry of suspended and settling
particulate matter in Lake Michigan:
1977, Implications of coalification levels ,
Eureka Sound Formation, northeastern
Arctic Canada: Canadian Journal of
brecht , P. , Cornford, C., de Groot, K.,
EgJinton, G., Galimov, E., Leythaeuser,
D., Pelel, A., RullkCitter, J. and Speers,
Geochimica et Cosmochim ica Acta, Earth Sciences, v. 14, p. 1588-1597. G., eds. , Advances in Organic Geo-
v. 48, p. 443-452 . Claypool , G.E. and Kvenvolden, K.A., 1983, chemistry 1981: Wiley, Chichester,
Styan, W.and Bustin, R.M., 1983, Petrogra- Methane and other hydrocarbon gases p.422-430.
phy of some Fraser River Delta peat de- in marine sediment: Annual Review of Mackenzie , A.S., Patience, R.L. and Max-
posits: coal maceral and microlithotype Earth and Planetary Sciences, v. 11, well, J.R., 1981, Molecular changes and
precursors in temperate climate peats: p.299-327. the maturation of sedimentary organic
Coal Geology, v. 2, p. 321·370. Debyser, Y. , Pelet, A. and Dastillung, M., matter, in Atkinson , G. and Zuckerman,
Trudinger, P.A., Swaine, D.J. and Skyring, 1977, Geoch imie organique de sed i- J., eds., Origin and Chemistry of Petro-
G.w., 1979, Biogeochemical cycling of ments marins recents : Mer Noire, Balti- leum: Pergamon, Oxford, p. 1-31.
elements - general cons iderations, in que, Atlantique (Mauritanie), in Cam- Macqueen , R.W. and Powell, T.G., 1983,
c Trudinger, P.A. and Swaine , D.J., eds.,
Biogeochemical Cycling of Mineral-
pos, R. and Goni, J., eds., Advances in
Organic Geochemistry 1975: Enadimsa ,
Organic geochemistry of the Pine Point
lead-zinc ore field and region, North-
forming Elements: Elsevier, Amster- Madrid, p. 289-320. west Territories , Canada: Economic Ge-
dam, p. 1-27. Debyser, Y.,Gadel, E, Leblond, C. and Mar- ology, v. 78, p. 1-25.
Waples, D.W., 1983, Reappraisal of anoxia tinez , M.J., 1978, Etude des composes Menzel, D.W. and Ryther, J.H., 1970, Dis-
and organic richness , with emphasis on humiques des kerogenes et de la frac- tribution and cycling of organic matter in
Cretaceous of North America: American tion hydrolysable dans les sediments, in the oceans, in Hood, DW., ed., Organic
r Association of Petroleum Geologists, Geochim ie organique des sediments Matter in Natural Waters: University of
Bulletin, v. 67, p. 963-978. marins protonds Orgon II. Atlantique, Alaska , Institute of Marine Science, Oc-
Welte, D.H., 1970,Organischer Kohlenstoff Nord-Est Bresil : Paris, Editions du casional Publication 1,p. 31-54.
und die Entwicklung der Photosynthese CNRS, p. 339·354. Oremland, R.S~ and Kvenvolden,K.A., 1981,
auf der Erde : Naturwissenschaften, Deuser, W.G., 1971, Organic-carbon budget Microbial formation of ethane in anoxic
v. 57, p. 17-23. of the Black Sea: Deep-Sea Research, estuarine sediments : Appl ied and
v. 18, p. 995-1004. Environmental Microbiology, v.42,
Eogenesis of Organic Matter Gautier, D.L., 1985, Interpretation of early p.122-129.
diagenesis in ancient marine sediments, Philp , R.P. and Calvin , M., 1976, Kerogen
Aiken , G.R., McKnight, D.M ., Wershaw, in Gautier, D.L., Kharaka, Y.K. and Sur- structures in recently-deposited algal
R.L. and MacCarthy, P., 1985, eds. , dam, A.C., eds., Relationship of Organic mats at Laguna Mormona, Baja Califor-
( Humic Substances in Soil , Sediment, Matter and Mineral Diagenesis: Society nia: a model system for the determ ina-
and Water: Wiley, New York, 692 p. of Economic Paleontologists and Miner- tion of kerogen structures in ancient
(
Alpern , B., 1980, Petrographie du kerogen, alogists, Short Course Notes, v. 17, sediments , in Nriagu, J.O., ed., Environ-
in Durand, B., ed., Kerogen: Editions p.6-78. mental Biogeochemistry, v.1 : Ann
Technip, Paris, p. 339-371. Hitchon, B., 1974, Occurrence of natural gas Arbor Science Publishers, Ann Arbor,
Anderson, G.M. and Macqueen, R.W., 1982, hydratesin sedimentarybasins,in Kaplan, p. 131-148.
Mississ ippi Valley type lead -zinc I.R., ed., Natural Gases in Marine Sedi- Powell, T.G., 1984, Some aspects of the
deposits : Geoscience Canada, v. 9, ments: Plenum, New York, p. 195-225. hydrocarbon geochemistry of a Middle
p. 108-117. Huc, A.Y. and B.M. Durand, 1977, Occur- Devonian barrier-reef complex, western
Baker, E.w., 1969, Porphyr ins , in Eglinton, rence and significance of humic acids in Canada ,in Palacas, J.G., ed., Petroleum
G. and Murphy, M.T.J., eds., Organic ancient sediments: Fuel, v. 56, p. 73-80. Geochemistry and Source Rock Poten-
Geochemistry: methods and results: J(lrgensen, B.B., 1983, The microbial sul- tial of Carbonate Rocks: American Asso-
Springer, New York, p. 464-497. phur cycle, in Krumbein, W.E., ed., ciation of Petroleum Geologists, Studies
Microbial Geochemistry: Blackwell, Ox- in Geology 18, p. 45-61.
ford, p. 91-124.
c
202 Diagenesis Geoscience Canada Reprint Series 4 c
c
Aashid, M.A. and King, L.H., 1969, Molecu- Cook, A., Hutton, A. and Kantsler, A., 1980, Hacquebard, P.A. and Donaldson , J.A .,
c
larweight distribution measurements on
humic and fulv ic acid fractions from
Oil shales: Scientific Australian, v. 4, no.
4, p. 6-14.
1970, Coal metamorph ism and hydro-
carbon potential in the Upper Paleo-
c
marine clays on the Scotian Shelf: Geo- Cooper, B.S. and Murchison , D.G., 1969, zoic of the Atlantic Provinces: Cana- (
chimica et Cosmochimica Acta, v. 33, Organic geochemistry of coal, in Eglin- dian Journal of Earth Sciences, v. 7,
p. 147-151, ton, G. and Murphy, M.T.J., eds., Organic p. 1139-1163.
(
Schnitzer, M., 1975,Chemical, spectroscopic Geochemistry: methods and results: Hood, A. and Castano, J.R. , 1974, Organic (
and thermal methodsfor the classification Springer, New York, p. 699-726. metamorph ism: its relationship to petro-
andcharacterizationofhumicsubstances,
in Povoledo, D. and Golterman, H.L.,eds.,
Creaney, S., 1980, The organic petrology of
the Upper Cretaceous Boundary Creek
leum generation and applicat ion to stu-
die of auth igen ic minerals : United
C
Humic Substances: their structure and
function in the biosphere: Centre for Agri-
Formation, Beaufort-Mackenzie Basin:
Bulletin of Canadian Petroleum Geol-
Nations ESCAp, CCOp' Technical Bul-
letin 8, p. 87-118.
C
cultural Publishing and Documentation, ogy, v. 28, p. 112-129. Kalkreuth, W., 1982, Aankand petrographic (
Wageningen, p. 293-310. Curtis, C.D., 1977, Sedimentary geochem- composition of selected Jurassic-Lower
Schnitzer, M. and Khan, S.U., 1972, Humic istry: env ironments and processes Cretaceous coals of British Columbia, C
Substances in the Environment: Marcel dominated by involvement of an Canada: Bulletin of Canadian Petro-
Dekker, New York, 327 p. aqueous phase: Aoyal Society of leum Geology, v. 30, p. 112-139. C
London , Philosophical Transactions, Legall, ED., Barnes, C.R. and Macqueen,
Suess, E., 1979, Mineral phases formed
in anox ic sediments by microbial de- v. 32A, p. 353-372. R.W., 1981, Thermal maturation , burial
C
composition of organic matter : Geo-
chimica et Cosmochimica Acta, v. 43,
Deroo, G . , Powell , T.G . , Tissot , B. ,
McCrossan, R.G. and Hacquebard, P.A.,
history and hotspot deve lopment,
Paleozoic strata of southern Ontario-
C
p.339-352.
Sundby, B., Bouchard, G., Lebel, J. and
1977, The origin and migration of petro-
leum in the Western Canadian Sedimen-
Quebec, from conodont and acritarch
colour alteration studies : Bulletin of
C
Silverberg , N., 1983, Aates of organic tary Basin: a geochemical and thermal Canadian Petroleum Geology, v.29, C
matter oxidation and carbon transport in maturat ion study: Geolog ical Survey of p.492-539.
early diagenesis of marine sediments, in Canada , Bulletin 262. Mciver, A.D., 1967, Composition of kerogen C
BjorGly, M., Albrecht, P.,Cornford, C., de Dow, W., 1977, Kerogen studies and geo- - clue to its role in the origin of petro-
Groot , K., Eglinton, G., Galimov, E., logical interpretations: Journal of Geo- leum: 7th World Petroleum Congress, C
Leythaeuser, D., Pelet, A., Rullkotter, J.
and Speers, G., eds., Advances in Or-
chemical Exploration, v. 7, p. 79-99.
Durand, B. and Oudin, J.L., 1980, Exemple
Proceedings, v. 2, p. 25-36.
McWhae, J.A.H., Elie, A., Laughton, K.C.
C
ganic Geochemistry 1981: Wiley, Chi- de migration des hydrocarbures dans
une ser le deltaique: Ie Delta de la
and Gunther, P.R., 1980, Stratigraphy C
chester, p. 350-354. and petroleum prospects of the
Ting, ET.C., 1977, Microscopical investiga- Mahakam, Kalimantan, lndonesie: 10th Labrador shelf: Bulletin of Canadian C
tion of the transformation (diagenesis) World Petroleum Congress, Proceed- Petroleum Geology, v. 28, p. 460-488.
from peat to lignite : Journal of Micro- ings, v. 2, p. 3-11, Milner, C.W.D., Aogers, M.A. and Evans, C
scopy, v. 109, p. 75-83. Durand, B., Espitalie, J., Nlcatse, G. and C.R., 1977, Petroleum transformations
Tissot, B., Durand, B., Espitalie, J . and Combaz, A., 1972, Etude de la matiere in reservoirs : Journal of Geochemical C
Combaz, A., 1974, Influence of the
nature and diagenesis of organic matter
organique insoluble (kerogene) des
argiles du Toarcien du Bassin de Paris: J.
Exploration, v. 7, p. 101-153.
Monnier, F., Powell , T.G. and Snowdon,
C
in formation of petroleum : American
Association of Petroleum Geologists,
Etude par les precedes optiques, ana-
lyse elementaire, etude en microscopie
L.A., 1983, Qualitative and quantitative
aspects of gas generation during mat-
C
Bulletin, v. 58, p. 499-506. et diffraction electroniques: Aevue des uration of sed imentary organic mat- C
Wakeham, S.G., Schaffner,C. andGiger,W., Institute Fran9aise du Petrole: v.27, ter. Examples from Canadian frontier
1980, Polycyclic aromatic hydrocarbons p.865-884. basins, in Bjor~y, M., Albrecht , P., Corn- C
in Aecent lake sediments - II. Com- Espttalle, J., Laporte, J.L., Madec , M., Mar- ford, C., de Groot, K., Eglinton , G.,
pounds derived from biogenicprecursors quis, F., Leplat, P., Paulet , J. and Bou- Galimov, E. , Leythaeuser, D., Pelet, A., C
during early diagenesis: Geochimica et
Cosmochimica Acta, v. 44, p. 415-429.
tefeu, A., 1977, Methode rapide de
characterisation des roches meres, de
Aullkotter, J. and Speers, G., eds.,
Advances in Organic Geochemistry
C
catagenesis and Metagenesis
leur potentiel patroller et de leur degre
d'evolution: Aevue des Institute Fran-
1981: Wiley, Chichester, p. 487-495.
Ogunyami, 0., Hesse, A. and Heroux, Y.,
C
catss du Petrole , v. 32, p. 23-42. 1980, Pre-orogenic and synorogenic C
Bostick, N.H., 1979, Microscopic meas- Foscolos, A.E. and Powell , T.G., 1980, Min- diagenesis and anchimetamorph ism in
urement of the level of catagenesis of eralogical and geochemical transfor- Lower Paleozoic continental margin C
solid organic matter in sedimentary mations of clays during catagenesis sequences of the northern Appala-
rocks to aid exploration for petroleum and their relation to oil generation, in chians in and around Quebec City, Can-
and to determine former burial tempera-
tures - a review, in Scholle, P.A. and
Miall , A.D., ed., Facts and Principles of
World Petroleum Occurrence: Cana-
ada: Bulletin of Canadian Petroleum
Geology, v. 28, p. 559-577.
E
Schluger, P.A., eds., Aspects of Diagen- dian Soc iety of Petroleum Geology, Powell, T.G., 1978, An assessment of the (
esis: Society of Economic Paleontolo- Memoir 6, p. 153-172. hydrocarbon source rock potential ofthe
gists and Mineralogists, Special Pub- Hacquebard, P.A., 1975, Pre- and post- Canad ian Arctic Islands: Geological C
lication 26, p. 17-43. deformational coalification and its sig- Survey of Canada , Paper 78-12.
Claret , J., Jandine, S. and Aobert, P., 1981, nificance for oil and gas exploration, in Powell, T.G., 1982, Petroleum geochemis- (
Le d iversite des roches meres Alpern , B., ed., Petrographie organique try of the Verrill Canyon Formation: a
petrolleres: aspects geologiques et et potential petrolier: Paris, Editions du source for Scotian Shelf hydrocarbons:
(
CNAS, p. 225-241.
implications economiques a partir de
quatre exemples: Bulletin des Centres
Bulletin of Canadian Petroleum Geol-
ogy, v. 30, p. 167-179.
C
de Aecherches Exploration-Production
Elf-Aquitaine, v. 5, p. 383-417.
C
C
C
C'
( Chemistry and Diagenesis of Organic Matter 203
c
c Powell, T.G., 1986, Petroleum geochemis- Sawatzky, H., George , A.E., Banerjee, Crawford, R.J., Spyckerelle, C. and West-
( try and depositional setting of lacustrine R.C ., Sm iley, G.T. and Montgomery, lake, D.W.S., 1978,Biodegradation of oil
source rocks: Marine and Petroleum D.S., 1977, Maturation studies on Cana- reservoirs , in Strausz, O.P. and lown ,
c Geology, v. 3, p. 200·219.
Powell, T.G., Foscolos, A.E., Gunther, P.R.
dian east coast oils: CANMET Report
77·42.
E.M., eds ., Oil Sand and Oil Shale
Chemistry : Verlag Chemie, New York,
and Snowdon, L.R., 1978, Diagenesis of Snowdon, L.R. and Powell, T.G., 1982, Im- p. 163-176.
organic matter and fine clay minerals : a mature oil and condensate : modification Deroo, G., Tissot, B., McCrossan, R.G. and
( of hydrocarbon generation model forter-
comparative study: Geochimica et Cos- Der,E , 1974, Geochemistry ofthe heavy
(' mochimica Acta, v. 42, p. 1181-1198. restrial organic matter : American Asso- oils of Alberta , in Hills, L.V., ed., Oil
Powell,T.G.and Snowdon, L.R., 1979,Geo- ciation of Petroleum Geologists, Bul· Sands: fuel of the future: Canadian So-
( chemistry of crude oils and condensates letin , v. 66, p. 775-788. ciety of Petroleum Geologists, Memoir
from the Scotian Basin, offshore eastern Thomas , B.M ., Mtblle r·Pedersen, P., 3, p, 148·167.
(, Canada: Bulletin of Canadian Petro- Whitaker, M.F. and Shaw, N.D., 1985, Deroo, G. and Powell, T.G., 1978, The oil
leum Geology, v. 27, p. 453·466. Organic facies and hydrocarbon dis - sanddepositsof Alberta : their origin and
( Powell, T.G. and Snowdon , L.R. , 1980,Geo- tributions in the Norweg ian North Sea, geochem ical history, in Strausz, O.P.

o chemical controls on hydrocarbon gen·


eration in Canadian sedimentary
in Geochemistry in the Exploration ofthe
Norwegian shelf: Norwegian Petroleum
and lown , E.M., eds., Oil Sand and Oil
Shale Chemistry: Verlag Chemie, New
r basins, in Miall, A.D., ed., Facts and
Principles of World Petroleum Occur-
Society, p. 3-26.
Tissot, B.P., Bard, J.F. and Espitalie, J.,
York, p. 11·32.
Evans, C.R., Rogers, M.A. and Bailey,
rence: Canadian Society of Petroleum 1980, Principal factors controlling the N.J.L., 1971, Evolution and alteration of
Geologists, Memoir 6, p. 421-446. timing of petroleum generation , in Miall , petroleum in western Canada: Chemi-
c Powell, T.G. and Snowdon, L.R., 1983, A A.D., ed., Facts and Principles of World cal Geology, v. 8, p. 147·170.

o composite hydrocarbon generation


model: implications for evaluation of
basins for oil and gas: Erdol und Kohle-
Petroleum Occurrence : Canadian So-
ciety of Petroleum Geologists , Memoir
6, p. 143-152.
Krouse, H.R. and McCready, R.G.L., 1979,
Reductive reactions in the sulfur cycle,
in Trudinger, P.A. and Swaine, D.J., eds.,
( Erdgas-Petrochemie, v. 36, p. 163-170. van Krevelen, D.W., 1961, Coal: Elsevier, Biogeochemical Cycling of Mineral-
o Purcell , L.P., Rashid, M.A. and Hardy, LA.,
1979, Geochemical characteristics of
Amsterdam, 514 p.
van Krevelen, OW. and Schuyer, J., 1957,
forming Elements : Elsev ier, Amster-
dam, p. 315-368.
sedimentary rocks in Scotian Basin : Coal Science: aspects of coal constltu- Milner, C.W.O., Rogers, M.A. and Evans,
American Association of Petroleum tion : Elsevier, Amsterdam, 352 p. C.R., 1977, Petroleum transformations
c Geologists, Bulletin, v. 63, p. 87-105.
Rashid, M.A., 1978, The influence of a salt
Wedeking, K.W.and Hayes, J.M., 1983,Car-
bonization of Precambrian kerogens, in
in reservoirs: Journal of Geochemical
Exploration , v. 7, p. 101-153.
dome on the diagenesis of organic mat- Bjortby, M., Albrecht, P., Cornford, C., de Montgomery, D.S., Clugston, D.M., George,
ter in the Jeanne d'Arc subbasin of the Groot , K., Eglinton, G., Galimov, E., A.E., Smiley, G.T. and Sawatzky, H., 1974,
northeast Grand Banks of Newfound- leythaeuser, D., Pelet, R., Hullkotter, J. Investigation of oils in the Western
land: Organic Geochemistry, v. 1,p. 67- and Speers, G., eds., Advances in Canada tar belt, in Hills, L.V., ed., Oil
77. Organic Geochemistry 1981: Wiley, Sands: fuel of the future: Canadian So-
o Rash id, M.A ., 1979, Pristane-phytane
ratios in relation to source and diagene-
Chichester, p. 546-553. ciety of Petroleum Geology, Memoir 3,
p.168·183.
sis of ancient sediments from the lab- Te/ogenesis Rubinstein, I., Strausz, O.P., Spyckerelle,
rador shelf: Chemical Geology, v. 25, C., Crawford, R.J. and Westlake ,
o p.109-122.
Rashid, M.A., Purcell, L.P. and Hardy, LA.,
Bailey, N.J.L., Jobson, A.M . and Rogers ,
M.A., 1973a, Bacterial degradation of
D.W.S., 1977, The origin of the oil sand
bitumens of Alberta: a chemical and a
(, 1980, Source rock potential for oil and crude oil: comparison offield and expert- microbiological simulation study: Geo-

o gas of the east Newfoundland and la-


brador shelf areas, in Miall, A.D., ed.,
mental data : Chemical Geology, v. 11,
p.203-221.
chimica et Cosmochimica Acta , v. 41,
p. 1341-1353.
Facts and Principles of World Petroleum Bailey, N.J.L. , Krouse, H.R., Evans, C.R . Rubinstein , I. and Strausz, O.P., 1978, The
Occurrence: Canadian Society of Petro- and Rogers, M.A., 1973b, Alteration of biodegradation of crude oils: the origin
leum Geologists, Memoir 6, p. 589-607. crude oil by waters and bacteria: evi- of the Alberta oil sands, in Strausz, O.P.
Robin, PL, Rouxhet , P.G. and Durand, B., dence from geochemical and isotope and lown, E.M., eds., Oil Sand and Oil
o 1977, Characterisation des kerogenes et
de leur evolution par spectroscopie in-
stud ies: American Association of
Petroleum Geologists, Bulletin, v. 57,
Shale Chemistry: Verlag Chemie, New
York, p. 177·189.
frarouge, in Campos, R. and Goni, J., p. 1276-1290. Thode, H.G., Wanless, R.K. and Wallouch,

r. eds., Advances in Organic Geochemis-


try 1975:Enadimsa, Madrid, p. 693·716.
Bailey, N.J.L., Evans, C.R. and Milner,
C.W.O., 1974, Applying petroleum geo-
R., 1954, The origin of native sulphur
deposits from isotope fractionation
( , Rogers, M.A., 1980, Application of organic chemistry to search for oil: examples studies [Texas-louisiana] : Geo-
facies concepts to hydrocarbon source from Western Canada Basin: American chimica et Cosmochimica Acta, v. 5,
r
rock evaluation : Tenth World Petroleum Association of Petroleum Geologists , p.286-298.
Congress, Proceed ings, v. 2, p. 23·30 . Bulletin, v. 58, p. 2284·2294. Winters , J.C. and Williams , J.A., 1969,
Sajg6, C., McEvoy, J., Wolff, G.A. and Hor- Bustin, R.M., 1982, The effect of shearing Microbiological alteration of petroleum
vath, Z.A. , 1986, Influence of tempera- on the quality of some coals in the south- in the reservoir: Petroleum Transforma-
ture and pressure on maturation - I. eastern Canadian Cordillera: Canadian tions in Geologic Environments Sym-
,.... Preliminary report , in leythaeuser, D. Institute of Mining and Metallurgy, Bul- posium, American Chemical Society, Di-
and Rullkotter, D., eds ., Advances letin, v. 75, p. 76-83. vision of Petroleum Chemistry, Paper
in Organic Geochemistry 1985, Chandra , D., 1962, Reflectance and micro- PETR 86, p. E22-E31.
p.331-338. structure of weathered coals: Fuel, v. 41,
p.185·193.
c
204 Diagenesis Geoscience Canada Reprint Series 4 c
c
Winters, J.C., Williams, J.A. and Lewan , c
M.D., 1983, A laboratory study of petro-
leum generation by hydrous pyrolysis, in c
Bjonby, M., Albrecht, P.,Cornford, C., de
Groot, K., Eglinton, G., Galimov, E.,
c
Leythaeuser, D., Pelet, R., Rullkotler, J. (
and Speers, G. , eds ., Advances in
Organic Geochemistry 1981: Wiley, r
Chichester, p. 524-533.
c
Other References Cited in Text
c
Bily, C. and Dick, J.W.L., 1974, Naturally
occurring gas hydrates inthe Mackenzie
c
Delta, N.W.T.: Bulletin of Canadian Pe-
troleum Geology, v. 22, p. 340-352.
c
Choquette, P.W. and Pray, L.C., 1970, Geo- c
logical nomenclature and classification
of porosity in sedimentary carbonates: c
American Association of Petroleum
Geologists, Bullet in, v. 54, p. 207-250. c
Schmidt. V. and McDonald , D.A., 1979, The
role of secondary porosity in the course
c
of sandstone diagenesis, in Scholle, P.
and Schluger, P.R., eds., Aspects of Dia-
c
genesis : Society of Economic Paleon- c
tologists and Mineralogists , Special
Publication 26, p. 175-207. c
Teichmiiller, M. and Teichmiiller, R., 1982,
The geological basis of coal formation , c
in Stach, E., Mackowsky, M.-Th., Teich-
muller, M., Taylor,G.H., Chandra , D. and
c
Teichmiiller, R., Stach 's Textbook of
Coal Petrology: Borntrager, Berlin ,
c
p.5-86. c
(

Originally published in c
Geoscience Canada v. 11 Number 3 c
(September 1984)
Revised 1988 c
c
c
c
c
c
c
c
e
(

c
c
C
\.
C
(
c Determining Levels of Organic Diagenesis 205
c
c strata may be inferred. In the following Middleton, 1982) to greater than 5.5% at
( sections we summarize the literature a level equivalent to the lower green-
on quantification and modelling of or- schist metamorphic facies. As diagene-
( ganic diagenesis. Recent reviews and sis increases, vitrinite becomes pro-
( books that present the techniques in gressively more anisotropic and thus
greater detail include Heroux et a/. the standard deviation of measure-
( (1979), Brooks (1980), Durand (1980), ments increases. Typically, the mean
( Staplin et al. (1982), Bustin et a/. (1985), maximum vitrinite reflectance for each
Robert (1985) , and Tissot and Welte grain is recorded, which requires using
(1985). Some of the more widely applied polarized light and rotation of the micro-
Determining Levels of methods are outlined below. scope stage. Random (unpolar ized
( light) reflectance is much quicker to
Organic Diagenesis in
o Sediments and Fossil
METHODS OF QUANTIFYING
ORGANIC DIAGENESIS
measure and has a high correlation
coefficient with maximum reflectance
c Fuels
Both petrographic and chemical meth- (England and Bustin, 1986). The mean

o ods methods have been used to quan-


tify organic diagenesis (Figure 1;Tables
is typically determined from measure-
ments on 50 or 100 particles.
o A.M. Bustin
M.A. Barnes
1 and 2). The petrographic methods
have been developed mainly by coal
Vitrinite is derived from cellulose, lig-
nin and tannins, and is an abundant
W.C. Barnes petrologists and include vitrinite reflec- constituent of continental sedimentary
Department of Geological Sciences tance, liptin ite fluorescence, and ker- rocks (Stach et al., 1982). Even clastic
University of British Columbia ogen colour and translucency. marine rocks contain sufficient fine
o 6339 Stores Road Vitrinite Reflectance.
Vitrinite reflectance is not only the most
dispersed vitrinite (phytoclasts of Bos-
tick, 1979) to enable analysis after con-
o Vancouver, British Columbia V6T 2B4

INTRODUCTION
widely used but also the most reliable
and precise method of quantifying or-
centration by demineralization (using
HCI followed by HF) or light liquid meth-
( In an accompanying paper (this volume, ganic diagenesis . It provides a standard ods. Thus, vitrinite reflectance is appli-
p. 189-204), we outlined the types of scale against which other diagenetic cable to most sedimentary rocks, the
organic matter, their progressive diage- indicators can be compared. The term principal exceptions being coarse
netic transformations and concomitant " vit rinite reflectance" refers to the grained, permeable rocks in which the
chemical reactions and products. Inthis amount of light reflected from a polished percolation of oxygenated groundwater
second part, we review some of the surface of vitrinite , a common coal may lead to the oxidation of the vitrin ite,
c more accepted methods of quantifying
levels of diagenesis, correlate these dif-
maceral.
Vitrinite reflectance measurements
carbonates , evaporites and bitumen
impregnated rocks.
ferent methods with one another, and are made with a reflected light micro- Vitrinite reflectance offers a number
discuss the application of numerical scope equipped with a stabilized light of advantages as a measure of organic
models in predicting diagenetic state source, photometer and digital voltme- diagenesis: (1) it is a broadly accepted
o and basin history. ter for recording. A narrow band filter and standardized procedure (Ting,

c Because of both the complexity of


kerogen and its importance in the petro-
centered on 546 nm is placed between
the objective lens and the photometer.
1978; Davis, 1978; ASTM, 1980); (2)
vitrinite is sensitive to minor changes in
o leum and coal industries, considerable
research has been directed toward
The optical properties required of the
. microscope , and necessary accesso-
the level of diagenesis and matures in a
regular manner; (3) it is a microscopic
o quantifying levels of kerogen diage-
nesis (Durand, 1980) . Organic matter,
ries, are outlined in Bustin et al. (1983).
Reflectance is related to the refractive
method, so determinations are always
made on the same physical component;
o unlike mineral assemblages, rarely and absorptive indices of the material (4) vitrinite is a common constituent of
(
undergoes retrograde diagenes is. The by Beer's equation: many rocks or can readily be concen-
highest level of diagenesis reached is trated and isolated; and (5) the method
the level observed, regardless of whe- (/L - /Lo)2 + /Lk2 is applicable throughout the ent ire
ther the strata have been uplifted and range of diagenesis from recent sedi-
C (/L + /Lo)2 + /L2k2
exposedto lowertemperatures andpres- ments to metamorphic rocks of lower
l sures or to different groundwater chem-
istry. The only exception results from
where /L and k are the refractive and
absorptive indices, respectively, of the
greenschist facies.
Some of the limitations of the tech-
C the introduction of oxidizing agents vitrinite, and /Lo is the refractive index of nique are (1) recycled vitrinite may be
such as molecular oxygen or sulphate, the immersion oil. In practice , this rela- present, so that care must be taken to
which enable the bacterial degradation tionship is seldom if ever used, but a discriminate between separate popula-
and oxidation of organic matter. Inas- standard of known reflectance is com- tions ; (2) oxidation may reduce vitrinite
much as the level of organic diagenesis pared to the vitrinite. With increasing reflectance (Bustin , 1982) or, in rare
reached has been shown to be almost levels of diagenesis (and aromatiza- instances, increase reflectance (Mar-
entirely a product of temperature and tion) of organic matter, vitrinite reflec- chioni, 1983); and (3) vitrinite is rare in
time, it follows that if the level of diagen- tance increases regularly from a mini- Devonian and older strata because of
esis is known, the thermal history ofthe mum of 0 .15% (0.2% according to the absence of higher plants. Recent
(
206 Diagenesis Geosc ience Canada Reprint Series 4 r
r
studies have demonstrated the poten- spores , pollen , resin and cut in, auto- rapid shift to higher wavelengths and C
tial utility of reflectance measurements
of organic constituents in addition to
fluo resces when irradiated by ultravio-
let light. The intensity and fluorescent
loss of fluorescent intensity occurs at a
leve l of diagenesis equivalent to a
C
vitrinite. The reflectance of solid bitu- colours of the Iiptinite, although not well vitrinite reflectance of 0.8% to 0.9% C
men has been described and compared understood , are thought to result from (TeichmOller and Durand, 1983). Above (
to vitrinite reflectance by Jacob et al. excitation of 11" electrons in conjugated a level of diagenesis equivalent to a
(1985), and Ogunyami et a/. (1980) have systems (Cook, 1980). Fluorescent in- vitrinite reflectance of 1.2% , fluores - C
described the reflectance of pyrobitu- tensity and colour vary with the type of cent intensi ties are so low as to be
men. The reflectance of graptolites, Iiptinite and the level of diagenesis. unmeasurable . C
chitinozoans and acritarchs have also Studies by Ottenjahn et al. (1975), van
been shown to increase with increased Gijzel (1979), TeichmOller and Durand
Quantifying the fluorescent proper-
ties of liptinite entails exciting the sam-
C
levels of organic diagenesis (Teich - (1983) and others have demonstrated ple with ultraviolet light and recording C
muller, 1978; Goodarzi, 1985), although that with increasing level of diagenesis the intensities ofthe fluorescent colours
additional studies are required to define the fluorescen t intensity decreases and emitted in the visible range between C
their correlat ion with other maturation
indices.
there is a shift in colour from lower to
higher wavelengths. Relative to vitrinite
400 and 700 nm. The wavelength of
maximum intensity progressively shifts
C
Fluorescence Microscopy. reflectance the changes in fluores- with increasing levels of diagenesis C
Fluorescence microscopy is based on cence are somewhat irregular. At a re- and can be correlated with vitrinite re-
the premise that the liptinite component flecta nce between 0.35% and 0.5% the flectance. An alternative method now C
of organic matter, derived from algae , fluorescence changes rapidly. The most widely employed is measurement of the C
..... (
MET AGENESIS
I CATAGENESIS
I EOGENESIS DIAGENETIC LEV EL
...,
!!:~I llJ
act
en ge'-
Medium
volat ile ,. ,=';,~rb-b""m,~
I I
r-
ifj
I
I "ll
COAL RANK
C
:;!. I An t hracite a ct
~1lJ I ;fa
.~ 00
~. >
I I
; I ! C
!" ' I •IlJ - l bituminous High vol. bltum . I c:> I (j I
:
.. 01
-
0
.
0
e.>
0
...
0
I 'I
01
0
C
0
....0 VOLATILE MATTER
COAL (def)
w
C
36,000 36,000 29,000 23,000 17,000 CALORIFIC VALUE "" C
kJ/kg kJ/kg kJ/kg kJ/kg kJ/kg

,0.
. ,. 01
0. , !
-
0
.
01
... H 2O
e.>
01
....
01
!
MOISTURE (ash Iree)
Hydrogen (daf)
V1 C
C
"'H

Dry Gas
G):E
IlJCD
1lJ_ - - - -Oil and Gas - - - - - - - Early Gas
HYDROCARBON
GENERATION
'" C
. .. ww ..- -
- -- - - - " C

----
c.> 0 0 ~ 0 0 0 0 ~ VITRINITE
01
o b b b en 01
b Co
0
a.0 ....
0
c0 in
0
~
0
c..0 01
RE FLECT (R"m811 ...)
1100 SPORINITE (» 0 C
FLUOR., max~
no fluorescence ODD "'ll
700 -l
0 C
- cor SPORINITE ~ >
r-
C
---------
no fluorescence .. gg FLUOR .

., .'"
"'ll
., "~ Spectral
>
O'~
~ 3 quotient
..... >
:0 C
;: '"!.
0' dark dar k ~CD O'!! 0
0 ~
i'
......
n
brown-black
e.>
brown
e.> e.>
01:1.
:> e.>
~ 1lJ
0 :>
:>1lJ
:>
", .. IE
0'
- SPORE COLOUR
and TAl
m
-l
m
C
b a. :.. 0. b I CD",I 0
very dark brown to very pale ",ct
< CONODONT .....
.....
:0
(J) C
black pale yellow
black grey brown dark brown brown
-
ct~

-'" COLOUR and


C
1--01 ·1· ... ·1· e.>
·1· .. I.
·1·... 1
• 0'0 AL TERATlO N INDEX
IEIlJ
it (CAl)
..... C
- ...,
in 0

Actua l valu •• ahow


conalderable .catt.r about lin••
-
-- _ct
"'~
.,,0
ct'"
ct
'" 0.5 :t ATOMIC
1.0 0
1.1l
"-
RATIO
0
:D
,.
G) (
...

.... 01
... ..
e.> ..
...
:>

0'"

. ..
3
W
OZ
..... .... 0
"'I:)
e
01
()
0
0
0
0
0
0
o
01
0
0
(II

0
0
II

0
(/)
PYROLYSIS mm
:DO
00
I:):t
c
Ba••d on:
[(C 23-C31) odd + ~_.
(C25-~3)] !l: .ca
1.0
1.0 CARBON
..... mm
"" z~
en
l
2(C24 -C 32)even
a. ~c
::: g:
1.4
1.2
1.0
PREFERENC E
INDEX (CPI)
-i
:D
-<
c
C
Figure 1 Correlation of major organic maturation indices. The correlations shown are based on vitrinite reflectance. (Modified from (1) Barnes
et al ., 1984; (2,3,4,5,7) Teichmiiller and Teichmiiller in Stach et aI., 1982, p . 45 ,47; (6) Dow, 1977; (8,9) van Gijzel, 1979 and Teichmiiller and C
Durand, 1983; (10) Jones and Edison, 1978; (11) Epstein et al ., 1977; (12) Durand and Monin, 1980; (13) Espitalie e t aI., 1977b; (14) Allan and
Douglas, 1977). .
C
C
C
c
c Determining Levels of Organic Diagenesis 207
(
(
red/green ratio, Q (Stach et al. , 1982): (3) for interlaboratory correlation of in transmitted white light changes pro-
( results corrections must be made for gress ively. Such studies originated with
Q = relative intensity at 650 nm differences in microscope optics and palynologists, who observed changes
( sample background ; (4) with prolonged in the colour of pollen and spores from
relative intensity at 500 nm
( exposure to ultraviolet radiation, fluo- translucent and nearly colourless to
The use of fluorescence microscopy to rescent intensity may either decline or greenish yellow, yellow, amber, brown
( quantify diagenesis has both advan- increase; and (5) the precision of the and finally to black and opaque with
( tages and disadvantages. In samples method is less than that for vitrinite increasing diagenetic level (Gutjahr,
where vitrinite is absent, it provides an reflectance measurements. 1966; Correia, 1967; Staplin, 1969).
( alternative to vitrinite reflectance, and For quantitative fluorescence micro - An arbitrary numeric scale has been
in samples from rocks of low diagenetic scopy, a microscope equipped with a applied to these colour changes (Stap-
( level (R o < 0.3%), the vitrin ite reflec- photometer, similar to that described for lin, 1982) and has been standardized by
( tance is low whereas fluorescent inten- reflectance measurements, is required. use of a series of reference samples.
sity is high. In addition, measurements In addition, a stabilized high pressure One widely adopted scale is the "ther-
c are actually performed on that part of mercury lamp , ultraviolet filter, barrier mal alteration index" (TAl) proposed by

o the kerogen that can generate liquid


hydrocarbons rather than on the vitrin-
filter (to prevent scattered ultraviolet
radiation from entering the eye) and
Jones and Edison (1978; Figure 2).
The use of kerogen colour as an index
o ite, which is not generally considered to
be a source of liquid hydrocarbons and
variable grating filter (to enable inten-
sity measurements to be made on in-
of diagenesis has the advantage that
only standard palynological preparation
which may be reworked. The disadvan- dividual wavelengths) are required techniques and microscopic observa-
tages of fluorescence microscopy in- (Robert, 1985). tion are required. Palynomorphs occur
clude (1) the method is only applicable Kerogen Co/ouration. in most fine-grained sedimentary rocks
o to rocks of low diagenetic level; (2) there
are no widely accepted standards;
With increasing levels of organic dia-
genesis the colour of kerogen observed
so that recovery of sufficient material for
analysis is seldom a problem. The tech-
o
Table 1 Relative value of organic diagenetic indicators.

c Class
Optical
Technique
- vitrinite reflectance
Analysis Required
- microscopic
Precision
- excellent (standard)
Range of Application
- complete range of
diagenesis

c - Fluorescence - microscopic - moderate (requires further


study)
- up to RD = 1.2"10

- up to R. = 2.4"10
o - Palynomorph color -
- Conodont color
- microscopic
- microscop ic
- moderate
- moderate - complete range of

o Organic - Extractable organic matter - extraction-gas - moderate (?)


diagenesis
- to above zone of wet gas
( Geochemistry chromotography generation
- Carbon preference index - extraction-gas - moderate - diagenesis to zone of
c chromotography hydrocarbon generation
where CPI-1
- "10 Paraffins , aromatics, & - ext. -Iiq. chromatography

o polar compounds
- Glc profiles paraffins - ext. -gas chromatography - good within stratigraphic - diagenesis to zone of

o (Glc) sequence
see Table 2
hydrocarbon cracking
see Table 2

c.
r
- GC-MS profiles biological
markers
- ext. -gas chromatography-
mass spectrometry
- Light hydrocarbon analysis - extraction or head-space - poor - complete range
gas samples -Glc
( - Pyrolysis - heating and/or extraction - moderate at low levels of - complete range
and gas chromotography diagenesis
l - Ultimate analysis - separation and various - good at low levels of - complete range
chemical analysis diagenesis
6 - Proximate analysis - heating in-different - good at low levels of - complete range
atmospheres diagenesis
Physiochemical - Infrared Spectroscopy - separation and infrared - moderate-insufficient data - unknown
l - Electron Paramagnetic
spectrometry
- separation and EPR - insufficient data - unknown
Resonance
- C,H,S Isotopes - separation and mass- - insufficient data - up to Ro - 1.5
spectrometry
- Caloric value - separation and calorimetry - moderate-good at low - complete range
levels of diagenes is
208 Diagenesis Geoscience Canada Reprint Series 4

c
Table 2 Changes in biological markers with increasing diagenesis. C
C
--_~ Increasing maturity, as measured by increasing vitrinite reflectance or burial depth _
(
Bi910gical Configuration Geochemical Fossil Changes in Ratio (with increasing maturation)
Steranes
(
Ring alteration:
5,14,17aH(20R)-sterane 5aH,14~H,17~H(20R)-sterane2 (20R)-sterane: ~~/aa increases (Mackenzie et aI., 1980,
C
(see Fig. 4: 2a-e, h, i) (Fig. 4: 3a-e, h, i) 1983; McKirdy et el., 1983; Seifert and Moldowan, 1981,
1986; Philp, 1985)
C
5,14 ,17aH(20R )-sterane
(Fig . 4: 2a-e , h, i)
13~H,17aH(20R)-rearranged sterane
(diasterane)I.2.3 (Fig. 4: 6a-e, h, i)
«20R)-rearranged sterane)l5a-sterane increases (Pym et C
81., 1975; Seifert and Moldowan, 1978; Seifert et al., 1983)
5,14,17aH-sterane (Fig. 4 : 2g) Monoaromatic steranes (Fig. 4: 9g)2 MAI5a-steranes increases (Seifert et aI., 1983) C
Monoaromatic steranes
(Fig. 4 : 9g)
Triaromatic steranes
(Fig. 4 : 10g)
TNMA increases
(Seifert et el; 1983)
C
(Fig. 4: 4f) (Fig. 4 : 5f)
Triaromatic diasteranes2
(Mackenzie et al., 1982; 1983a; 1983b) C
Monoaromatic diasteranes TN(MA + TA) increases
(Fig . 4 : 7g) (Fig . 4 : 8g) (Mackenzie et el., 1981) C
Side chain isomerization:
5,14,17aH(20R)-sterane' 5,14,17aH(20S)-sterane2 2OS120R increases in aaa-steranes (Mackenzie et el.,
C
(Fig. 4: 2a-1) (Fig. 4: 2]-1) 1980,1981,1982, 1983a; McKirdy etal., 1983; Philp , 1985; (
Seifert and Moldowan, 1978, 1981, 1986; Seifert et aI., 1983)
5,14 ,17aH(20R)(24S)-sterane
(Fig. 4: 2b, d)
5,14,17aH(20R)(24R)-sterane2.3
(Fig. 4 : 2c , e)
24R'24S increases in aa(20R)-steranes (Mackenzie et aI.,
198O,1981,1983a)
C
13~H,17aH(20R)-diasterane' 13~':l,17al-!(20S)-diasterane2 20S120R increases in ~-diasteranes (Mackenzie ot al., C
(Fig. 4: 6a) (Fig. 4: 6J) 1980; Pym et al., 1975)
C
Hopanes
Ring alteration: C
17~H,21 ~H(22R)-hopane
(Fig. 4: 11m-q)
17aH,21 ~H(22R)-hopane
(Fig. 4: 12m-q)
~~-hopanes/(total hopanes) decreases to 0 (Mackenzie
aI., 1980, 1981; Philp, 1985; Seifert and Moldowan, 1980,
et C
17aH,21 ~H(22R)-hopane
1986) C
17~H,21 aH(22R)-moretane ~-moretane/a~-hopanedecreases (Mackenzie et al., 1980,
(Rg. 4 : 13m-q) (Fig. 4: tzm-q) 1981; Seifert and Moldowan, 1980 , 1986) C
17aH-22,29,30-trisnorhopane2 18aH-Cv trisnor-neohopane 1 C a TmfTs decreases2 (Seifert and Moldowan, 1978, 1980,
(Tm shown in Rg. 4: 14m) (Ts sHown in Fig . 4: 15m) 1981, 1986; McKirdy et al., 1983; Seifert et 81., 1983) C
Side chain isomerization:
17aH,21 ~H(?2R)~hopanefor 17aH,21 ~H(22S)-hopane 22S/22R increases in a~hopanes (Mackenzie at al., 1980,
C
C31 - C35 (Fig. 4. 12q) (Fig. 4: 12r) 1981,1983a; McKirdy etal., 1983; Seifert etal., 1979;
Seifert and Moldowan, 1980)
C
Porphyrins C
Free base C21- C 32 DPEP C a - C 32 ETIO porphyrin DPEPIETIO decreases (Mackenzie at al., 1980, 1981; Baker
(Fig. 5: 17) (Fig. 5: 18) and Louda ,1983, 1986; Barwise and Park, 1983) C
C2B- C32 Ni-DPEP
C27 - CM VO-DPEP'
Ca - C 32 Ni·ETIO
C a - CM VO-ETIO
Ni-DPEPlNi-ETIO decreases
VO-DPEPNO-ETIO decreases and Cv - CM shifts to C 30 - CSC)
C
Isoprenoids
C
(6R,10S) pristane (6R,10R) pristane + (6S, 1OS) (RS pristane)/(total pristane) decreases to 50% (final C
(Fig. 5: 22) pristane (Fig. 5: 23) mixture: RS :RR :SS = 2: 1: 1) (Mackenzie et al., 1980,
1981, 1983a; Volkman and Maxwell, 1986) C
C'S (3R,7R)-isoprenoid acid
(Fig. 5 : 26)
CIS (3S,7R) + (3R,7S) acids
(Fig . 5: 27)
RR'(total isoprenoid acids) decreases to 0 as acids iso-
merize and then decarboxylate to hydrocarbons c
C16 (4R,8R)-isoprenoid acid
(Fig. 5: 28)
C I I (4S,8R) + (4R,8S) acids
(Fig . 5 : 29)
RR'(total isoprenoid acids) decreases to 0 as acids iso-
merize and then decarboxylate to hydrocarbons
e
l
I Source parameter for oiVsource rock correlation C
2 Maturation parameter
3 Migration parameter C
• VO :0 vanadyl

c
c
(
c
c' Determining Levels of Organic Diagenesis 209
C'
c nique is applicable to levels of diagene- useof a light source illuminating at 3200 morphs. At the highest temperatures of
sis equivalent to vitrinite reflectances K and a "daylight" filter. An alternative diagenesis or metamorphism, the col-
from 0.15% to about 2.4%, and thus method of determining palynomorph our may change to an opaque white, if
( colour is the measurement of their
covers the range of petroleum genera- the partial pressure of oxygen is high
r tion and cracking. The major disadvan- translucency. Translucency measure- enough to permit oxidation ofthe graph-

c tage of the method is that it is subjec-


tive and only semi-quantitative. Palyno-
ments are made on specific taxa; at
least 30 measurements must be made
ite (Harris, 1979). The progressive col-
our changes havebeendivided intoeight

r morph colour is influenced by particle


thickness and initial pigmentation .
and averaged (Grayson, 1975).
In addition to palynomorphs, other
visually determined levels, giving acono-
dont alteration index (CAl)scale. CAlcan
c Standardization of sample processing, forms of kerogen display progressive be correlated with vitrinite reflectances

c microscope light source and reference


samples is required. Reworking of ker-
changes in colouration with increasing
diagenesis. Of particular importance
from Ro<0.8% to Ro>3.6% .
Conodonts can be recovered from

c' ogen from older rocks or caving of


boreholes may complicate the analysis.
are colour changes in conodonts. Cono-
donts, although composed mainly of
carbonates or shales by acid treatment
and heavy liquid or magnetic separation
c The only equipment necessary for TAl
determination is a transmitted light
apatite, contain organic matter which
changes sequentially from pale yellow
methods (Harris, 1979). The conodont
alteration index has the advantage that
microscope and a series of reference to black (Epstein et a/., 1977; Harris, the method can be used over a wide
o samples. In an attempt to refine the
method, Staplin (1982) suggested the
1979)with increasing levels of diagene-
sis, in a manner analogous to palyno-
diagenetic range (up to and including
the greenschist metamorphic facies),
c
c
c
o

r:

r:

Figure 2 Examples ofkerogen, illustrating the progressive change in colour with increasing level ofdiagenesis. Samples were prepared using
standard palynological techniques (Hel followed by HF) by Dr. G.E. Rouse. Photographs were taken in transmitted light.
(A) Sheet of leaf epidermis, on the left, with stomata and cuticle (colourless; TAl = 1). On the right is a reworked smooth-walled spore (yellow ;
TAl = 2). Magnification 600 x .
(B) Fragments of leaf, showing cell outlines. TAl = 2; magnification 1000 x .
(C) Mass of amorphous granular plant debris, slightly darker than (8). TAl = 2; magnification 1000 x .
(D) Smooth-walled spore with yellow-brown colour. TAl = 2.5; magnification 1000 x .
(E) Fragment of waxy leaf cuticle, amber-brown. TAl = 2.5; magnification 1000 x .
=
(F) Leaf fragment with brownish-yellow colour. TAl 2.75; magnification 1000 x .
(G) Leaf cuticle showing reddish-brown colour. TAl = 3.0; magnification 1000 x .
(H) Mesozoic pollen grain with dark brown wall. TAl = 3.8; magnification 1000 x.
(I) Same pollen type as (H), but completely carbonized. TAl = 4; magnification 1000 x .
c
210 Diagenesis Geoscience Canada Reprint Series 4 (

1.5
100 C
cr::
N
~"
I C
....
N I ~
II) • cr.
>- C
N
N 1.0 :r:
W
Z
a.
cr. C
0 50
<
a.
a.
a.
C
o
:r:
~.
0 5
w
a.
0
C
~ C
O-+--=---.----r--r--.----, 0 C
0.2 0 .4 0 .6 0 1.0
A VI TRINITE REFLECTANCE (%Ro) B VITR INITE REFLECTANCE (%Ro )
C
C
0.61 C
0.54
Pannonian Basin (Hod) 3 .3 C
3. ·1
z
0
15Ma f3 = 2 .0
3 .0
Z
Q
....
C
....
-e
!:::!
cr.
w
8 2 .8 -e
N
cr.
w
:!:
C
C
:!:
0
0
~
C
~
W
Z
W
Z
<
70· 7'· G C
<
cr.
a.
0 70·
C
W
.... :r:
CIJ
North Sea C
100Ma
0 0 C
C
0
AROMATIZA TION 0
0
AROMA TIZA TION
C
DIHYDROPORPHYRINS
C
100
10 0 80 80 40 20 0
1 3. 2
.....
... C
.....
..
I/) 0: Type III Kerogen C
-CP
CP
....E
20 0
~
w
cr.
....:!:
X
w
2.0 Bituminous
Coal C
E 30 :J
....
0
~ 1.5 C
-0

0
,J:J
500 -e
cr.
W
a.
w
zW C
'.-,
40 cr.
I
,J:J :!: :r: 1.0
.... C
::l
I/) ....W z
:r: 50 ~
-e C
....0.. 900 Z 0.5
W
I/)

.:
W
:r:
a.
C
0 80 ..J
>- 0.0 C
....:r:w
0 20 40
PORPHYRINS
80 80 100
:!:
0 .0 0.5 1.0 1.5
MEAN VITRINITE REFLECTANCE (%Ro)
2.0 2.5
c
E F e
Figure 3 Changes in biolog ical markers with increasing diage nesis. (
(A) Changes in side-chain isomeriz ation at C-22 for the C3 1 a(3-hopanes in Jurassic Kimmeridg e oil shales (Douglas et aI., 1983).
(8) Decrease in ratio of DPEP to total porphyrins in gilsonite with increasing reflectance (Barwise and Park, 1983).
(C) Changes in side-chain isomer ization atC·20 for the C2 9steranes for Pannon ian Basin sediments relati ve to the shif t from mono- to triaromatic
steranes. The Pannonian Basin is assumed to have formed by rapid extension 15 million years ago . Solid dots are observed values, with depths
shown in km; unde rlined values were calculated tram Mackenzie and McKenzie (1983; extension tactor ((3) '" 2.0).
c
(0) Changes in side-chain isomerization at G-22 for the C3 2 hopanes from North Sea sediments relative to the shif t from mono- to triaromatic
steranes; theoretical curves tor two extens ion factors ((3 '" 1.2 and 1.5) are shown; soliddots are observedvalues; under lined values at inter vals of
5°C were calculated from the model (Mackenzie and McKenzie, 1983). c
(E) Aromatization of dihydroporphyrins to DPEP with increasing depth and temperature in Black Sea sediments (Baker and Louda, 1983).
(F) Methylphenanthrene index first rises and then falls with increasing reflectance; dashed lines represent one standard deviation (Radke and
c
Welte, 1983).
<-
c
c.
c Determining Levels of Organic Diagenesis 211

r
and conodonts can be recovered from amounts of the compounds present, Generally, thermal alteration of bio-
pre-Devonian rocks where vitr inite is coupled with the extensive chemical logical markers increases with burial
rare or absent. Conodonts are, however, separation procedures employed, can depth and with increasing vitrin ite
( restricted in their stratigraphic range lead to a loss of material, oxidation or reflectance values (Figures 3a and 3b).
( from the Cambrian to the Triassic, and a chemical change in the individual Commonly used are a combination of
the technique, like palynomorph colour- compounds. Phthalates, which are parameters determined for compounds
atlon (TAl), lacks the refinement, preci- used as plasticizers, and naphthenic whose structures differ in thermal sta-
sion and acceptance of vitrinite re- compounds, from greases used in driJI- bility. This permits a more sensitive dis-
flectance as a diagenetic indicator. ing, are common contam inants (Powell , crimination of degrees of thermal matu-
1978). Biological markers are especially ration between samples in a strati-
GEOCHEMICAL METHODS useful in oil-source rock correlation. graphic sequence than is possible using
Organic geochemistry has also been Although the isolation and ident ification reflectance data alone . Because of their
used to determine degree of organic of individual organic compounds are widespread occurrence, structural spe-
diagenesis. A variety of geochemical both more expensive and time consum- cificity and stability, steranes, hopanes,
methods have been developed to iso- ing than measurement of vitrinite reflec- porphyrins, and isoprenoids are com-
late and investigate the soluble and tance, they too can be used for assess- monly used as biological markers.
insoluble fractions of organic matter in ment of the degree of diagenesis , Eogenetic and catagenetic changes
sediments and sedimentary rocks . particularly at very low and intermedi- that result in ring alteration and side
Petroleum geochemists (Durand, 1980, ate levels of maturity. chain isomerization are summarized in
p. 24; Waples, 1981, p. 2) define bitumen Biological Markers. Table 2 and Figures 4, 5 and 6.
as the fraction soluble in organic sol- The terms "biological marker" (Eglin- During early eogenesis, sterols
vents. Kerogen is defined by some as ton, 1969) and "geochemical fossil " [Figure 4: compound 1,side chain (A) =
all organic matter that is not soluble in (Tissot and Welte, 1984) have been used a-e, h, i] are converted by biologically
organic solvents (Durand, 1980, p. 27; to refer to organic compounds in sedi- mediated processes in the sediment to
Waples, 1981, p. 20) and by others as ments which reflect the chemistry of the the corresponding stanols and ster-
organic matter wh ich is insoluble in contributing organism, the effect of enes, which form steranes (Figure 4: 2,
both organic solvents and in aqueous depositional environment and the effect A = a-e, h, i); the aaa-steranes retain
bases (Tissot and Welte, 1984). As a of burial and subsequent maturation. their original biological configuration
great many methods have been devel- The carbon skeletons ofthe compou nds [5, 14, 17aH (20R)] in both the ring and
oped, only the most widely used wiJI be show little or no alteration from the pre- side chain (de Leeuw and Baas, 1986).
discussed. cursor forms; however, the effects of Depending on the biological precursor,
Extractable Organic Compounds. eogenesis and catagenesis are re- there can be some variation in the stereo-
The chemical composition of sedimen- flected in changes which may include chemistry of the alkyl side chain, par-
tary organic matter, including petro- (1)an alteration in stereochemistry; (2) a ticularly in marine sources (Scheuer,
r
leum, reflects both source material loss or change in functional groups; (3) 1973, 1978), but the more common ste-
("biological marker" compounds) and reduction and saturation; or (4) aroma- reochem istry has the R configura-
the level of diagenesis. Ultrasonication tization . Changes in the distribution and tion at C-20 (Figure 4: A = a-f) and a
or soxhlet extraction with organic sol- structure of biological markers are mixture of R (Figure 4: A = c.e) and S
vents (such as chloroform/methanol, used (1) to correlate oils with their (Figure 4: A = b, d) at C-24. The Rand S
benzene/methanol or dichloromethane) source rocks; (2)to evaluate the degree stereochemistry is defined in Figure 7.
is used to isolate extractable organic of maturation; and (3) to identify migra- These are the dominant forms in imma-
matter (EOM), the quantity of which is tion or biodegradation that may have oc- ture sediments. With increasing matu-
used as a bulk parameter. Because of curred during the diagenetic conver- ration , there is a shift to thermally more
the complexity of the extract and the sion of biological lipids to petroleum stable geochemical fossils. Isomeriza-
large number of organic compounds (Meinschein, 1983; see references in tion of the alkyl side chain occurs with
present, extensive chem ical separa- Table 2). Aecent in-depth reviews of bio- the shift from S to R at C-24, followed by
tions are necessary to isolate and iden- markers, their precursors and diagene- R to S at C-20. Alteration of the ring
tify the specific organic compounds sis, and their use as indicators of occurs with the formation of 5aH, 14,BH,
which are used as molecular parame- source, maturation, migration and bio- 17,BH steranes (Figure 4: 3). Aromatiza-
ters . Column chromatography, thin- degradation in petroleum exploration tion occurs with the formation of mono-
layer chromatography and adduction as have been published by Johns (1986), aromatics (Figure 4: 4, 7, 9) followed by
clathrates are used prior to analysis by Sohn (1986), Mackenzie (1984) and triaromatics (Figure 4: 5, 8, 10). An
high performance liquid chromatogra- Philp (1985: includes 373 mass spectra increase in rearranged steranes [dia-
phy (HPLC), gas-liquid chromatography indexed by molecular weight and for- steranes (Figure 4: 6)] relative to non-
(GLC) or on-line gas chromatography- mula). Biomarkers in coal are reviewed rearranged steranes (Figure 4: 2) re-
mass spectrometry (GC-MS). The small by Chaffee et at. (1986). flects both source and SUbsequent mi-
Figure 4 (next page) Eogenetic and catagenetic changes in steranes andhopanes. Note the use ofboth the Roman font A and the italic font Ron
this diagram. A refers to alkylside chains, whereas Rand S refer to the stereochemistry ofthe alkyl side chains. See Figure 7 for definition of Rand S.
The ring systems lie approximately in the plane of the page. The tilde symbol (- ) indicates the point of attachment of A groups to the ring. Solid
triangles indicate groups above the plane of the rings (in front of the page); broken triangles indicate groups below the plane of the rings (behind the
page) . If an "An is not shown, the group is a methyl. A solid circle indicates a (3hydrogen above the plane of the rings; an open circle indicates an ex
hydrogen below the plane of the rings ; ,r' indicates undefined stereochemistry.
STERANES
..
I\)
I\)
Biological Configuration Geochemical Fossil
R R

1. 2.
SaH, 14, 17{3H
EOGENESIS CAT AGENESIS

~ ~
• ....0
• R
HO ~o
STEROL R = a-e, h, i
'?~

R=
C 27
~,~
120R 241 a. ~. ~~~~1-;..
~-91-, .
Ring R
C 26
'''~.'''~c. 6.

~,
~.
./ ':' '" ~
R R e. ~
S R k.
CATAGENESIS
a

C2~~ /,~. yJyg. ~. CH3 R CH3

~.~~,~( -
10.

1 I h. r'V"ll. ..
H
HOPANES o
~.
(I)
~
C 27 R=H m. 11. (I)
UI
(ii '

C 26 CH 3 n.

C2~

C 30
-CH 2-CH 3

-CHCCH 3 )2
c.

p.
HOPANE
R=m-q ~
"to
'O\'O
f<,+-<c;.
~t-C)
r
CD'
::J
g
q. r.
13.
R
14 . ~
III

~~(CH1) ~
- CHI CATA- ~(CH2)n - CH J
::0
22R n GENESts
Ring C II _ S ~
n : 0 - 4 C 27 17aH
S'
....
Tm ~
ii)'
UI
~

nf'nnrn n~nnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnnn
r.
( Determining Levels of Organ ic Diagenesis 213

r
c
r:
PORPHYRINS
(
(
c
( EOGENESIS CATAGENESIS
..

25· - 40· C

(
18 .

DPEP ETIO
FREE BASE C 28 - 3 2 FREE BASE C 28 - 3 2
CHLOROPHYLL
ICHELATE
• Ni 2+

Free C 28 -32 Ni DPEP ~


- - -..... Free C 28 - 3 2 Ni ETJO c - C 32 - 36 Ni DPEP and ETIO


CATAGENESIS
Rele ••• ot:
~

S2~
zo!!
IU.
~~
EOGENESIS
8s.ci hound DPEP - - - - . . . Bound C 27 - 34 ETIO 5~
... -
' ;.
C 32 - 36 Ni DPEP and ETIO

Bound VO DPEP - - - -... Bound C 27 - 34 VO ETIO :< - C 30 - SO VO DPEP and ETtO

PHYTANE
'1I
20. z
.
o
-e
N

'"
IU
:I
o
'" RS : RR : $S
2 : 1 : 1
22.
PRISTANE

COOH COOH

24. 25 .
PHYTANIC ACID

z
(
o
..
N -COOH ISOPRENOID

B HYDROCARBONS
0::

IU~
:I-

~coo"-+I
J('6 ISOPRENOID ACID 28 .
I
~COOH
: ~ Cl:

Figure 5 Eogenetic and ca tagene tic changes in porphyrins and isopreno ids . Symbols are defined in Figure 4.
c
214 Diagenesis Geoscience Canada Reprint Series 4 c
(

gration and maturation effects (McKirdy product; it is thermally less stable than a(j(j -steranes and extended a(j-
(
et et., 1983; Seifert and Moldowan ,
1983, 1986); diasteranes are thought to
Ts, a neohopane. The 18aH-C 2 7 trisnor-
neohopane (Ts, Figure 4: 15) has a dif-
hopanes in immature hypersaline sedi-
ments, provid ing another route in addi-
C
arise from acid catalyzed ionic rear- ferent precursor and is more source tion to the thermal maturation of aaa- (
rangement of aa-steranes or sterols and specific. Thermal isomerization of the steranes or (j(j-hopanes. Biodegrada-
occur more commonly in oil shales than alkyl side chain in C 3 1 to C3 5 hopanes tion removes regular aa-steranes pre- C
in carbonate-sourced oils (McKirdy et
af., 1983). Table 2 and Figure 4 summar-
occurs with the shift in stereochemistry
from R (Figure 4: R = q) to S (R = r) at
ferentially to diasteranes and diaster-
anes containing a side chain with 20S
C
ize some of the parameters commonly C-22. The sensitivity of the SIR ratio for preferentially to those with a side chain (
used in oil-source rock correlations and the a(j-C 3 1 hopanes to changes in containing 20R . The source rock is (
as measures of thermal maturation , vitrinite reflectance in the region Ro 0.4 depleted and migrated oil is enriched in
migration and biodegradation. through 0.6 is shown in Figure 3: a. the ,s(j-(20R)-steranes relative to the C
Seifert and Moldowan (1981)have de- Chemical , microbial and biodegrad- aa-(20R)-steranes due to the greater
fined a maturity index for non-migrated ing processes, differences in biogenic mobility of the (j,s-(20R)-steranes. C
oils (Biomarker I) and a migration index
(Biomarker II) from a first order kinetic
sources, and migration can affect the
concentrations of biomarkers common-
Mackenzie and McKenzie (1983) and
Mackenzie (1984) have used side-chain
C
plot of the side chain isomerization in ly used to assess maturity. As a result, isomerization in steranes and hop- C
C2 9 steranes (Figure 4: 2112f) relative to these indicators of maturity must be anes, and the shift from monoaromatic
ring alteration (Figure 4: 3f12f). used with care; several different matu- to triaromatic steranes, to model the C
The hopanoic acids and hydro- rity ratios are necessary to confirm a thermal, subs idence and uplift histor- (
carbons occur in cyanobacteria (blue- trend. An increase in a(j-hopanes is ies of stretched basins. Their ideas are
green algae) and bacteria and are com- usually taken as a measure of increas- discussed in the section on numerical C
monly used as indicators of microbial ing maturity; however, 17aH, 21(jH methods.
sources in sediments (Ourisson et a/., extended hopanes with 22R in the side Early in eogenesis, porphyrins aris- C
1979). The ISIS-hopanes (17,sH, 21,sH;
Figure 4: 11, R = m through q) with the
chain have been found in lichens, fungi
and sphaghum peat (Philp, 1985). In-
ing from chlorophyll (Figure 5: 16) lose
magnesium and the phytol side chain
C
R configuration at C-22 (R = q) are creases in monoaromatic steranes, dia- (Figure 5: 19); phytol in turn may be C
the more common biological isomers; steranes, and (j(j-steranes relativetothe oxidized to the corresponding acid (Fig-
lesser amounts of (ja-moretanes occur aa-steranes are all used as measures of ure 5: 24), reduced to the C20 isoprenoid
C
(17(jH, 21aH; Figure 4: 13, m through q). increasing maturity. The ~3,5 stera-
dienes can give rise to "1\' -ring mono-
phytane (Figure 5: 20) or shortened to C
With increasing thermal maturity, both pristane (Figure 5: 21) in the guts of zoo-
the (ja-moretanes and the (j(j-hopanes aromatic steranes in shallow or im- plankton. In each case, the original bio- C
undergo ring alteration and form the
a(j-hopanes (Figure 4: 12, m through q);
mature sediments and have formed
"C"-ring monoaromatics under labora-
logical configuration is retained. With
thermal maturation, both pristane and
C
alteration of (j(j-hopanes to a(j-hopanes tory simulation; ~5 sterenes may give phytane isomerize from RS (Figure 5: 20 C
occurs prior to the zone of oil generation rise to either "C"-ring monoaromatics and 22) to a mixture ofthe RS, RR and SS
(Mackenzie et et., 1980; Seifert and or, under acid conditions, to the re- isomers (Figure 5: 21 and 23). Similar C
Moldowan, 1980, 1986). A decrease in
the Tm/Ts ratio can be used as a mea-
arranged diasterenes. Recent hyper-
saline sediments have been shown to
thermal isomerization of the biological
configuration to an isomeric mixture
C
sure of increasing maturity for oils or contain relatively uncommon sterols C
source rocks derived from a common with a double bond in the ~7 position.
organic source (Seifert and Moldowan, Ten Haven et a/. (1985, 1986) have sug- H3C,~H H 3C,~H €
1978,1986; Philp, 1985). The 17aH-C2 7
hopane (Tm, Figure 4: 14) shares the
gested that the alteration and hydro-
genation of these ~ 7 sterols and of
A
R2-- R,
A
R,-R 2
C
same precursors as other hopanes and extended hop-17(21)-enes may lead to R
Clockwise
S
Anliclockwise
C
may be an acid-catalyzed diagenetic the formation of side-chain isomerized
C
PHENANTHRENES C
Figure 7 Rand S stereochemistry for a c
tetrahedral carbon atom with four different
groups attached. Alkyl groups R, and R2/ie e
CATAGENESIS
in theplane of the page; themethyl group lies
in front of the page and hydrogen behind.
c
• Group R, is larger than group R2> which in
turn is larger than a methyl group. Size is
c
defined by the total atomic number of the c
attached groups. Thus , -COOH >
-CH(CH:J2 > -CH2CH3 -CH3 • In R stereo- c
chemistry, group size decreases in a clock-
wise direction; in S stereochemistry, it c
Figure 6 Catagenetic changes in phenanthrenes. decreases in an anticlockwise direction.

(
C
c
c Determining Levels of Organic Diagenesis 215
c
(
occurs in the isoprenoid acids (Figure 5: methyl homologues. Methyl groups resembling natural crudes and contain-
c 24 goes to 25; 26 goes to 27; 28 goes
to 29); with increasing burial depth, the
adjacent to the ring junction [1-methyl-
phenanthrene (Figure 6: 30) and 9-
ing a smooth distribution of n-alkanes
up to about n-C 3 0 was produced from
(
C'5 and C'6 acids (Figure 5: 26 and ethylphenanthrene (Figure 6: 31)] the torbanite, with 35% by weight being
( 28) disappear as they decarboxylate to are thermally less stable than methyl converted to oil by 300°C. As with hy-
the corresponding hydrocarbons. Other groups in non-adjacent positions drous pyrolysis, olefins were not pro-
( sources of isoprenoids include car- [2-methylphenanthrene (Figure 6: 32) duced, and it was established that
( otenoid pigments, archaebacterial cell and 3-methylphenanthrene (Figure 6: water is not required forthe formation of
wall lipids and bacteriochlorophyll 33)], which are SUbject to less steric petroleum under laboratory conditions
( (Volkman and Maxwell, 1986). hindrance. TwoMPI indexes are defined: if very slow rates of heating are used.
After the successive loss of magne- An important result of this study is that
C' sium and of phytol and other functional MPI 1 = 1.5 (2-MP + 3-MP) products very similar to natural crude
o groups from the porphyrin ring, hydro-
gen is lost and the free base is aro-
(P + 1-MP + 9-MP)
oils were produced in only a few years,
but at temperatures considerably
matized under anoxic conditions to higher than for natural crudes. Thus,

o DPEP (Figure 5: 17) with a range in


carbon number from C2 8 to C3 2 . The
MPI 2 = 3 (2-MP)
(P + 1·MP + 9-MP)
very long periods of time may not be as
important in organic maturation as was
o aromatization of the porphyrin ring
system with the formation of DPEP A strong positive correlation with reflec-
formerly thought, a conclusion sup-
ported by the recent development of oil
o takes place in the temperature range of tance is observed for MPI 1, which in- fields with Pleistocene source rocks.

o 30°-60°C for samples taken from the


8IackSea(Figure3E). 8akerand Louda
creases within the oil window, but then
decreases abruptly with the onset of the
Hydrous Pyrolysis.
In hydrous pyrolysis, petroleum gen-
o (1983, 1986) also suggest that reche-
lation with Ni to form Ni-DPEP occurs
wet gas zone below (Figure 3: F). A
"calculated reflectance" for coal and
eration is simulated in the laboratory
by heating source rocks in a liquid
between 30 0C and 60°C. DPEP is kerogen extracts can be derived from water phase for 1-5 days at tempera-

o thermally altered to the ETIO form (Fig-


ure 5: 18) with the loss of ring V. As a
the MPI (Radke and Welte, 1983):
ForRo <1.35%: Rc = 0.6(MPI1) + 0.4
tures less than the critical point of water
(374°C);in a closed system pressuresof
c result, increasing thermal maturation is
evident and can be measured by de-
For Ro > 1.35%: a, = -0.6(MPI1) + 2.3
20-35 MPa develop (Winters et et.,
1983;Lewan, 1985).Three fractions are
o creases in the DPEP/ETIO ratio , which
occurfirstforthe free bases and then for
The "calculated reflectance" shows a
linear correlation with Ro and makes it
recovered: (1) an expelled oil phase
floating on the water surface; (2) a ben-
(
their Ni chelates. The decrease in the possible to compare the thermal matu- zene-methanol soluble bitumen re-
o DPEP/ETIO ratio for porphyrins iso- rity of sediments with their extractable covered by soxhlet extraction of the

o lated from gilsonite is shown in Figure


38. 8arwise and Park (1983) suggest
organic content.
Pyrolysis.
crushed sample and (3) kerogen iso-
lated after HF-HCI demineralization of
c porphyrins are a sensitive index to
maturation in the region Ro 0.4 to 0.6,
Pyrolytic methods have recently been
developed that mimic in the laboratory
the crushed sample. The expelled oil
contains a smooth distribution of
c and can be used in algal rich samples the natural generation of petroleum. n-alkanes with the production of few

o that commonly lack vitrinite particles.


Finally, kerogen-bound DPEP and its
Saxby et a/. (1986)heated samples of a
Permian torbanite (algal kerogen) and a
alkenes or volatiles. Based on the rela-
tive proportions of kerogen, bitumen
o vanadyl chelates are released , and sub-
sequently altered to the ETIO form; with
Tertiary lignite under nitrogen in closed
tubes, raising the temperature 1°C per
and expelled oil generated during
hydrous pyrolysis, four stages of petro-
o both the addition and loss of alkyl side weel< from an in itial temperature of leum generation have been defined

o chains, a series of C3 0 to Csaporphyrins


is produced.
100°C over a period of six years. The
samples had previously been extracted
(Lewan, 1985):
1. Pre-oil stage: the original immature
( A methylphenanthrene index (MPI) with chloroform and demineralized with sample prior to heating;
has been developed to measure in- HCI and HF, but, unlike hydrous pyroly- 2. Incipient oil stage: bitumen increases
c creases in coal rank and thermal matu-
ration in sediments (Rad ke et a/. ,
sis experiments, they were dry. Samples
were removed and analyzed at one-year
to a maximum, with a corresponding
decrease in kerogen, but little produc-
( 1982a,b; Radke and Welte, 1983). Me- intervals. Vitr inite reflectances in the tion of expelled oil;
8 thylphenanthrenes (MP) and naphtha-
lenes, and dimethylphenanthrenes are
lignite samples increased in a regular
manner from initial values of about 0.3
3. Primary oil generation: bitumen
decreases; expelled oil reaches a
extracted and separated by liquid chro- to 2.8 at the final temperature of 400°C. maximum;
matography. The quantity and distribu- NMR spectra on the same samples 4. Post-oil stage: cracking and produc-
( tion of methyl homologues of phenan- were typical of bituminous coals after tion of pyrobitumen .
threne (P) and naphthalene in the C'5+ heating for two years (200°C) through The end of the incipient oil stage and the
soluble organic fraction are strongly four years (300°C), but resembled stage of primary oil generation are de-
'-..- controlled by changes in rank. At Ro = anthracites in the samples heated to fined by a maximum followed by a de-
0.9, the Iiptinite fluorescence ratio (0) higher temperatures. The lignite sam- crease in the amounts of bitumen and
shows a sharp increase; a correspond- ples did not generate significant quan- expelled oil, respectively.Hydrous pyro-
ing shift occurs in the structure of the tities of oil at any temperature, but oil lysis is currently a very active subject.
,-
c
216 Diagenesis Geoscience Canada Reprint Series 4 c
(

There are many recent investigations and algae have a large odd CPI, some bans are minor or absent (Leythaeuser
c
assessing the advantages and limita- marine sponges, freshwater aquatic et al., 1979). At the diagenetic level of c
tions of hydrous pyrolysis as a means
of modelling the effects of thermal ma-
plants, ferns, lycopods, fungi, yeasts
and bacteria havesmalloddcarbon pref-
oil generation, the light gases contain
a great many compounds in the C2 c
turation on steroids (Lewan et et.,
1986), stable carbon isotopes (Lewan,
erences. Hydrocarbons from the cuti-
cles of higher plants rangefrom n-C 2 3 to
through C4 range, whereas at the meta-
genic level methane is again the domi-
c
1983), exchange reactions with heavy n-C 3S' with n-C 29 or n-C a, dominant; nant gas (Figure 1) and gasoline range c
water (Hoering, 1984), biomarker iso-
merization and mineral catalysis (Eglin-
ferns, lycopods, fungi, yeasts and bac-
teria commonly have a broader carbon
hydrocarbons are minor. Bailey et al.
(1974) used such methods in their eval- c
ton et et., 1986),and on the generation of
aromatic compounds (Rowland et al.,
range. Algae have majorcomponents at
n-C'71 n-C 17: , (heptadecane with one
uation of maturation in western Can-
ada. The ratio of C2 through C4 gasesto
c
1986), hopanoids (McEvoy and Giger, double bond), n-C,s or n-C'3 (Gelpi et total gases (C, through C4 ) has also c
1986) and cycloalkanes (Fowler et et.,
1986).
al., 1970). Fungi have n-C 2 9 dominant,
while yeasts and bacteria show both
been found to indicate diagenetic level
and was used in maturation studies in c
Total Extractable Organic Matter. unimodal and bimodal distributions the Canadian Arctic (Snowdonand Roy, c
The ratio of the total amount of extrac-
table organic matter (EOM) to total
with both n-C,s and n-C 2 7 as dominant
hydrocarbons (Weete, 1974; Bird and
1975; Monnier et aI., 1983); a number
of other ratio methods for gasoline c
organic carbon (TOC) is related to the
level of diagenesis attained by sedi-
Lynch, 1974). During eogenesis,the CPI
approaches unity in hydrocarbons
range hydrocarbons have also been
used to assess maturity and migration
c
mentary rocks (Tissot and Welte , altered by the aerobic and anaerobic (Thompson, 1979; Snowdon and c
1984). Although the EOM/TOC ratio is
high in immature surface sediments,
decay of algae (Cranwell, 1976). Cran-
well suggested that both an odd-even
Powell,1982) .
Light gases are extracted from cut- c
it decreases rapidly during early eo-
genesis as humic substances form ,
index near unity and an increase in
hydrocarbons in the region of n-C,s to
tings or core samples by heating, treat-
ment with acid or mechanical disaggre-
c
then increases during catagenesis n-C 2 6 are indicators of microbial altera- gation in a blender, followed by c
with the formation of hydrocarbons
from the cracking of kerogen. At higher
tion. Brooks et a/., (1976) found that
extraction method can influence car-
collection of the gases from the head
space above the sample and analysis c
diagenetic levels, the loss of aliphatic,
alicyclic and low molecular weight aro-
bon preference index. Hydrocarbons
released by a simple solvent extraction
by gas chromatography.
As a measure of diagenesis, light
c
matics and the formation of the rela- at a nearly neutral pH had a large even hydrocarbon analysis has the advan- c
tively less soluble large, multi-ring
aromatic compounds results in the
CPI, reflecting higher plant sources,
whereas those bound into microbial cell
tages that both extraction and ana-
lysis are rapid, requiring only simple c
progressive decline of EOM/TOC . The
method is limited by the dependence of
walls and released only by acid hydro-
lysis of sediments have much smaller
techniques, and can be applied over
a wide diagenetic range. The method
c
the EOM/TOC ratio not only on the level odd-carbon preferences, reflecting lacks precision, however, and is influ- c
of diagenesis, but also on the type of
organic matter present. In addition, the
bacterial alteration. As catagenesis
progresses thermal degradation of ker-
enced by migration. The best resultsare
obtained when a sequence of strata are c
ratio will decrease during catagenesis
if hydrocarbons migrate out of their
ogen generates alkanes with no odd-
even preference, so the CPI of extrac-
examined. c
source rocks. Tocompensate for some table hydrocarbons approaches unity. GEOCHEMISTRY OF KEROGEN c
of these problems, the ratios of aroma-
tics to saturated hydrocarbons and of
Thus, CPI may be used as an indicator
of maturation (Figure 1).
Pyrolysis.
Pyrolysis involves heating a sample
c
aromatics to total EOM have been used Light Hydrocarbon Analysis. at a pre-selected rate in an inert atmo- c
(Albrecht et a/., 1976); both ratios
increase with increasing levels of dia-
The abundance and type of light hydro-
carbons, defined as having between
sphere and monitoring the type and
amount of gases evolved. A number of c
genesis, but are affected by the type of
kerogen present. These ratios are most
one and eight carbon atoms, have been
found to reflect the level of diagenesis.
methods of determining diagenetic
level from pyrolysis products have been
c
significant if used in a sequence of As living organisms produce few light proposed. One such method is based c
strata of constant kerogen type, where
values from different stratigraphic lev-
hydrocarbons except for methane
(Oremland et al. , 1982),most hydrocar-
on the Rock-Eval~ instrument (Espitalie
et al. , 1977a,b, 1985; Peters, 1986), c
els, or from a given stratigraphic unit
down into or across a basin, can be
bons in the C2 through Cs range reflect
the diagenetic level of the kerogen in
which is essentially a furnace with an
on-line gas chromatograph. The analy-
e
compared.
Carbon Preference Index.
the rocks. Light hydrocarbons are com-
monly divided into two groups by petro-
sis simulates maturation (diagenesis)
by progressively heating rock samples
c
Carbon preference index (CPt) is the leum chemists : C, through C4 gases to temperatures up to 550°C. Three
(
ratio of odd carbon number to even car- from head space gases or drill cuttings, types of gases have been recognized, (
bon number n-alkanes in extractable and gasoline range (Cs through Cs) based on the temperatures at which
organics. During eogenesis CPI is con- compounds from cores and cuttings. At they are evolved: (S,) hydrocarbons l
trolled by the alkane ratio present in low diagenetic levels (eogenesis), the already present in the sample, which
precursor organisms (Barnes and light gases consist mainly of biogenic are evolved below 300°C; (S2) hydro-
<.
Barnes,1978). While most higher plants methane and gasoline range hydrocar- carbons generated by thermal cracking
c
C Determining Levels of Organic Diagenesis 217
l
(
between 300°C and 550°C; and (S3) content of rocks , commonly by use of a groups, a loss of saturated hydrocar-
C CO2 (Figure 8). The level of diagenesis
is obtained from the Sl/S2 ratio and the
C-H-N analyzer. H/C and O/C ratios are
plotted against one another to give a
bons, the formation and removal of aro-
matic C-H groups, and the evolution of
c'
(
temperature at which maximum gener-
ation of S2occurs. A plot, analogous to a
"van Krevelen" diagram which can
then be used to determine both ker-
hydroxyl and ether groups (Rouxhet
et al., 1980). Quantification of these
"van Krevelen" diagram (atomic H/C ogen type and level of diagenesis. Dur- groups gives a measure of the level of
( versus O/C; Barnes et et. , 1984), is ing eogenesis, oxygen is lost as CO2 diagenesis attained and of kerogen

c obtained byusingthe "hydrogen index"


(S2/TOC) versus the "oxygen index"
(S3/TOC) and can be used to estimate
and H20 , which results in a decrease in
the O/C ratio with little corresponding
change in the H/C ratio; catagenesis
type , as the initial proportions of these
groups is a function of the precursors
organisms. The advantage of the
(
both the kerogen type and the degree results in a rapid loss of hydrogen in the method is that sample preparation,
c of maturation. The production index,
defined as S/(Sl + SJ, increases with
form of hydrocarbons, causing a de-
crease in the HIC ratio.
apart from isolation of the kerogen, is
simple. The kerogen is separated and
depth as the amount of free hydrocar- The advantage of ultimate analysis is then pressed into a KBr pellet which is
o bons (Sl) increases . The production
index thus increases with the level of
that it provides both a measure of diage-
netic level and kerogen type. The disad-
used in the infrared spectrophotometer.
Only a few hundred milligrams of ker-
diagenesis. vantages are that kerogen must be sep- ogen are required for the analysis. The
The advantages of the Rock-Eval arated before analysis by using HCI and disadvantages of the method are that it
method are that no sample preparation HCIIHF digestion of mineral matter and, is only semi-quantitative and is not
c is required and that level of diagenesis,
oil and gas potential and hydrocarbons
less commonly, by specific gravity or
hand-picking methods . Mixed kerogen
widely used.
Electron Paramagnetic Resonance.
o already present are all determined. Dis- types also give results that are difficult Electron paramagnetic resonance

o advantages include problems associ-


ated with mixed kerogen types of vary-
to interpret, and the method lacks
accuracy.
(EPR) studies of kerogen assess the
presence of free radicals (polyatomic
o ing chemistry and with the presence of Infrared Spectroscopy. moieties with unpaired electrons). All

o carbonates, which evolve CO2 during


pyrolysis.
The infrared spectroscopy of kerogen
enables the quantification of the main
kerogens give EPRspectra that depend
on the type of kerogen and the level of
o Ultimate Analysis.
"Ultimate" analysis involves the deter-
functional groups present. As the level
of diagenesis increases, there is a pro-
diagenesis. With increased diagenetic
level the number of free radicals first
o mination of the elemental C, Hand 0 gressive loss of carboxyl and carbonyl increases to a maximum and then de-
clines because of recombinations that
( occur as the mean distance between
T max
c (increases with
degree of diagenesis)
the radical groups decreases. The dia-
genetic level atwhich free radicalsare at
( l a maximum varies with the type of ker-
Generated
o Hydrocarbons
ogen. An advantage of EPR is that it is
non-destructive, but the technique has
several disadvantages. The kerogen
must be separated carefully from the
( Distilled CO 2 from rest of the rock; impurities such astrace
Hydrocarbons
o Organic
Matter
metals affect the spectra. Also, the type
of kerogen affects its EPR spectrum ,
o and the EPR signal decreasesover long
periods of geologic time and in post-
o mature rocks as free radicals combine

o (Brooks, 1980).
Carbon Isotope Studies.
c The stable carbon isotope composition
reflects both the initial c5 13C value of the
C' organic source material (DeNiro, 1983)
and the isotopic fractionation that takes
INCREASING TEMPERATURE place during diagenesis (Hayes, 1983).
l 82
TOC = Hydrogen Index
83
TOC = Oxygen Index
Higher plants utilizing the C3 pathway
(Calvin cycle), which constitute the bulk
of terrestrial organic matter, have mean
8 1/8 1 + 8 2 = Production Potential ~ ex Level of Diagenesis c5 13C values of -27 permil (%0), with
82 a spread from about -23%0 to -34%0
(Galimov, 1985; Schidlowski, 1986).
Figure 8 Rock-Eva" pyrolysis products. The three gas pulses shown can be used to Most organic matter formed in marine
characterize the kerogen type present, the level of organic diagenesis and the type of and lacustrine environments derives
hydrocarbons the kerogen will yield. (Modified from Espitalie at aI., 1977a; and Miller, 1982). from the eukaryotic algae, which have
c
218 Diagenesis Geoscience Canada Reprint Series 4 c
c
013C values which mainly range from carbon is determined by difference. magnetic resonance, differential ther- c
around -18%0 to -31%0, with a mean of The method has been used for many
years for analysis of coal and is widely
mal analysis, fluorescence spectra of
extractable organics and thermogravi-
c
about -22%0, significantly heavier than
that of higher plants. The cyanobac- accepted, well documented and stand- metric analysis,havebeenusedin matu- c
teria, which are the principal formers of
stromatolites, are even heavier, with a
ardized (ASTM 03172-73, 1979). The
disadvantages of the method are that
ration studies. The applicability of these
methods has not been fully evaluated, c
mean of around -16%0. Heterotrophs are the technique is useful only for organic however, and they are not widely used. c
isotopically similar to the organic sub-
strates they use. Many lignites show
rich rocks, such as coals, and for ker-
ogen separates. Kerogen type affects
Correlation between diagenetic
indicators. c
considerable variation in the isotopic
composition of their macrolithotypes,
the results and,while this is not a signifi-
cant factor in coals, which are generally
The correlation between the main dia-
genetic indicators discussed in this
c
but, at higher coalification levels, coals composed mainly of type 3 kerogen, review is shown in Table 1 and Figure 1. c
lack this variability, suggesting that
isotopic homogenization takes place
other organic rocks commonly contain
a mixture of kerogen types, leading to
All relationships are based on estab-
lished or estimated correlations with c
during coalification (Schoell, 1984).
Petroleum source rocks commonly
results that are difficult to interpret.
Caloric Value.
vitrinite reflectance.
c
show considerable regional isotopic The caloric (heating) value of organic PREDICTIVE DIAGENETIC MODELS c
variation, which is generally thought to
reflect variations in terrestrial and
matter increases at higher levels of dia-
genesis in response to decreased
Models to predict the levels of organic
diagenesis attained with depth were ini- c
aquatic inputs. moisture and volatile content and in-
creased relative amounts of fixed car-
tially developed to determine the occur-
rence of the liquid (oil) window in time
c
During thermal maturation there is a
preferential breaking of 12C_12C bonds bon. Caloric value is generally deter- and space (Landes, 1967) or the degree c
with respect to 12C_13C bonds, so that
the remaining kerogen is enriched in
mined with a bomb calorimeter; it is
commonly used as a technique for
of coalification (Karweil, 1956). Subse-
quent studies have shown that the level c
13C whereas the expelled liquids and
gases have more 12C. As thermal matu-
determining coal rank, but can be used
to determine the diagenetic level of any
of organic diagenesis, when interpreted
in the context of burial history, can be
c
ration continues, the reservoir of iso- organic rich rock. The method has the used to interpret the thermal history of c
topically light methyl groups is depleted
and more of the heavier methyl groups
advantage that it is standardized
(ASTM 02015-77, 1974) and has been
strata. Early studies assigned particu-
lar temperatures to the liquid window. It
c
are subject to cracking. As a result, the widely applied to coals. Disadvantages is now widely recognized (but see Neru- c
013C of methane generated at higher
levels of diagenesis increases, and
of the method include the necessity for
correcting for mineral matter in the
chev in Bostick, 1979) that the thermal
history (both temperature and time) c
the difference in isotopic composition
between the gases and the original ker-
rocks and that kerogen type influences
caloric value, a significant factor for
must be considered. Numerical models
and graphical techniques have been
c
ogen decreases. The carbon isotope rocks other than coal. developed to predict organic matura- c
trend toward lighter (more negative)
values for gas relative to oil, which in
Other Methods.
A number of other techniques, such as
tion from an assumed thermal history or
to determine the thermal history from c
turn is lighter than source rock kero-
gen, is widely used for oil-source rock
nuclear magnetic resonance, proton measured levels of organic diagenesis.
c
correlation. VITRINITE
. '"
Ro ci -o
ci
r-,
ci
CD
ci 3 ~
0
N
0
.,;
o 0
..; W"i -0" %RoMa c
Proximate Analysis.
Proximate analysis determines the : 2~
SCALE IN MILLION YEARS
0 o 00 0 c
c
M ... on 0
-IL
N
240
fixed carbon, ash, volatile and moisture I Vh ",0
contents of kerogen containing rocks.
The technique has been used most ex- 200
I

~
/1
1..1::/
// 1/ ~
~ I ~ c
tensively for the analysis of coals, but
can also be used on kerogen separated cP ~ v: V / .....11 / ),1 c
from other rocks. With an increasing w
DC
~
160
I
I
V
V
V /' .....1.1
t%:~ 1/ ..... '"
/ /
c
level of diagenesis there is an increase
in fixed carbon and a corresponding
«
....
ffi
e,
120
._- -- l/
I.;
~I':
V
V c
decrease in volatiles and moisture in the
organic matter.
~
~ 80 ",
V V
i.;' ~ ~~
:,...-
v.

i> ~
. / ...... ~
./
e
Proximate analysis involves heating
the sample to a low temperature (about 40
.......... ~ V ...... c
110°C) to determine moisture, heating
io--'..... !-' ~ (
to intermediate temperatures in an inert
atmosphere to determine volatile con-
o l
tent, followed by heating to high temper- Figure 9 Correlation between temperature, time and level of organic diagenesis (mean l
atures in a stream of oxygen to oxidize maximum vitrinite reflectance, RaJ. The dashed line shows an example in which organic
all remaining organic matter so that the matter exposed to temperatures of 100°C for 10 Ma would have an expected level of
residual ash may be determined. Fixed maturation equivalent to an Ro of 0.56%. (Modified from Bustin et aI., 1977).
C
L
c./
C Determining Levels of Organic Diagenesis 219
C'
( .
Models of organic diagenesis fall into genesis. Shibaoka and Bennett (1977) Many recent studies have attempted
r:
two broad groups, numerical models used a graphical technique similar to to refine the numerical models of
and comparative models. Numerical that of Hood et al. (1975), but related organic diagenesis by consideration of
( models are based on reaction kinetics, thermal history directly to vitrinite such factors as kerogen type and by
whereas comparative models utilize reflectance rather than to LOM. use of empirically determined activa-
established relationships between dia- Numerical calculations. From a tion energies and appropriate fre-
( genetic level and known thermal history consideration of first-order reaction quency factors (Tissot and Espltalie,
in one set of strata to predict either the kinetics (Arrhenius equation) and from 1975; Tissot and Welte, 1985). These
( thermal history or levels of diagenesis empirical data on activation energies, approaches facilitate evaluation of not
,-
in another set of strata where the diage- Lopatin (1971; see also Lopatin and only the degree of diagenesis, but also
~
netic levels have been measured or Bostick, 1974; Waples, 1980; Cohen, the proportion of the kerogen which
J which are known to have had a similar 1981) showed thatthe rate of maturation was transformed to hydrocarbons.
thermal history. Comparative models doubles with every 1Q°C increase in Tissot and Welte (1985) havedescribed
0 can also be used to extrapolate mea- temperature (an exponential relation - the model in detail, and Chiaramonte
0 sured levels of diagenesis to higher or
lower strata.
ship) but increases only linearly with
time. Lopatin's method calculates inter-
and Novelli (1986) have applied the
techniques to modelling maturation of
0 Numerical Models. val maturation by integrating the length source rocks in northern Italy.
of time spent by the stratum in each Using numerical models, it is possi-
0 Graphical methods. Models de-
1QoC temperature interval. The total ble to predict the approximate level of
e,..., veloped to predict levels of organic dia-
genesis during a predetermined or
assumed thermal history are based on
maturation (diagenesis) is the sum of
the interval maturation:
maturation from the thermal history of
the strata (Figure 10). Predicting the
~
first-order reaction kinetics and thus thermal history from a single matura-
"mu
0 approximate the Arrhenius equation TTl = 2: (dT.){r·), tion level is difficult becausemany com-
(Huck and Karweil, 1955):
."", binations of time and temperature will
yield the same maturation level. Where
K = A e(·E/RT), where TTl = time-temperature index;
measured maturation levels are avail-
0 where K = reaction rate, A = a fre-
nm a x = highest 10°C interval; nm ln =
lowest 1Q°C interval; ~Tn = time (Ma)
able through a stratigraphic succes-
quency factor, E = activation energy, R
0 = gas constant, and T = absolute tem- spent by strata in each 1QoC interval;
sion, however,they can be compared to
calculated maturation gradients (rather
and r = 2, assuming rank doubles for
perature. Huck and Karweil (1955) than a single point) to infer the thermal
each 1O°Crise in temperature. Lopatin
r: assumed an activation energy of 35 history. This method involves calculat-
L- (1971) set n = 1 for the 1QO°C to 110 0C
kJ 'mol-' for the entire range of coal- ing maturation gradients using a range
r-.. interval. At lower temperatures, n is
ification (for a complete discussion and of geothermal gradients or depths of
zero or negative, and, at higher temper-
solution of the Arrhenius equation, see burial and matching the calculated
atures, n is greater than 1. Lopatin's
Welte and Yukler, 1980). Karweil (1956) curves with the measured curves (Fig-
method enables periods of uplift and
combined empirical rank data (diage- ure 11). Using this method, it is possible
0 netic level) and theoretical calculations
subsidence to be considered, so that
to estimate paleogeothermal gradients
the entire thermal history is used in
0 to relate the level of coal diagenesis to
thermal history (Figure 9). This relation-
calculating the maximum level of dia-
(or paleo-heat flow) irrespective of the
absolute level of maturation. Such a
D ship between rank and thermal history
genesis attained by a stratigraphic hori-
zon that was deposited at time = O. For
method has been used by Bustin (1984)
has SUbsequently been modified to estimate paleo-heat flow in the
0 (Bostick, 1973)to better fit established
calculations by computer, the following
Bowser Basin of northern British
r: generalized relationship is more suita-
'-"
relationships. Bostick (1973)suggested Columbia and by England and Bustin
ble (McKenzie, 1981):
r: that the activation energy used by Huck (1986b)to interpret the effects of thrust
'-' and Karweil (1955) predicts too fast a . faulting on organic maturation in the
0 reaction rate for coalification at low lev-
els of diagenesis (Ra < 0.6) and too slow
TTl = f
10
2(T(11 -'0.5Y'O dt southeastern Canadian Cordlllera.
Other Canadian studies utilizing
C a rate at higher levels. Lopatin-type models include Kalkreuth
r Bostick (1973, 1979) adapted Kar- where T(t) is temperature (0C) as a func- and McMechan (1984)and Hughes and
weil's (1956) method to regions with tion of time (t) from the time of deposi- Cameron (1985) in the Cordillera, and
r varied thermal histories. Castano and Bustin (1985) in the Arctic Archipelago.
tion (to)to the present (tp ) .
,
\......
Sparks (1974) and Hood et al. (1975)
proposed a graphical relationship
Using the data presented by Waples
(1980), the following relationship
Kerogenisthe product of manychem-
ical reactions, which act at different
r: between thermal history and an arbi- between TTl and mean maximum rates on a complex mixture of organic
..... trary scale of diagenesis to define a vitrinite reflectance may be defined: compounds. Its reflectance (and fluo-
r:
"Level of Organic Maturation" (LOM). rescence) is a physical property which
'---' Ro = -0.10528 log TTl + 0.20647
,- They further suggested the use of an develops asthe sum of all these temper-
'-, "effective heating time", which they (log TTI)2 + 0.5011 (r2 = 0.99) . ature-dependent reactions, and thus is
defined as the time during which the Ro is not defined by this equation if TTl affected by differences in source mater-
'- values are less than 3. An example of ials and their reaction rates as well
rock is within 15°C of its maximum tem-
'-,
perature, in predicting the level of dia- Lopatin's method is shown in Figure 10. as by temperature history (Jones et

"-
(
220 Diagenesis Geoscience Canada Reprint Series 4 (
c
aI., 1984). As a result, calibration of lar first-order reaction which follows heat flux , time , depth, the quartz-elay C
vitrinite reflectance scales is empirical,
and differs from basin to basin. By
Arrhenius' Law; (4) the reactions are
free of matrix effects; if mineral cata-
content and estimates of the extension
factor ({3) from sediment thickness
C
selecting specific chemical reactions as lysis occurs, the number of active sites (Sclater and Christie, 1980; Wood, 1981; C
a basis for modelling, Mackenzie and is assumed to be large relative to the McKenzie, 1981). Kinetic parameters
McKenzie (1983) developed a model concentration of reactant and the reac- for the chemical reactions are indepen- C
which reflects kinetic effects of thermal
diagenesis in stretched basins, but is
tion is pseudo first order. While the side-
chain isomerizations are reversible, the
dent of basin history while calculated
temperatures are dependent on basin
C
independent of variations in deposi- aromatization is irreversible. Activation age and extension. These values are C
tional history or in organic precursors. energies (E), and frequency factors (A) used to generate theoretical curves for
An intramolecular chemical change, are derived from Arrhenius plots of the isomerization relative to aromatization C
which is temperature dependent, but
independent of the source or of other
logarithm of the rate constants versus
the reciprocal of the borehole tempera-
from equations for the change in rates
with temperature and time in a subsid-
C
chemical reactions, is measured for sin- tures. Rate constants (k) and 0, the ratio ing basin. The fit of observed values for C
gle chemical compounds. of the forward to reverse reaction for the extent of reaction and borehole tem-
Side-chain isomerization in steranes side-chain isomerizations are derived peratures or depth are shown for the
C
and hopanes and the shift from mono- from the ratio of products to reactants North Sea (Figure 3D) and the Panno- C
aromatic (M] to triaromatic steranes measured by GC·MS for samples from nian Basin of Hungary (Figure 3C).
[T] , are used to monitorthe subsidence the North Sea and the Pannonian Plots of hopane relative to sterane iso- C
and thermal history of stretched basins
in the North Sea and the Pannonian
Basin . Kinetic parameters are esti-
mated as:
merization are independent of the basin
thermal history.
C
Basin (Hungary), and to model subsi- A = 1.8 X 101 4 s-1, E = 200 kJ· mot-t for Mackenzie and McKenzie's model C
dence and subsequent uplift in the the aromatization; has the advantage that it is based on
Lower Saxony Basin (West Germany) A = 0.006s-1,E = 91 kJ'moJ-1,O = 1.174for kinetics that measure rates for known C
and the Paris Basin (France). Three
reactions which occur prior to and dur-
side-cnaln isomerization in steranes;
A = 0.016s", E = 91 kJ . rnol-', 0 = 1.564
single reactions rather than on the
unknown multiple reactions that cause
C
ing the early stages of oil formation were for side-chain isomerization in changes in vitrinite reflectance. By C
selected: (1)the shift from R to S at C-20 hopanes . using pairs of reactions, it is possible to
in the C2 9 sterane (Figure 4: 2f goes to Temperature was calculated from equa- determine uniquely the entire time-tem- C
21); (2) the shift from R to S at C-22 in the
0I{3-C 3 2 hopane (Figure 4: 12q goes to
tions forthe variation in temperature in a
subsiding basin (McKenzie, 1978;
perature history of a basin, inclUding
not only its development, but also sub-
C
12r); and (3) the shift from the 501 or 5{3 Mackenzie and McKenzie, 1983) with sequent uplift after extens ion. As a C
C29 monoaromatic (Figure 4: 4f) to the
C2 8 triaromatic steranes (Figure 4: 5f) .
B C
These three reactions fit the following Interval .... Interval Cumulative Time Hydrocarbon C
assumptions reasonably well: (1) initial (oC) TTl TTl (Ma B.P.) Generation
concentrations of thermal products are
20.0 30.0 2-8 0.04 0.0 140.00
C
small or negligible in immature sedi-
ments; (2) thermal alteration spans the
30.0 40.0 2-7 0.08 0.1 130.00 C
40.0 50.0 2-6 0.16 0.3 120.00
oil window; (3) a single reactant gives
50.0 60.0 2-5 0.31 0.6 110.00 C
rise to a single product in a unimolecu-
60.0
70.0
70.0
80.0
2-4
2-3
0.63
1.25
1.2
2.5
100.00
90.00
C
(

,-,_-
80.0 90.0 2-2 2.50 5.0 80.00
90.0 100.0 2-1 5.00 10.0 70.00
.e
~
100.0 110.0 2-0 10.00 20.0 60.00
C
G
110.0 100.0 2-0
2-1
10.00 30.0 50.00 C
oS 100.0 90.0 5.00 35.0 40.00
:I: 90.0 80.0 2-2 2.50 37.5 30.00 (
l-
e,
W .- 80.0 70.0 2-3 1.25 38.7 20.00
c
.-
Q
70.0 60.0 2-4 0.63 39.3 10.00
60.0 50.0 2-5 0.31 39.6 0.0 e
A
-- -. Log,. TTl
Total Maturation = 39.6 TTl
Equivalent Reflectance = 0.86 Ro %
(

Figure 10 Lopatin's method of predicting organic maturation.


(A) shows the burial history of a hypothetical rock that was deposited at 140Ma, buried to 3000m by 60 Ma, followed by uplift to 1000m by time = O.
c
(B) (right) shows the method ofincrem.entaHy calculating maturation using Lopatin 's formula (see text) for the burial history shown in (A). With a (
constant geothermal gradient of 30°C per km and a surface temperature of 20°C, the present maturation of the rock would be 39. 6 TTl or O. 86%
Ro• If the oil window is assumed to occur between 0.500/0and 1.35% Ro (Dow, 1977), then the rock entered the oil window at a depth of about C
2600m at 72 Ma and still lies within the oil window.
L
C
C
(
c Determining Levels of Organic Diagenesis 221
c
C' result, the time of hydrocarbon genera- (diagenetic) gradients of strata from the Cerro Prieto geothermal field. In both
r..... tion may be determined and compared Canadian Rocky Mountains and Foot- studies, known temperatures and coali-
with the time of formation of suitable hills with the gradients established in fication levels from boreholes were
C' traps, creating a powerful tool for petro- the Peel area of the Netherlands (see used to develop general relationships
C leum exploration.
Comparative Methods.
also Nurkowski, 1984). Bustin et al.
(1977) noted the similarity of coalifica-
between thermal history and coalifica-
tion levels so that the thermal histories
c Comparative methods have been used tion gradients of Tertiary strata from the of adjacent areas can be interpreted.

r to establish either levels of organic dia-


genesis if thermal history is known or
Canadian Arctic with those of the Tejon
area of California reported by Castano
On the assumption that changes in
level of diagenesis with depth are pre-
c assumed, or thermal history if the level and Sparks (1974). Because of the sim-
ilar burial histories of strata in both
dictable, a number of studies have
extrapolated measured diagenetic gra-
c of organic diagenesis is known. These
methods are based on the premise that areas, Bustin et al. (1977)assumed that dients to higher or lower stratigraphic

c a given thermal history will result in par-


ticular levels of diagenesis, and have
the paleogeothermal gradient in the
Arctic was similar to the known geother-
levels. This method was applied by Hac-
quebard (1977)to calculate the amount
c been used mainly to compare geother-
mal gradients in different areas. Hac-
mal gradient of the Tejon area.
Similar methods were used by Bunte-
of overburden that had been removed
by erosion from the Mannville coals in
quebard and Donaldson (1974), for barth (1978) in the upper Rhine graben southern Alberta. Hacquebard extrapo-
example, compared the coalification and by Barker and Elders (1979) in the lated the moisture content ofthe coals at
the surface to that prior to burial, based
o REFLECTANCE on assumed changes in moisture con-
tent with depth.
o 0.2 0.3 0.4 0.6 0.8 1.0 1.5 2.0
o SUMMARY
Quantification and modelling of organic
o diagnesis have proven to be useful in

o assessing petroleum source rocks, coal


rank and thermal history of strata. A
o
r:
large number of methods have been
utilized to quantify organic diagenesis.
Almost all involve detailed and generally

o 1 expensive analytical procedures and


require isolation or at least concentra-
tion of either the kerogen or bitumen
prior to analysis. At present, the most
c
r: - E
widely accepted and precise method
methods are petrographic: vitrinite re-

o

-.::J:.

J:
l-
2
flectance, fluorescence and kerogen
colour. Of these, fluorescence micro-
scopy and kerogen colour are only use-
ful for a limited range of diagenesis (less
e..
o W
C Increasing
than 1.2% Ra ) and vitrinite reflectance,
although useful for the entire range of
o Gradient diagenesis, has its greatest utility only
in Carboniferous and younger strata.
r
(calculated)
A large number of geochemical
0, methods have been developed.Ofthese
3 ultimate analysis, proximate analysis
cr , and caloric value are best suited to coal,
where the relative abundanceof kerogen
is high. One of the most useful methods
of evaluating finely dispersed organic
matter is by the pyrolysis method pro-
posed by Espatalie et al. (1977a,b) which
4....L. --:-_--..:L.- -.L._ _ ~
provides an indication of diagenetic level
and kerogen type without requiring
concentration of the organics. A number
Figure 11 M~thod of predicting paleogeothermal gradients or paleo-heat flow based on
organic maturation. Maturation gradients are calculated iteratively using a Lopatin-type method
of geochemical techniques, such as car-
with varying temperatures, subsidence rates, etc. until the slope (in metres per log cycle) of the bon preference index (CPI), total ex-
calculated gradient is the same as the measured gradient. In the example shown, the pa/eo- tractable organics and light hydrocar-
geothermal gradient would be between 20°C and 30°C. The method requires knowledge of the bon analysis, are influenced by the type
burial history of the strata. of organic matter present and by
c
222 Diagenesis Geoscience Canada Reprint Series 4
(
C
migration and thus are most useful for Durand , B., 1980, ed., Kerogen : insoluble eds. , Aspects of Diagenesis : Society of
C
resolving the relative degree of diagen- organic matter from sedimentary rocks :
Editions Technip, Paris .
Econom ic Paleontologists and Miner-
alogists, Spec ial Publication No. 26,
C
esis in astratigraphic succession . While
isolation and identification of individual 15papers on the petrography, chemistry p.17-43 . C
and diagenesis of kerogen. Bustin, A.M., 1982, The effect of shearing
organic compounds are more expen-
sive and time consuming than measure-
Heroux, Y. , Chagnon, A. and Bertrand, R., on the quality of some coals in the south- C
1979,Compilation and correlation of major eastern Canadian Cordillera: Canadian
ment of vitrinite reflectance, biological thermal maturation indicators: American Institute of Mining and Metallurgy, Bul- C
markers can be used for a more sensi-
tive assessment of diagenesis, es-
Association of Petroleum Geologists, Bul-
letin, v. 63, p. 2128-2144.
letin, v. 75, p. 76-83 .
Davis, A., 1978, The reflectance of coal, in
C
pecially at low and intermediate levels
of maturity. In addition, they are now
Johns, R.B., 1986, ed., Biological Markers
in the Sedimentary Record: Elsevier,
Karr, C., Jr., Analytical Methods for Coal
and Coal Products: Academic Press,
C
commonly used in oil-source rock cor- New York, 364 p. New York, v. 1, p. 27-81. C
relation and as measures of thermal 10 papers on precursors, diagenesis and England, T.D.J. and Bustin, A.M., 1986a,
maturation, migration and biodegrada- use with fossil fuels. Thermal maturation of the Western C
Meinschein, W.G., 1983, ed., Organic Geo- Canadian Sedimentary Basin south of
tion. Geochemical techniques which
chemistry of Contemporaneous and An- the Red Deer River - I: Alberta Plains: C
have not been totally assessed as to
their ut ility as diagenetic indicators
cient Sediments: Society of Economic
Paleontologists and Mineralogists,
Bulletin of Canadian Petroleum Geol-
ogy, v. 34, p. 71-90.
C
include infrared spectroscopy, electron
paramagnetic resonance and nuclear
Great Lakes Section , Short Course
notes, 143 p.
Goodarzi, F., 1985, Reflected light micro-
scopy of chitinozoan fragments: Marine
C
magnetic resonance. Such methods re- Philp, A.P., 1985, Fossil Fuel Biomarkers: and Petroleum Geology, v. 2, p. 72-78. C
quire highly specialized equipment that applications and spectra: Elsevier, New Jacob , H., Hiltmann, W., Wehner, H.,
is not readily available outside major York, 294 p. Raschka, H. and Weiser, T., 1985, Dis- C
Includes 373 mass spectra . perse, feste Erdolbitumina als Migra-
research centres.
Models of organic diagenesis have Robert, P., 1985, Historie geothermique et tions - und Maturitatsind ikatoren im Rah- C
been developed to predict levels of
diagenese organique: Bulletin des Cen-
tres Recherches Exploration-Produc-
mender Erdol-/Erdgas Prospektion .
Eine Modellstudie in NW-Deutschland:
C
organic diagenesis and have also been
used to interpret thermal history of
tion Elf-Aquitaine, Memoire 8, 346 p.
Sohn, M.L. , 1986, ed., Organic Marine Geo-
Deutsche Gesellschaft fur Miner-
alolaissenschatt und Kohlechemie E.V.,
C
strata where the level of diagenesis is
known. Although the accuracy of the
chemistry: American Chemical Society, Projekt 267. C
Symposium Series 305, 428 p. Jones,J .M., Davis, A., Cook, A.C., Murchin-
models has not been fully tested , it is Stach, E., Mackowsky, M.-Th., Teichmiiller, son, D.G. and Scott, E., 1984, Provin- C
now possible to predict diagenetic lev- M., Taylor, G.H., Chandra, D. and Teich- cialism and correlation between some
els and thermal history which compare muller, A. , 1982, Stach 's Textbook of properties of vitrinite: Journal of Coal C
favourably with measured values. One
of the most useful methods is that ini-
Coal Petrology: Gebriider Borntrager,
Berlin, 535 p.
Geology, v. 3, p. 315·331.
Marchioni, D.L., 1983, The detection of
C
tially proposed by Lopatin (1971), which Staplin, F.L., Dow, W.G., Milner, C.W.O.,
O'Conner, 0.1., Pocock, SA, van Gijzel ,
weathering in coal by petrographic,
rheolog ic and chemical methods : Inter-
C
predicts that the level of diagenesis
increases exponentially with tempera-
J.P., Welte, D.H. and Yukler, M.A ., 1982, national Journal of Coal Geology, v. 2, C
How to Assess Organic Maturation and p.231-259.
ture and linearly with time . Paleotemperatures: Society of Eco- Ogunyami, 0., Hesse, R. and Heroux, Y., C
nomic Paleontologists and Mineralo- 1980, Pre-orogenic and synorogenic
REFERENCES gists, Short Course No. 7, 289 p. diagenesis and anchimetamorphism in C
General
Tissot, B.P.and Welte, D.H., 1984, Petroleum
Formation and Occurrence, Second Edi-
Lower Paleozoic continental margin
sequences of the northern Appala-
C
Barnes, M.A., Barnes, W.C. and Bustin,
tion: Springer-Verlag, New York, 699 p.
Waples, D., 1981, Organic Geochemistry for
chians in and around Quebec;City, Can-
ada : Bulletin of Canadian Petroleum
C
A.M ., 1984, Chemistry and evolution of
organic matter: Geoscience Canada,
Exploration Geologists: Burgess Pub-
lishing Company, 151 p.
Geology, v. 28, p. 559-577.
Teichmuller, M., 1978, Nachweis von Grap-
C
v. 11, p. 103-114.
Brooks, J., 1980, ed., Organic Maturation
tolithen periderm in geschieferten Ge- C
Vitrinite, Graptolite, Chitinozoan and steinen mit Hille Kohlenpetrologisches
Studies and Fossil Fuel Exploration: Bitumen Reflectance methoden: Neues Jahrbuch fUr Miner- C
Academic Press, Toronto, 441 p. alogie, Geologie und Palaeontologie,
22 papers covering organic maturation American Society for Testing and Materials Monatshefte 7, p. 430-477.
and kerogen description.
Brooks, J. and Welte, D., 1984, eds .,
(ASTM) , 1980, Microscopical deter-
mination of the reflectance of the Fluorescence
e
Advances in Petroleum Chemistry, v. 1: organic components in a polished speci- (
Academ ic Press, Toronto, 344 p. men of coal: American Society for Test- Cook, A.C., 1980, Optical techniques forthe
Bustin, A.M. , Cameron, A.A., Grieve, D.A.
and Kalkreuth, W.O., 1985, Coal Petrol-
ing and Materials, Philadelphia, Stand- examination of organic matter in oil C
ard 02798-79, 4 p. shales, in Cook, A.C. and Kantsler, A.,
ogy, its principles, methods and applica-
tions: Geological Association of Can -
Bostick, N.H ., 1979, Microscopic mea- eds., Oil Shale Petrology Workshop: C
ada , Short Course Notes Volume 3,
surement of the level of catagenesis of
solid organic matterin sedimentary rocks
Keiraville Kop iers, Wollangong, Aus-
tralia, p. 1-15.
C
273 p.
A description of methods and applica-
to aid exploration for petroleum and to
determine former burial temperatures-
l
tions of kerogen analysis. a review, in Scholle, P. and Schluger, P. A., C
(
C
c
c Determining Levels of Organic Diagenesis 223
r
r>
'-- Ottenjann, K., TeichmQller, M. and Wolf, M., Conodont Colour
c 1975, Spectral fluorescence measure-
Barker, C., 1974, Pyrolysis techniques for
source-rock evaluation: American Asso-

c ments of sporinites in reflected light


and their applicability for coalification
Epstein, A.G., Epstein, J.B. and Harris,
L.D., 1977, Conodont Color Alteration-
ciation of Petroleum Geologists, Bul-
letin, v. 58, p. 2284-2294.

c studies, in Alpern, B., ed., Petro-


graphie organique et potential petrollsr:
an index to metamorphism: United
States Geological Survey, Professional
Barnes, M.A. and Barnes, WC., 1978,
Organic compounds in lake sediments,
Paper 995, 27 p.
C· C.N.R.S., Paris, p. 49-65.
Robert, P., 1981, Classification of organic Harris, A.G., 1979, Conodont color altera-
in Lerman, A., ed., Lakes: chemistry,
geology and physics: Springer, New
( matter by means of fluorescence: appli- tion, an organo-mineral metamorphic York, p. 127-152.
cation to hydrocarbon source rocks: index, and its application to Appalachian Barwise, A.J.G. and Park, P.J.D., 1983,Pe-
C International Journal of Coal Geology,
v. 1, p. 101-137.
Basin geology, in Scholle, P. and
Schluger, P.R., eds., Aspects of Diagen-
troporphyrin fingerprinting as a geo-
chemical marker, in Bjortby, M., Albrecht,
TeichmQller, M. and Durand, B., 1983, Fluo- esis: Society of Economic Paleontolo- P., Cornford, C., de Groot, K., Eglinton,

c rescence microscopical rank studies on


Iiptinites and vitrinites in peat and coals,
gists and Mineralogists, Special Pub-
lication No. 26, p. 3-16.
G., Galimov, E., Leythaeuser, D., Pelet,
R., Hullkotter, J. and Speers, G., eds.,
and comparison with results ofthe Rock- Perry, WJ., Wardlaw, B.R., Bostick, N.H. Advances in Organic Geochemistry
Eval pyrolysis: International Journal of and Maughan, K., 1983, Structure, bur- 1981: Wiley, Chichester, p. 668-674.
c Coal Petrology, v. 2, p. 197-320.
van Gijzel, P., 1979, Manual of the techniques
ial history, and petroleum potential of
frontal thrust belt and adjacent foreland,
Bird, C.W and Lynch, J.M., 1974, Formation
of hydrocarbons by micro-organisms:
and some geological applications of fluo- southwest Montana: American Associa- Chemical Society Reviews, v.3,
rescence microscopy: American Associa- tion of Petroleum Geologists, Bulletin, p.309-328.
tion of Stratigraphic Palynologists, 12th v. 67, p. 725-743. Brooks, P.W., Eglinton, G., Gaskell, S.J.,

c Annual Meeting, Dallas, 55 p.

Kerogen Colour
Geochemical Methods
McHugh, D.J., Maxwell, J.R. and Philp,
R.P., 1976, Lipids of Recent sediments,
part I: Straight-chain hydrocarbons and
Albrecht, P., Vandenbroucke, M. and Man- carboxylic acids of some temperate
Correia, M., 1967, Relations possibles entre dengue, M., 1976,Geochemical studies lacustrine and sub-tropical lagoonall
l'etat de conservation des elements on the organic matter from the Douala tidal flat sediments: Chemical Geology,
figures de la matiere organique (micro Basin (Cameroon) - I. Evolution of the v. 18, p. 21-38.
fossils palynoplanctonologiques) et extractable organic matter and the for- Chaffee, A.L., Hoover, D.S., Johns, R.B.
l'exlstence de gisement d'hydrocar- mation of petroleum: Geochimica et and Schweighardt, F.K., 1986, Biologi-
bons: Revue de I'lnstitute Franc;:ais du Cosmochimica Acta, v. 40, p. 791-799. cal markers extractable from coal, in
Petrole, v. 22, p. 1283-1306. American Society for Testing and Materials Johns, R.B., ed., 1986, Biological
Grayson, J.F., 1975,Relationship of palyno- (ASTM), 1974, Test for gross calorific Markers in the Sedimentary Record:
morph translucency to carbon and value of solid fuels by adiabatic bomb Elsevier, New York, p. 311-345.
o hydrocarbons in clastic sediments, in
Alpern, B., ed., Petrographie de la
calorimeter: American Society for Test-
ing and Materials, Philadelphia, Stan-
Cranwell, P.A., 1976, Decomposition of
aquatic biota and sediment formation:
O· matiere organique des sediments, rela-
tions avec la paleotemperature et Ie
dard D2015-77.
American Society for Testing and Materials
compounds in detritus resulting from
microbial attack on the alga Ceratium
potentiel petroller: C.N.R.S., Paris, (ASTM), 1979, Proximate analysis of hirundinella: Freshwater Biology, v. 6,

o p.261-273.
Gutjahr, C.C.M., 1966,Carbonization mea-
. coal and coke: American Society for
Testing and Materials, Philadelphia,
p.41-48.
de Leeuw, J.W and Baas, M., 1986, Early-
r surements of pollen-grains and spores Standard D3172-73. stage diagenesis of steroids, in Johns,
and their application: Leidse Geolog- Allan, J. and Douglas, A.G., 1977, Varia- R.B., ed., Biological Markers in the Sedi-
ische Mededelingen, v. 38, p. 1-29. tions in the content and distribution of mentary Record: Elsevier, New York,
Jones, R.W. and Edison, T.A., 1978, Micro- n-alkanes in a series of carboniferous p. 101-123.
scopic observations of kerogen related vitrinites and sporinites of bituminous Deniro, M.J., 1983,Distributionofthestable
to geochemical parameters with empha- rank: Geochimica et Cosmochimica isotopes of carbon, nitrogen, oxygen
o sis on thermal maturation, in Oltz, D.F., Acta, v. 41, p. 1223-1230. and hydrogen among plants, in Mein-

o ed., Low Temperature Metamorphism of


Kerogen and Clay Minerals: Society of
Bailey, N.J.L., Evans, C.R. and Miller,
C.WD., 1974, Applying petroleum geo-
schein, W.G., ed., Organic Geochemis-
try of Contemporaneous and Ancient

r. Economic Paleontologists and Miner-


alogists, Pacific Section, Los Angeles,
chemistry to search forcil: example from
Western Canada Basin: American Asso-
Sediments: Society of Economic
Paleontologists and Mineralogists,
C p. 1-12.
Staplin, F.L., 1969, Sedimentary organic
ciation of Petroleum Geologists, Bul-
letin, v. 58, p. 2284-2294.
Great Lakes Section, Short Course
notes, p. 4-1-4-27.
8 matter, organic metamorphism, and oil
and gas occurrences: Bulletin of Cana-
Baker, E.w. and Louda, J.W, 1983,Thermal
aspects of chlorophyll geochemistry, in
Douglas, A.G., Hall, P.B. and Solli, H., 1983,
Comparative organic geochemistry of
dian Petroleum Geology, v. 17, p. 47-56. Bjortby, M., Albrecht, P.,Cornford, C., de some European oil shales, in Miknis, F.P.
Staplin, F.L., 1982, Determination of Groot, K., Eglinton, G., Galimov, E., and McKay, J.F., eds., Geochemistry
thermal alteration index from color of Leythaeuser, D., Pelet, R., Rullkotter, J. and Chemistry of Oil Shales: American
exinite (pollen, spores), in Staplin, F.L., and Speers, G., eds., Advances in Chemical Society, Symposium Series
Dow, WG., Milner, C.W.D., O'Conner, Organic Geochemistry 1981: Wiley, 230, p. 59-84.
D.I., Pocock, S.A.J., van Gijzel, P., Chichester, p. 401-421. Durand, B. and Monin, J.C., 1980, Elemental
Welte, D.H. and Yukler, M.A., eds., How Baker, E.w. and Louda, J.w., 1986, Porphy- analysisof kerogens(C, H, 0, N, S, Fe),in
to Assess Organic Maturation and rins in the geological record, in Johns, Durand, B., ed., Kerogen: insoluble
Paleotemperatures: Society of Eco- R.B., ed., Biological Markers in the Sedi- organic matter from sedimentary rocks:
nomic Paleontologists and Mineralo- mentary Record: Elsevier, New York, Editions Technip, Paris, p. 113-142.
gists, Short Course 7, p. 7-11. p.125-225.
c
224 Diagenesis Geoscience Canada Reprint Series 4 (
C
Eglinton, G., 1969, Organic geochemistry: Lewan, M.D., Bjor0y, M. and Dolcater, D.L.. McEvoy, J. and Giger, W., 1986, Origin of
C
the organic chemist 's approach,in Eglin-
ton, G. and Murphy, M.T.J., eds., 1969,
1986, Effects of thermal maturation on
steroid hydrocarbons by hydrous pyro-
hydrocarbons in Triassic Serpiano oil
shales - hopanoids: Organic Geo-
C
Organic Geochemistry: methods and
results: Springer-Verlag, New York,
lysis of Phosphoria retort shale: Geo-
chi mica et Cosmochimica Acta, v. 50,
chemistry, v. 10, p. 943-949.
McKenzie, D., Mackenzie, A.S., Maxwell,
C
p.828. p. 1979-2. J.R. and Sajgo, C.S., 1983, Isornerlza- C
Eglinton, T.I., Rowland, S.J., Curtis, C.D. Leythaeuser, D., Schaefer, R.G. and tion and aromatization of hydrocar-
and Douglas, A.G., 1986, Kerogen-min- Weiner, B., 1979, Generation of low bons in stretched sedimentary basins: C
erai reactions at raised temperatures in
the presence of water: Organic Geo-
molecular weight hydrocarbons from
organ ic matter in source beds as a func-
Nature, v. 301, p. 504-506.
McKirdy, D.M., Aldridge, A.K. and Ypma,
C
chemistry, v. 10, p. 1041-1052.
Espitalie, J., Deroo, G. and Marguis, F.,
tion of temperature and facies: Chemi-
cal Geology, v. 25, p. 95-108.
P.J.M., 1983, A geochemical comparison
of some crude oils from pre-Ordovician
C
1985, La pyrolyse Rock-Eval et ses Mackenzie, A.S., 1984, Applications of bio- carbonate rocks, in Bjorey, M., Albrecht, C
applications: Revue de I'lnstitute Fran- logical markers in petroleum geochem- P., Cornford, C., de Groot, K., Eglinton,
cals du Petrole, v. 40, p. 563-579. istry, in Brooks, J. and Welte, D., eds., G., Galimov, E., Leythaeuser, D., Pelet, C
Espitalie, J., Laporte, J.L., Madec, M., Mar- Advances in Petroleum Chemistry: Aca- R., Rullkotter, J. and Speers, G., eds.,
quis, F., Leplat, P., Paulet, J. and Bou- demic Press, Toronto, v. 1, p. 115-214. Advancesin Organic Geochemistry 1981: C
tefeu, A., 1977a, Methode rapide de Mackenzie, A.S., Hoffmann, C.F. and Max- Wiley, Chichester, p. 99-10?
characterisation des roches meres, de well,J.R., 1981, Molecular parameters of Milner,C.w.D., 1982,Geochemical analysis C
leur potential petrolier et de leur degre
d'evolutlon: Revue de I'lnstitut Francais
maturation in the Toarcian shales, Paris
Basin, France- III. Changesin aromatic
of sedimentary organic matter and inter-
pretation of maturation and source po-
C
du Petrole, v. 32, p. 23-42.
Espitalie, J., Madec, M., Tissot , B., Mennig,
steroid hydrocarbons: Geochimica et
Cosmochimica Acta, v. 45, p. 1345-1355.
tential, in Staplin , F.L., Dow. W.G.,
Milner, C.W.D., O'Conner, D.1., Pocock,
C
J.J. and Leplat, P., 1977b, Source rock Mackenzie, A.S., Lamb, N.A. and Maxwell . S.A.J., van Gijzel , P., Welte, D.H. and C
characterization method for petroleum J.R., 1982, Steroid hydrocarbons and YukJer, M.A., eds., How to Assess Or-
exploration: 9th Offshore Technology the thermal history of sediments: Na- ganic Maturation and Paleotempera- C
Conference, Proceedings, OTC#2935, ture, v. 295, p. 223-226. tures: Society of Economic Paleontolo-
p.439-444. Mackenzie, A.S. and McKenzie, D., 1983, gists and Mineralogists, Short Course 7, C
Fowler,M.G., Abolins, P.and Douglas, A.G.,
1986, Monocyclic alkanes in Ordovician
Isomerization and aromatization of
hydrocarbons in sedimentary basins
p.217·252.
Monnier, F., Powell . T.G. and Snowdon,
C
organic matter: Organic Geochemistry,
v. 10, p. 815-823.
formed by extension: Geological Maga-
zine , v. 120, p. 417-528.
L.R., 1983, Qualitative and quantitative
aspects of gas generation during matu-
C
Galimov, E.M., 1985, The Biological Frac- Mackenzie, A.S., Patience, R.L., Maxwell. ration of sedimentary organic matter - C
tionation of Isotopes : Academic Press, J.R., Vandenbroucke, M. and Durand. examples from Canadian frontier ba-
Toronto, 261 p. B., 1980, Molecular parameters of matu- sins,;n Bjorey, M., Albrecht, P., Cornford, C
Gelpi, E., Schneider, H., Mann, J. and Oro. ration in the Toarcian shales, Paris C., de Groot, K., Eglinton, G., Galimov,
J., 1970, Hydrocarbons of geochemical Basin, France - I. Changes in config- E., Leythaeuser, D., Pelet, R., Rullk6tter, C
significance in microscopic algae:
Phytochemistry, v. 9, p. 603-612.
uration of acyclic isoprenoid alkanes,
steranes and triterpanes: Geochimica et
J. and Speers, G., eds., Advances in
Organic Geochemistry 1981: Wiley,
C
Hayes, J.M., 1983, Practice and principles
of isotopic measurements inorganic
CosmochimicaActa, v. 44, p. 1709-1721.
Mackenzie, A.S., Patience, R.L. and Max-
Chichester, p. 487-495.
Oremland, R.S., Marsh. L. and Desmarais,
C
geochemistry, in Meinschein, W.G., ed., well, J.R., 1981, Molecular changes D.J., 1982,Methanogenesis in Big Soda C
Organic Geochemistry of Contempora- and the maturation of sedimentary Lake, Nevada - an alkaline, moderately
neous and Ancient Sediments : Society organic matter, in Atkinson, G. and hypersaline, desert lake: Applied and C
of Economic Paleontologists and Miner- Zuckermann, J.J. , eds., Origin and Environmental Microbiology, v. 43, p.
alogists, Great Lakes Section , Short Chemistry of Petroleum: Pergamon, 462-468. C
Course notes. p. 5-1-5-31.
Haering, T.C., 1984, Thermal reactions of
Oxford, p. 1-31.
Mackenzie, A.S., Quirke, J.M.E. and Max-
Ourisson, G., Albrecht , P. and Rohmer, M.,
1979,Paleochemistry and biochemistry
C
kerogen with added water, heavy water
and pure organic substances : Organic
well, J.R., 1980, Molecular parameters
of maturation in the Toarcian shales,
of a group of natural products: Pure and
Applied Chemistry, v. 51, p. 709-729.
C
Geochemistry, v. 5, p. 267-278. Paris Basin, France - II. Evolution of Peters, K.E., 1986, Guidelines for evaluat- C
Huang, W.-Y., and Meinschein, W.G., 1979, metalloporphyrins, in Douglas, A.G. ing petroleum source rocks using pro-
Sterols as ecological indicators: Geo- and Maxwell , J.R., eds., Advances in grammed pyrolysis: American Associa- (
chimica et Cosmochimica Acta, v. 43,
p.739-745.
Organic Geochemistry 1979: Perga-
mon, Oxford, p. 239-248.
tion of Petroleum Geologists, Bulletin,
v. 70, p. 318-329. c
Lewan. M.D. , 1983, Effects on thermal
maturation on stable organic carbon iso-
Mackenzie, A.S., Ren-Wei, L., Maxwell,
J.R., Moldowan, J.M. and Seifert, W.K.,
Peters, K.E., Rohrbach, B.G. and Kaplan.
I.R., 1981, Carbon and hydrogen stable
e
topes as deterined by hydrous pyrolysis
of Woodford Shale: Geochimica et Cos-
1983, Molecular measurements of
thermal maturation of Cretaceous shale
isotope variations in kerogen during lab-
oratory-simulated thermal maturation:
c
mochimica Acta, v. 47, p. 1473-1474. from the Overthrust Belt, Wyoming, American Association of Petroleum c
Lewan, M.D., 1985,Evaluation of petroleum
generation by hydrous pyrolysis experi-
USA, in Bjorey, M.• Albrecht, P., Corn-
ford, C., de Groot, K., Eglinton, G.,
Geologists, Bullet in, V. 65, p. 501-508.
Powell, T.G., 1978, An Assessment of the c
mentation: Royal Society of London,
Philosophical Transactions, v.315A ,
p.123-134.
Galimov, E., Leythaeuser, D., Pelet, R.,
Rullkotter, J. and Speers, G., eds.,
Hydrocarbon Source Rock Potential of
the Canadian Arctic Islands: Geological c
Advances in Organic Geochemistry Survey of Canada, Paper 78-12, 82 p. (
1981: Wiley, Chichester, p. 496-503. Pym,J.G ., Ray,J.E., Smith, G.W.and White-
head, E.V., 1975, Petroleum triterpane
fingerprinting of crude oils: Analytical
c
Chemistry, v. 47, p. 1617·1622. (
c
c
c Determining Levels of Organic Diagenesis 225
c
r Radke, M. and Welte, D.H., 1983, The meth- Seifert, W.K. and Moldowan, J.M., 1978, Tissot, B. and Welte, D.H., 1984, Petroleum
c. ylphenanthrene index (MPI) - a matu- Applications of steranes, terpanes and Formation and Occurrence: a new ap-

o rity parameter based on aromatic hydro-


carbons, in Bjorl,6y, M., Albrecht, P.,
monoaromatics to the maturation, migra-
tion and source of crude oils: Geochimica
proach to oil and gas exploration, Second
Edition: Springer-Verlag, Berlin, 538 p.

r Cornford, C., de Groot, K., Eglinton, G.,


Galimov, E., Leythaeuser, D., Pelet, R.,
et Cosmochimica Acta, v. 42. p. 77-95.
Seifert, W.K. and Moldowan, J.M., 1979,
Volkman, J.K. and Maxwell, J.R., 1986,
Acyclic isoprenoids as biological mark-
(J Hullkotter, J. and Speers, G., eds., The effect of biodegradation on steranes ers, in Johns, R.B., ed., Biological
Advances in Organic Geochemistry and terpanes in crude oils: Geochimica Markers in the Sedimentary Record:
C 1981: Wiley, Chichester, p. 504-512.
Radke, M., Welte, D.H. and Willsch, H.,
et Cosmochimica Acta, v. 43, p. 111-126.
Seifert, W.K. and Moldowan, J.M., 1980,
Elsevier, New York, p. 1-42.
Weete, J.D., 1974,Aliphatic hydrocarbons,
( 1982a, Geochemical study on a well in The effect of thermal stress on source in Weete, J.D., ed., Fungal Lipid Bio-
the Western Canada Basin - relation of rock quality as measured by hopane chemistry: Plenum, New York,p. 39-65.
l the aromatic distribution pattern to stereochemistry, in Douglas, A.G. and Winters, J.C., Williams, J.A. and Lewan,
maturity of organic matter: Geochimica Maxwell, J.R., eds., Advances in Or- M.D., 1983, A laboratory study of petro-
C et Cosmochimica Acta, v. 46, p. 1-10. ganic Geochemistry 1979: Pergamon, leum generation by hydrous pyrolysls,

o Radke, M., Willsch, H., Leythaeuser, D. and


TeichmQller, M., 1982b, Aromatic com-
Oxford, p. 229-237.
Seifert, W.K. and Moldowan, J.M., 1981,
in Bjorl,6y, M., Albrecht, P.,Cornford, C.,
de Groot, K., Eglinton, G., Galimov,
ponents of coal- relation of distribution Paleoreconstruction by biological mark- E., Leythaeuser, D., Pelet, R., Rullkotter,
pattern to rank: Geochimica et Cosmo- ers: Geochimica et CosmochimicaActa, J. and Speers, G., eds., Advances in
o chimica Acta, v. 46, p. 1831-1868. v. 45, p. 783-794. Organic Geochemistry 1981: Wiley,

o Rouxhet, P.G., Robin, P.L. and Nicaise, G.,


1980, Characterization of kerogens
Seifert, W.K. and Moldowan, J.M., 1983,
Use of biological markers in petroleum
Chichester, p. 524-533.
See for diagram of apparatus.

o and of their evolution by infrared spec-


troscopy, in Durand, B., ed., Kerogen:
exploration, in Meinschein, W.G., ed.,
Organic Geochemistry of Contempora- Predictive Diagenetic Models

o insoluble organic matter from sedimen-


tary rocks: Editions Technip, Paris,
neous and Ancient Sediments: Society
of Economic Paleontologists and Miner- General
o p.163-190.
Rowland, S.J., Aareskjold, K., Xuemin, G.
alogists, Great Lakes Section, Short
Course notes, p. 3-1-3-31. Bostick, N.H., 1979, Microscopic measure-
o and Douglas, A.G., 1986, Hydrous pyro-
lysis of sediments - composition and
Seifert, W.K. and Moldowan, J.M., 1986,
Use of biological markers in petroleum
ment of the level of catagenesis of solid
organic matter in sedimentary rocks to
o proportions of aromatic hydrocarbons in exploration, in Johns, R.B., ed., 1986, aid in exploration for petroleum and to

o pyrolysates: Organic Geochemistry,


v. 10, p. 1033-1040.
Biological Markers in the Sedimentary
Record: Elsevier, New York, p. 261-290.
determine former burial temperatures
- a review, in Scholle, P.A. and

c -Saxby, J.D., Bennett, A.J.R., Corcoran,


J.F., Lambert, D.E. and Riley, K.W.,
Seifert, W.K., Moldowan, J.M. and Jones,
R.W., 1980, Application of biological
Schluger, P.R., eds., Aspects of Diagen-
esis: Society of Economic Paleontolo-
o 1986, Petroleum generation - simula-
tion over six years of hydrocarbon forma-
marker chemistry to petroleum explora-
tion: 10th World Petroleum Congress,
gists and Mineralogists, Special Pub-
lication 26, p. 17-43.
c tion from torbanite and brown coal in a
subsiding basin: Organic Geochemis-
Bucharest, Romania, September 1979,
Proceedings, Heyden, London, Paper
Dutcher, R.R., Hacquebard, P.A., Schopf,
J.M. and Simon, J.A., 1974, eds., Car-
c try, v. 9, p. 69-81. SP-8, p. 425-440. bonaceous Materials as Indicators of

o Scheuer, P.J., 1973, ed., Chemistry of


Marine Natural Products, Volume 1:Aca-
Snowdon, L.R. and Powell, T.G., 1982,
Immature oil and condensate - modi-
Metamorphism: Geological Society of
America, Special Paper 153, 108 p.

o demic Press, Toronto, 201 p.


Scheuer, P.J., 1978, ed., Chemistry of
fication of hydrocarbon generation
model for terrestrial organic matter:
Karweil, J., 1956, Die metamorphose der
Kohlen vern Standpunkt der physikal-
o Marine Natural Products, Volume 2:
Academic Press, Toronto, 308 p.
American Association of Petroleum
Geologists, Bulletin, v. 66, p. 775-788.
ischen Chemie: Deutsches Geolog-
ischen Gesellschaft Zeitschrifte, v. 107,
o Schidlowski, M., 1986, 13C/12C ratios as
indicators of biogenicity, in Johns, R.B.,
Snowdon, L.R. and Roy, K.J., 1975,
Regional organic metamorphism in the
p.132-139.
Landes, K.K., 1967, Eometamorphism and
o ed., Biological Markers in the Sedimen- Mesozoic strata of the Sverdrup Basin:
Bulletin of Canadian Petroleum Geol-
oil and gas in time and space: American

o tary Record: Elsevier, Amsterdam,


p.347-361. ogy, v. 23, p. 131-148.
Association of Petroleum Geologists,
Bulletin, v. 51, p. 828-841.

r. Schoell, M., 1984, Stable isotopes in petro-


leum research, in Brooks, J. and Welte,
D., eds., Advances in Petroleum Chem-
ten Haven, H.L., de Leeuw, J.W., Peakman,
T.M.andMaxwell,J.R.,1986,Anomalies
in steroid and hopanoid maturity
Numerical Models

istry: Academic Press, Toronto, v. 1, indices: Geochimica et Cosmochimica Bostick, N.H., 1973, Time as a factor in
8· p.215-245.
Seifert, W.K., Carlson, R.M.K. and Mol-
Acta, v. 50, p. 853-855.
ten Haven, H.L., de Leeuw, J.W. and
thermal metamorphism of phytoclasts
(coaly particles): 7th Congress Interna-
r. dowan, J.M., 1983, Geomimetic syn-
thesis, structure assignment, and geo-
Schenck, P.A., 1985, Organic geochem-
ical studies of a Messinian evaporitic
tionale de la Stratigraphie et Geologie
Carbonifere, Krefeld, 1971, Compte
chemical correlation applications of basin, northern Apennines (Italy) - 1. Rendu, v. 2, p. 183-193.
monoaromatized petroleum steroids, in Hydrocarbon biological markers for a Bustin, R.M., 1983, Heating during thrust
Bjorl,6y, M., Albrecht, P.,Cornford, C., de hypersaline environment: Geochimica et faulting - friction or fiction?: Tectono-
Groot, K., Eglinton, G., Galimov, E., Cosmochimica Acta, v. 49, p. 2181-2191. physics, v. 95, p. 305-328.
Leythaeuser, D., Pelet, R., Rullkotter, J. Thompson, K.F.M., 1979, Light hydrocar- Bustin, R.M., 1984, Coalification levels and
and Speers, G., eds., Advances in Or- bons in subsurface sediments: Geo- their significance in the Groundhog
ganic Geochemistry 1981: Wiley, Chi- chimica et Cosmochimica Acta, v. 43, coalfield, northcentral British Columbia:
chester, p. 710-724. p.657-672. Coal Geology, v. 4, p. 21-44.
c
226 Diagenesis Geoscience Canada Reprint Series 4 c
c
Bustin, A.M., 1986, Maturity of Late Creta- Lopatin, N.Y. and Bostick, N.H., 1974, The Comparative Models c
ceous and Tertiary coal measures,
Canadian Arctic Archipelago: Coal
geologic factors in coal catagenesis:
Illinois Geological Survey, Reprint 1974- Barker, C.F.and Elders, W.A.,1979,Vitrinite
c
Geology, v. 6, p. 71-106. Q, 15 p. [Originally published 1973, in reflectance geothermometry in the c
Bustin, R.M., Hills, L.V. and Gunther, P.A.,
1977, Implication of coalification levels,
Russian: Priroda organicheskogo vesh-
chestva sovremennykh i iskopaemykh
Cerro Prieto geothermal field, Baja Cal-
ifornia, Mexico: Geothermal Resources c
Eureka Sound Formation, northeastern
Arctic Canada: Canadian Journal of
osadkov: Nauka Press).
McKenzie, D.P., 1978,Some remarks on the
Council, Transactions, v. 3, p. 27-30.
Buntebarth, G., 1978, The degree of meta- c
Earth Sciences, v. 14, p. 1588-1597.
Castano, J.R. and Sparks, D.M., 1974, Inter-
development of sedimentary basins:
Earth and Planetary Science Letters,
morphism of organic matter in sedimen-
tary rocks as a paleo-geothermometer, c
pretation of vitrinite reflectance mea-
surements in sedimentary rocks and de-
v. 40, p. 25-32.
McKenzie, D.P., 1981, The variation of tem-
applied to the Upper Rhine Graben:
Paleogeophysics, v. 117, p. 83-91.
c
termination of burial history using vitrin-
ite reflectance and authigenic minerals,
perature with time and hydrocarbon
maturation in sedimentary basins
Bustin, R.M., Hills, L.V. and Gunther, P.R., c
in Dutcher, R.R., Hacquebard, P.A., formed by extension: Earth and Plane-
1977, Implication of coalification levels,
Eureka Sound Formation, northeastern c
Schopf, J.M. and Simon, J.A., eds., Car-
bonaceous Materials as Indicators of
tary Science Letters, v. 55, p. 87-98.
Middleton, M.F.,1982,Tectonic history from
Arctic Canada: Canadian Journal of
Earth Sciences, v. 14, p. 1588-1597. c
Metamorphism: Geological Society of
America, Special Paper 153, p. 31-52.
vitrinite reflectance: Royal Astronomical
Society, Geophysical Journal, v. 68,
Castano, J.R. and Sparks, D.M., 1974, Inter-
pretation of vitrinite reflectance mea- c
Chiaromonte, M.A. and Novelli, L., 1986,
Organic matter maturity in northern
p. 121-132.
Sclater, J.G. and Christie, P.A.F., 1980,Con-
surements in sedimentary rocks and
determination of burial history using
c
Italy - some determining agents, in
Leythaeuser, D. and Rullkotter, J., eds.,
tinental stretching - an explanation of
the post-mid-Cretaceous subsidence
vitrinite reflectance and authigenic min- c
Advances in Organic Geochemistry of the central North Sea basin: Journal
erals, in Dutcher, R.A., Hacquebard,
P.A.,Schopf, J.M. and Simon, J.A., eds., c
1985, pt. 2, p. 281-290.
Cohen, C.A., 1981, Time and temperature in
petroleum formation: application of
of Geophysical Research, v.85,
p. 3711-3739.
Shibaoka, M. and Bennett, A.J.R., 1977,
Carbonaceous Materials as Indicators
of Metamorphism: Geological Society of
America, Special Paper 153, p. 31-52.
c
Lopatin's method to petroleum explora- Patterns of diagenesis in some Aus- Hacquebard, P.A., 1977, Rank of coal as an
tion - discussion: American Associa-
tion of Petroleum Geologists, Bulletin,
tralian sedimentary basins: Australian
Petroleum Exploration Association
index of metamorphism for oil and gas in
Alberta: in The Origin and Migration of
c
v. 65, p. 1647-1648.
Dow, w.G., 1977, Kerogen studies and geo-
Journal, v. 17, p. 58-63.
Tissot, B.P. and Welte, D.H., 1984, Part V,
Petroleum in western Canadian Sedi-
mentary Basins: Geological Survey of
c
logical interpretations: Journal of Geo- Chapter 4: Geochemical modelling: A Canada, Bulletin 262, p. 11-23. c
chemical Exploration, v. 7, p. 79-99.
England, T.D.J. and Bustin, A.M., 1986b,
quantitative approach to the evalua-
tion of oil and gas prospects, in Tissot,
Hacquebard, P.A. and Donaldson, J.R.,
1970, Coal metamorphism and hydro- c
Effect ofthrust faulting on organic matu-
ration in the southeastern Canadian
B.P. and Welte, D.H., Petroleum Forma-
tion and Occurrence, Second Edition:
carbon potential in the upper Paleozoic
of the Atlantic provinces, Canada: Cana- c
Cordillera, in Leythaeuser, D. and
Rullkotter, J., eds., Advances in Organic
Springer-Verlag, New York, p. 583-609.
Tissot, B.P. and Espitalie, J., 1975, L'evolu-
dian Journal of Earth Sciences, v. 7,
p. 1139-1163.
c
Geochemistry 1985, p. 609-616.
Hood, A., Gutjahr, C.C.M. and Heacock,
tion thermique de la matiere organique
des sediments: Applications d'une sim-
Hacquebard, P.A. and Donaldson, J.R.,
1974, Rank studies of coals in the Rocky
c
A.L., 1975, Organic metamorphism and ulation mathematique: Revue de Mountains and inner foothills belt, Can- c
the generation of petroleum: American
Association of Petroleum Geologists,
Bulletin, v. 59, p. 986-996.
L'lnstitute Francals du Petrole, v.30,
p.743-777.
Waples, DW., 1980, Time and temperature
ada, in Dutcher, R.A., Hacquebard, P.A.,
Schopf, J.M. and Simon, J.A., eds., Car-
bonaceous Materials as Indicators of
c
Huck, G. and Karweil, J., 1955,Physikalisch- in petroleum formation: application of Metamorphism: Geological Society of
(
chemische Probleme der Inkohlung:
Brennstoff-Chemie, v. 36, p. 1-11-
Lopatin's method to petroleum explora-
tion: American Association of Petroleum
America, Special Paper 153, p. 75-94.
Nurkowski, J.R., 1984, Coal quality, coal
c
Hughes, J.D. and Cameron, A.R., 1985,
Lithology, depositional setting and coal
Geologists, Bulletin, v. 64, p. 916-926.
Welte, D.H. and Yukler, A., 1980,Evolution of
rank variation and its relation to recon-
structed overburden, Upper Cretaceous
c
rank-depth relationships in the Jurassic- sedimentary basinsfrom the standpointof and Tertiary plains coals, Alberta, Can- c
Cretaceous Kootenay Group at Mount
Allan, Cascade Coal Basin: Geological
petroleum origin and accumulation - an
approach for a quantitative basin study:
ada: American Association of Petroleum
Geologists, Bulletin, v. 68, p. 285-295. c
Survey of Canada, Paper 81-11, 41 p.
Kalkreuth, W. and McMech..an,-M., 1984,
Organic Geochemistry, v. 2, p. 1-8.
Wright, N.J.R., 1980,Time, temperature and
Suggate, R.P., 1956, Depth-volatile rela-
tions in coalfields: Geological Maga- c
Regional pattern orttlermal maturation
as determined from coal-rank studies,
organic maturation - the evolution of
rank within a sedimentary pile: Journal of
zine, v. 93, p. 201-217.
e
Rocky Mountain Foothills and Front
Ranges north of Grande Cache, Alberta
Petroleum Geology, v. 2, p. 411-425.
Yorath, C.J. and Hyndman, R.D., 1983,Sub-
c
- implications for petroleum explora- sidence and thermal history of Queen c
tion: Bulletin of Canadian Petroleum
Geology, v. 32, p. 249-271-
Lopatin, N.V., 1971, Temperature and geo-
Charlotte Basin: Canadian Journal of
Earth Sciences, v. 20, p. 135-159.
Wood, R.J., 1981, The subsidence history of
Originally publlshed in
Geoscience Canada v. 12 Number 1 c
logic time as factors in coalification: Conoco well 15/30-1 , central North Sea:
(March 1985)
Revised 1988
C
Akademie Nauk SSSR, Ser. Geol., Iz- Earth and Planetary Science Letters,
vestiya, no. 3, p. 95-108. [in Russian, v. 54, p. 306-312. l
translated by N.H. Bostick).
C
C
C
c
c Diagenesis of Biogenic Siliceous Sediments 227
c
c Disso/vedsilicon(orsimply silicon) isthe Flint is a name widely applied to chert
r term used for the undissociated mono- nodules in the Upper Cretaceous chalk
meric silicic acid Si(OH)4 which is the of northwestern Europe(Schmid, 1986),
( dominant species of dissolved Si0 2 in which have been used in artifacts and
(' most natural waters. Its anhydrous equiv- tools made by early man (arrowheads,
alentSi02 hasa molecularweightof about knives, drills, etc.). The term is synony-
c 60. One ppm Si0 2 by weight (or 1 mous with firestone or hornstone and

c mg'kg-') therefore corresponds to 16.6


microgram-atoms Si0 2 per litre (p.g-
has been commonly applied for more
than a thousand years to any very hard
at-L", the concentration unit commonly and dense rock with conchoidal fracture

c Origin of Chert:
Diagenesis of Biogenic
used in the oceanographic literature) or
16.6p.M where p.M stands for micromole
surfaces (Bates and Jackson, 1980).
Generally, jasper is a red, brown or
c Siliceous Sediments
per litre.This, inturn, isequivalentto 0.467
mg' L-' Si. Conversely, 1 mM (= 1 milli-
yellow variety of chert (also green or
black) that derives its colour from iron-
o mola-L") corresponds to 60 ppm Si02 •
In its various solid phases, Si02 will be
oxide impurities. It may be associated
with iron-ores or soil-forming pro-
Reinhard Hesse referred to as silica. These include amor- cesses. Novaculite is very dense, Iight-
o Department of Geological Sciences
McGill University
phous silica or opal-A, cristobalite-tridy-
mite or opal-CT, low-temperature cris-
coloured quartz-chert from the Ouach-
ita Mountains in Arkansas and Okla-
o 3450 University St. tobalite or opal-C, low-temperature tri- homa, which has undergone high-grade

c Montreal, Quebec H3A 2A 7 dymite, chalcedony, quartzine, lutecite


and quartz. Opal-CT lepispheres are
diagenesis and low- to intermediate-
grade metamorphism. The word is
INTRODUCTION small spheres less than 5 microns in dia- derived from the Latin word for razor
Highly silicified sedimentary rocks are meter of intergrown cristobaliteltridymite (novacu/a) and has been formerly used
o generally called chert, but are also blades precipitated into sediment pores. in England for rocks that served as

c known under generic or local names


such as radiolarite, porcelanite, flint,
Magadiite [NaSi 70,3(OHb' 3H 20j
is a silica precursor mineral in lake sedi-
whetstones or razor hones (Goldstein,
1959).
o jasper, Iydite, or novaculite. They may
contain 95% or more silica. The origin of
ments. Physical and mineralogical char-
acteristics of these species are dis- SOURCES OF NON-DETRITAL
o chert has been much debated in the
past. Systematic studies in the last
cussed in appropriate sections of this
and the following paper.
SILICA IN SILICEOUS SEDIMENTS
There are three main sources of non-
decade have advanced our knowledge Biogenic fine-grained siliceous sedi- detrital silica in sediments: (i) siliceous
o of chert genesis significantly, and have
shed light on many facets of the so-
ments are called siliceous oozes. The
term "siliceous mud" instead of ooze is
tests and skeletal elements of orga-
nisms, (ii) weathering solutions in semi-
o called "chert-problem". Thethree basic used for deposits which have a substan- arid climates, and (iii) silicon supplied in
aspects of the chert-problem, now un- tial detrital terrigenous component. Dia- solution by hydrothermal-volcanic sys-
derstood in principle, are: (1) the source tom ooze, radiolarian ooze and (sponge) tems. The predominant source of Phan-
c of the silica, (2) the depositional en-
vironment of siliceous sediments and
spicule ooze are distinguished accord-
ing to the main groups of organisms
e,rozoic cherts is biogenic, although
there also exist hydrothermal-volcan-
(3) the diagenesis of cherts and chert- contributing siliceous shells to pelagic ogenic deposits or low-temperature
o bearing rocks. A historical perspective
will be included in this review in order to
(or lacustrine) sediments. Their lithified
equivalents are diatomite, radiolarite
chemogenic deposits (in alkaline lakes
or arid to semi-arid soils). In the Pre-
o give the reader some idea of the de- and spiculite. The rock names por- cambrian, the cherty variety of banded

o velopments that led to our present un-


derstanding of silica diagenesis and to
celanite and chert are used to denote
fine-grained siliceous sedimentary
iron formations represents a wide-
spread type of chert almost unknown
o the problems on which current research
is focussed. Although the emphasis of
rocks according to their textural and
physical properties. "Porce/anite" re-
from younger geologic periods whose
origin is still being debated. Low-tem-
c this review is on diagenesis, it will start
with a brief outline of the first two as-
fers to a porous rock with dull or matte
lustre similar to unglazed porcelain,
perature chemogenic and lor hydrother-
mal-volcanogenic deposits are the
C pects of the former chert-problem whereas "chert" denotes a dense vit- dominant Precambrian types of chert.
6 because a discussion of silica dia-
genesis is not possible without frequent
reous, hard and brittle rock (Bramlette,
1946). The difference between the two
This review focusses on the diagenesis
of biogenic siliceous sediments. Inor-
( reference to these other subjects. is related to detrital content, especially ganic and replacement cherts are dealt
Terminology and Concentration Units clay content, which is higher (25-50%) with in the following article (Hesse, this
(
for Dissolved and Solid Si02 in porcelanite than in chert (0-25%, volume, p. 253-275).
L Phases and Fine-grained
Siliceous Sediments.
Jones and Murchey, 1986). Siliceous
rocks with more than 50% clay are
The total present-day silica produc-
tion by marine organisms such as dia-
C To facilitate communication, a few of the called siliceous claystone, mudstone, or toms, radiolarians, silicoflagellates or
terms and concentration units used for argillite. Lydite is a dark-grey to black siliceous sponges is estimated at
the variousdissolvedand solid speciesof variety of argillaceous chert or siliceous 2.5 x 10'6 grams per annum (g-a-'). This
l. Si02 , as well as for fine-grained siliceous argillite. Local names for various chert is roughly 25 times the input of silica
sediments, will be defined at the outset. types include flint, jasper, and nova- totheoceans(10.8 x 10'4g' a-'), towhich

(
c
228 Diagenesis Geoscience Canada Reprint Series 4
(
C
rivers contribute 4.3, pore-water reflux a global oceanic circulation system and depth (Figure 3). In the deepsea below 1
C
potentiaI5.?, submarine weathering 0.8, occurs (i) along equatorial divergences, or 2 km water depth, temperature C
and submarine volcanism 0.05 x 10'4 (ii) in the vicinity of subpolar conver- decreases only atew degrees Celsius .
g' a-1, according to Heath (1974). More gences, (iii) along the west coasts of The temperature effect thus becomes C
recent calculations by Edmond et al. continents, and (iv) in certain marginal very smaU-and can be offset by the effect
(1979a) attribute an additional 1.9 x 10'4 seas where surface currents diverge or of incr.!!asing pressure which raises
g' a" to hydrothermal influx, although are driven offshore. In the Pacific silica solubility. Pressure-corrected c
this still ,would not balance input and
output. The greater part of the output is
Ocean, regions of upwelling corre-
spond to 5 major belts of silica accumu-
curves for silica solubility (Figure 3)
therefore have a minimum at about 1.5 c
primary production by diatoms which
appear at the beginning of the marine
lation on the sea floor (Figure 2): an
equatorial belt (north of the equator),
km depth, below which solubility in-
creases slightly. However, an equiva-
c
food chain. the sub-Antarctic belt (north of the Ant- lent of the CCl for silica has not been c
The discrepancy between the fig-
ures for input and output, however, is
arctic convergence), the sub-Arctic belt
(south of the Arctic convergence), the
observed in the oceans. From the fore-
going it follows that silica dissolution is c
not a real difference because of inter- Gulf of California (continental west predominant in the upper 1000 m of the c
nal oceanic recycling which involves
dissolution of siliceous tests and up-
coast! marginal sea upwelling) and the
Okhotsk and Bering Seas (marginal sea
water column, in contrast with the dis-
solution of pelagic carbonates. c
welling of the dissolved silica (Figure 1).
According to estimates by different
setting).
In low-latitude areas of high primary
In the Gulf of California, siliceous
muds accumulate despite the supply of
c
authors (e.g., Calvert, 1968, Berger, surface production , pelagic carbonates terrigenous detritus to the gulf, because c
1970, Hurd, 1973) between 90% and
99% of the silica extracted from surface
are deposited together with siliceous
tests leading to mixed calcareous-sili-
the terrigenous input is seasonally and
locally suppressed by the prevailing c
seawater by shell-producing organisms
(in the form of solid amorphous silica)
ceous oozes. Pure siliceous ooze or
high-silica ooze-wi!! only accumulate in
wind and current patterns (Calvert,
1966a,b). Actual concentrations of dis-
c
redissolve before burial. Dissolution areas where dilutionby other compo- solved silicon in the ocean range from a c
starts after death of the organisms
when the tests settle through the water
nents is inhibited or decreased. This is
the case below the calcite compensa-
fraction of a part per million to 10-15 ppm
dissolved silicon (or up to 160-250 c
column, and continues while they rest
on the sea floor, and particularly after
tion level (CCl), e.g., in the equatorial
belt of siliceous oozes to the north ofthe
rrucromoles- L-'). That is, they are con-
siderably lower than the equilibrium sol-
c
burial in the sediment. A fraction of the mixed calcareous-siliceous belt. (An ubility of amorphous silica, which is c
silica dissolved during burial, however,
returns to the ocean by means of diffu-
equivalent belt south of the equator
does not exist, because the young , shal-
between 60 and 130 ppm at 25°C and a
pH < 9. Silica-secreting marine micro- c.
sion . This is evident from the strong low oceanic crust has not yet subsided organisms thus must extract dissolved (
silica concentration gradient in the below the CCl). Temperature affects silicon from seawater at concentra-
upper 20 cm of the sediment. De Master silica solubility more than pressure. Sil- tions well below the thermodynamic equi- c
(1981)includes the figure for pore-water
reflux quoted above (5.7 x 10'4 g' a-')
ica is therefore considerably more sol-
uble in surface waters than at great
librium solubility of opal-A. Thermo-
dynamically this is not possible. The c
with internal oceanic recycling. This is c
the diffusional flux across the sediment!
water interface. Most of the dissolution c
during burial, however, provides the sili-
con required for diagenetic reprecipita-
c
tion in the sediment, the mechanisms of
which are the central topic of this review.
c
c
DEPOSITIONAL ENVIRONMENTS VOLCANIC INPU C
Igla",hydroth 5Ol,.tcl
OF SILICEOUS SEDIMENTS ~ 8 L
Biogenic Siliceous Oozes on the halm

Modern Ocean Floors.


'". rolYSIS
' ,' Of boson C
Biogenic siliceous sediments occur
both in deep- and shallow-water deposi-
e
tional environments. Siliceous ooze is a C
typical pelagic sediment which accu-
mulates on the deep sea floor in regions c..
where silica production in surface wat-
ers is high. This is the case in zones of
c.
oceanic upwelling, where nutrients dis- (
solved at some depths in the oceans
are returned to the surface. Upwelling Figure 1 Global dissolved silicon budget of the oceans. (From Riech and 11. Rad, 1979;
l
is a characteristic phenomenon of the modified after Heath, 1974). All numbers are in 10' 3 g Si02 per annum. C
C
C
(
( Diagenesis of Biogenic Siliceous Sediments 229
c
c organisms must therefore be capable of waters from silicon-poor surface -water combined with plate motions and the
c· raising the concentration to saturation
under the catalyzing influence of enzy-
sources in polar regions, especially in
the North Atlantic. Bottom maxima in
thermal subsidence of ageing oceanic
crust , gives rise to a distinct strati-
( matic reactions. Concentrations are dissolved silicon, on the other hand, are graphic succession of pelagic sedi-
( lowest in surface seawater because of associated with belts of siliceous sedl- ments known as "plate stratigraphy"
the extraction by organisms. Con- ments, particularly d iatom oozes (Berger and Winterer, 1974) or "pelagic
( centration increases with water depth (Edmond et sl., 1979b), with Antarctic stratigraphy " (Hesse et et., 1974). It is
( because of the dissolution of siliceous bottom water, and with areas of hydro- typically developed on Cretaceous -
tests settling through the water column, thermal activity. Cenozoic crust of the major oceans and
( leading to a mid-depth maximum . A Cherts in Pelagic Stratigraphy. consists of (from bottom to top): mid-
subsequent decrease at greate r depths The zonal distribution of pelagic sedi- ocean ridge basalt overlain by pelagic
c is caused by the renewal of bottom ments described for the Pacific, when carbonates, then cherts and siliceous
o
o
o
o
o
o
o
o
c
o
o
o
o
o
(
o
o
o
o
o
8

~Iio ••nic cokar.ou. ~Aby..al clay § Voicano ••nic

I]Jlio.onic silic.ou. DHemipolagic § Turltidit••

Figure 2 Distribution of pelagic sediment types in the bottom sediments of the Pacific Ocean . (From Hesse et aI., 1974). Note that siliceous
sediments south of the A/eutian and Kurile Islands are mixed with volcanogenic material.

r
c
230 Diagenesis Geoscience Canada Reprint Series 4 c
c
oozes and brown abyssal clay (Figure orogenic belts, wherethey may occur as saw in the association of ultrasiliceous
c
4). Calcareous ooze is generally the first parts of ophiolite sequences (see next sediments (radiolarites) with ultrabasic c
pelagic sediment deposited on newly
created oceanic crust, at least since
paragraph).
Ophiolites, the "Steinmann trinity",
igneous rocks is no longer a problem.
The silica of the siliceous pelagic sedi- c
late Jurassic time. This is due to the
elevation of young oceanic crust at mid-
and Chert in Mountain Belts.
In the plate-stratigraphic succession,
ments is not derived directly from silica-
undersaturated basic and ultrabasic
c
ocean ridge crests, which normally pro- siliceous sediments typically occupy an rocks by submarine exhalative volca- c
jects above the CCL. With age-related
subsidence, the crust will eventually
intermediate position between pelagic
carbonate and brown abyssal clay. In
nism, as previously thought (asrecently
as 1971: see Gibson and Towe, 1971). c
pass below the CCl, leading to the
deposition of siliceous ooze and/or
mountain belts, the association of
radiolarian cherts in an ordered se-
Rather, it is supplied through upwelling
from the oceanic silica reservoir and
c
brown abyssal clay. The sequence may quence with other pelagic sediments, biogenic precipitation in surface wat- c
be duplicated, if the northwestward
motion of the Pacific plate carries it
and with mafic and ultramafic rocks of
the ophiolite suite, hasbeen recognized
ers, as discussed above. The "geotec-
tonic significance" of chert, where it c
under the equator, where the CCl is
sufficiently depressed to intercept the
for nearly a century. In the Alps, it was
called the "Steinmann trinity", after its
forms part of an ophiolite sequence, is
not affected by this re-interpretation.
c
sea floor for a second time (Figure 4). An discoverer Gustav Steinmann (1906, However, since the distribution of sili- c
equatorial carbonate/siliceous ooze may
thus accumulate on the older ridge-
1927). It was taken asa suite of rocks dia-
gnostic for "eugeosynclines", whose
ceous sediments and cherts is control-
led by (paleo-)oceanographic condi-
c
crest carbonate and adjacent off-ridge equivalence with oceanic crust wasonly tions, they are therefore not restricted to c
siliceous ooze and/or brown clay. On top
of this, more brown clay is added during
recognized with the advent of the plate
tectonics concept (e.g., Chipping,
oceanic crust. It is no surprise to find
ancient cherts underlain by continental c
the residence of the crust in the North
Pacific. Upon approaching the West
1971). Ophiolites and the Steinmann
trinity are thus today identified with the
crust as, for example in the Apennines
(McBride and Folk, 1979), where they
c
and North Pacific island arc/deep-sea remnants of oceanic crust and mantle occur next to ophiolitic cherts (Folk and c
trench systems, the oceanic crustal
section which carries this pelagic stra-
in mountain belts (Figure 5). The "petro-
genetic problem", which Wenk (1949)
McBride, 1978). It should also be men-
tioned that in the Alpine-Mediterranean c
tigraphy, collects an ultimate cap of
hemipelagic and volcanogenic sedi-
c
Rift 'snow '
'Snow 'Valley c
ments before it is destroyed in asubduc-
tion zone. During subduction, some of
the pelagic sediments may be scraped
N ,
Equator
Line Line c
from the downgoing crustal slab and
incorporated by tectonic accretion into
. ",
' . .. . o 00

.. ..
:: - ••• _.:::

o 0
0

0 c
an imbricated tectonic wedge under the c
c
o 0

trench-slope and fore-arc basin. In this


way, some siliceous deposits escape
subduction and may ultimately be re-
turned to the surface by tectonic uplift in
c
c
5
Temperature (OC)
10 15 20 25 c
/
, '.-:
~.'
c
2
~T.M"rO'u,.
I .
.'

c
,I .

c
J
I

c
1 I
.. Plate Motion

I
Depth 3 ~Sol"bllll, l"nCOffeCI.dJ
(km)
.. Increasing Age of Crust
Siliceous B' . P' Siliceous Ooze
c
5
B::;]
~ Calcareous iogeruc articles s. Carbonate Ooze e
6 rnm
Abyssal Clay :.:..=.; Basalt c
C.C.L. Calcite Compensation Level
800 950 1100 1250 1400 1550 1700 l.
Solubility (/OM s,02)
Figure 4 Pelagic stratigraphy model for the Pacific Ocean showing duplication of the biogenic C
sediment sequence due to the northwestward passage of the Pacific plate under the equatorial
Figure 3 Solubility of biogenic silica in the high-productivity belt. (From Hesse et aI., 1974). Section oriented approximately NW-5E. The
(
CentralequatorialPacific estimatedas a func-
tion oftemperature andpressure (dotted line).
calcite compensation level (CCL) acts as a "snow tine". The East Pacific Rise and other regions
rising above it are covered with Iight-coloured biogenic oozes; areas below the CCL and outside
c..
(From Hurd, 1983; after Griffin, 1980). the belts of siliceous ooze are characterized by red-brown abyssal clay (Figure 2). c
c
c
(
c Diagenesis of Biogenic Siliceous Sediments 231
c
c. ophiolite terrains radiolarian cherts Formation of Bedded Chert. (from the centre of beds upward to the
directly overlie the basalt. The se- Geological and sedimentological top and downwardto the base)andsym-
quence is the reverse of the standard evidence suggests a deep-water origin metrical grading of radiolarian abun-
G Pacific sequence, in which pelagic car- for most ancient bedded chert forma- dance (Mizutani and Shibata , 1983;
( bonates precede the cherts. This is pro- tions. Many of them appear to owe their Sano, 1983; Steinberg et el., 1983)
bably due to a much shallower CCl in emplacement to redeposition of sili- lendnew support to the diagenetic origin
( pre-late Jurassic oceans, a conse- ceous pelagic sediment by turbidity of some bedded cherts. (For recent
quence of the absence of widespread currents (e.g., lmoto and Saito, 1973; reviews of radiolarian cherts see
( calcareous planktonic organisms in Nisbet and Price, 1974; Robertson, Jenkyns and Winterer, 1982; andJones
C' these times (Bosellini and Winterer, 1977; McBride and Folk, 1979) or other
ocean currents. Sedimentary struc-
and Murchey, 1986).
1975). Although most ophiolite-associ- Shallow Water Cherts.
C· ated cherts are not volcanogenic, but tures and fabrics support a redeposi- The effects of upwelling are not re-
tion mechanism, as evidenced by flute stricted to open ocean environments
() biogenic, in origin, as we know now,the
geochemistryof some radiolarian cherts casts and other sole marks (e.g., Imoto or the continental slope. Upwelling
o nevertheless reveals a metasomatic
overprint which is due to igneous ac-
et al., 1974), common graded bedding,
parallel lamination, faint cross lamin-
zones may transgress from the slope
onto the shelf. Biogenic siliceous sedi-
tivity at a former mid-ocean ridge. Ex- ation, starved ripples, grain fabrics ments, therefore, are not restricted to
o amples are the above-mentionedJuras-
sic Mediterranean bedded cherts which
such as parallel alignment of sponge
spicules and radiolarians, shale clasts,
deep-water pelagic environments, but
may on-lap the continental shelves
o directly overlie basalt of the oceanic
crust. Their iron content decreases and
and sharp contacts with interbedded
shales. Another interpretation of bed-
and even occur on the inner shelf,
as for example, off Namibia (Calvert,
o their manganese concentration in- ded cherts is (i) diagenetic segregation 1983). Tertiary opaline claystonesof the
o creases in the section with increasing
stratigraphic distance from the basalt
of silica into chert-rich beds and silica-
poor clay- stones from initially homoge-
coastal plains of the southeastern
United States are ancient equivalents
o reflecting the effects of hydrothermal neous siliceous muds. Still other inter- associated with transgressive-regres-

o activity (Barrett, 1981). pretations include (ii) variations in sur-


face-water productivity, orland (iii)
sive cycles (Weaver and Wise, 1974).
The Monterey Formation of California,
o POST-SU8DUCTION
variations in the input rate of the ter-
rigenous component. These three
one of the better-studied ancient chert
formations on land, was deposited in
o DEPOSITS
~RSE
alternative processes, however, do not
adequately explain the sharp lithologic
a Miocene continental margin environ-
ment composed of deeper and shal-
( FLrSCH filE
boundaries between the chert and lower water sites (Isaacs et aI., 1983)
o fEUGIC DEPOSITS
(CHElITI LlKESTOKEJ
GflEfNSTOKES
- SPIL ITES
interbedded shale layers which should
have been obliterated by the activity of
comparable to the present California
borderland.The Monterey Formation is
burrowing organisms, if these sedi- one of the principal sources of, and
ULTflAIlASI&flOCKS
c (OPHIOLITES)

(0)
ments were deposited through slow
pelagic accumulation. Nearly all "bed-
an important reservoir for, California's
onshore and offshore hydrocarbon
o ded cherts" contain shale interbeds, accumulations, underlining the eco-

c often of red or green colour, that com-


prise between 5-40% of the sequence.
nomic significance of organic-matter
rich biogenic siliceous sediments
o Insome cases, the chert beds display
none of the evidence for redeposition
(Isaacs, 1984).
Biogenic silica accumulations in
o (b)
listed above, but still have sharp bottom
and top contacts. This is why some
near-shoreenvironments may occur in
close association with shallow-water
o investigators prefer variations in bio- carbonates and give rise to chert nod-
o C.nhn..t.1
PI.1t genic productivity andlor diagenetic
segregation as origin for these deposits
ules. Shallow-water sandstones and
siltstones, apart from common silica
l (e.g., Diersche (1980) for the well-bed- cementation, are remarkably poor
ded Upper Jurassic radiolarites of the in concretionary silica (Dapples, 1967),
C- Eastern Alps). However, the lack of pri- in contrast with continental deposits.
D (c) mary sedimentary structures may be The aforementioned Tertiary shallow
due to other reasonssuch as diagenetic marine examples of the Atlantic and
obliteration during recrystallization Gulf coastal plains of the US contain
Figure 5 (a) Schematic representation of

,..
the " Steinmann trinity " (= ophiolite stratig·
raphy) of ultrabasic rocks , altered basalts
and/or uniform small grain-size. From
the recent literature, a general con-
silica-cemented sandstones that ap-
pear to have received the silica from
sensus seems to emerge that the bed- the associated opafine claystones
and pelagic sediments (radiolarian cherts
and limestones); (b) origin of the ophiolite
ding in radiolarian cherts cannot be (Wermund and Moiola, 1966; Wise and
stratigraphy through ocean crustgeneration ascribed to a single process (e.g., Bal- Weaver, 1973; Weaver and Beck, 1977;
at mid-oceanic ridges; and (e) its destruc- tuck, 1983; Heinand Karl, 1983; Jenkyns Carver, 1980). In Paleozoic sequen-
I.
tion In subduction zones. (From Chipping, and Winterer, 1982). Recognition of ces, siliceous sponge spicules often
'-... .
1971). symmetrical geochemical changes abound, particularly in deep basinal
.,
..

'-..

(
c
232 Diagenesis Geoscience Canada Reprint Series 4 c
c
deposits , but have also been consid- scopically as cherts although they may chert predominantly of (micro-)quartz.
c
ered as shoreline indicators (Cavaroc
and Ferm, 1968,Lane, 1981). In a num-
still consist entirely of opal-CT. Diato-
maceous shale on the other hand, has
For this reason, Calvert (1971) first sug-
gested a nomenclature of siliceous
c
ber of cases, spicules provide an ade- the appearance of porcelanite, even rocks strictly based on mineralogy, a c
quate source of silica. Their diagenetic
end-products are nodular cherts or
after having reached the quartz stage.
Because these rock names were origi-
usage largely followed by the DeepSea
Drilling Project (e.g., Riech and v. Rad,
c
chert nodules which frequently occupy nally designed for the field description 1979). However, for the alternative c
only a small fraction of the total volume
of the carbonate or evaporite host rock,
of siliceous rocks (Bramlette , 1946),
they will be used in this review in the
descriptive approach, see Pisciotto
(1981 ). c
These nodular cherts are distinctly dif-
ferent from the ancient bedded cherts in
sense of Isaacs et al. (1983). That is, the
distinction between porcelanite and
The characteristics of the different
silica phases and the diagenetic transi-
c
the rock record and from the biogenic chert will be based primarily on detrital tions from one phase to the other will be c
siliceous oozes, muds and cherts on
and under the modern ocean floors.
content. Often, however, porcelanite
consists predominantly of opal-CT, and
described in the following paragraph.
Important questions to be discussed c
Diagenesis of the latter will be dis-
cussed in this paper. The diagenesis of
are: What are the physicochemical
mechanisms involved in the transfor-
c
the former may proceed under condi-
2.5 A 3.0 3.5
I
4 .0
I
50
mations? Are the transformations of c
tions considerably different from those
of the deep-water cherts, and those of
opal-A to opal-CT and of opal-CT to
(micro-) quartz exclusively due to dis- c
the siliceous deposits in alkaline lakes
A
solution-reprecipitation reactions as c
and in soils.Thediagenesis ofthese and
other types of chert , including silicified s------- favoured by recent findings, or is there
any evidence for the solid state reac- c
wood, will be discussed in the com-
panion paper (Hesse, this volume , p.
tions originally suggested by Ernst and
Calvert (1969)? What are the rate- c
253-275), ending with a note on the
C
controlling factors? In particular, how c
cherty varieties of Precambrian banded
iron formations.
does lithology influence transformation
rates? Why is an intermediate state of c
STAGES OF BURIAL DIAGENESIS IN o
metastable opal-CT required in thetran-
sition from opal-A to quartz?
c
BIOGENIC SILICEOUS SEDIMENTS c
During burial, biogenic siliceous sedi-
ments undergo a characteristic se-
CHARACTERISTICS OF THE SILICA
PHASES IN BIOGENIC SILICEOUS c
quence of mineralogic transformations
which may be subdivided into three E
SEDIMENTS
Opal-A: Physical Characteristics,
c
stages, each defined by the predomi- Solubility, and Polymerization. c
nance of one of the common low-tem-
perature silica phases (Calvert, 1971):
The tests of siliceous microfossils as
well as silica precipitated inorganically c
(1) the opal-A stage of siliceous oozes
or muds; (2) the opal-CT stage of por-
under earth surface conditions, as in
hot-spring areas or desert soils, consist
c
celanites; and (3) the microquartz or of an X-ray amorphous substance C
quartz stage of chert sensu stricto named opal-A (Jones and Segnit, 1971),
(quartz chert). Silica recrystallization in due to its mineralogical similarity to E
petrified wood follows the same se-
quence, whereas some cherts in car-
precious opal. The X-ray pattern of this
near-amorphous substance resembles
C
bonates and some non-biogenic cherts glass, with a broad hump near 4~ C
may follow different diagenetic path- (Figure 6A). This material is very po-
ways as discussed in the companion rous and has a substantial water con-
C
paper. I
30
CUKlI
I
28
I
26
I
20
I
18 0 29 tent (4-9% in precious opal). Opal-A C
Porcelanite and chert do not simply dissolves easily in seawater, which is
reflect the mineralogical difference highly undersaturated with respect to (
between opal-CT and quartz as a result
of progressive diagenesis. As sug-
Figure 6 (A) X-ray diffractogram for opal-
A (broad hump at about 41\) and detrital
opaline silica everywhere in the modern
oceans.
e
gested by Isaacs et a/. (1983), primary
compositional differences, such as the
quartz (Q) in diatomaceous shale. (8 to
I) peak-sharpening and shift in position of
In inorganic systems, equilibrium sol-
ubility of silica depends on a number of
c
ratio of clay minerals to silica minerals, the (101)diffraction of opal-CT with progres-
factors besides temperature (Figure L
sive burial in the Monterey Formation of Cal-
areoften moreimportant in determining
textural and physical properties on
ifornia . Doublet peaks at 4.11\ and 4.31\ for
7a), notably surface area and particle
size of the solid silica phase (Figure 7b),
C
cristobalite (Cr) and tridymite (Tr), respec -
which the distinction of rock types is tively. Numbers in brackets: cristobalite- and to a lesser extent pressure, as C
based. In the Monterey Formation, the d(101)ofopal-CTinangstroms. (J) Diffracto- stated in a previous section (Figure 7c).
most silica-rich sediments (pure dia- gram of quartz chert. (Modified from Murata It increases significantly with a pH C
tomites) form rocks that appear macro- and Larson, 1975, fig, 5). greater than about 9 (Figure 7.d, C
C
C
c
C' Diagenesis of Biogenic Siliceous Sediments 233
C
c' Williams et al., 1985, Williams and shell wall (Hurd and Theyer, 1975). solid phases. For this reason, a some-
c Crerar 1985).Other ions in solution can Equilibrium solubilities of the other low- what closer look will be taken at the

c have distinct effects on dissol ution rates


of solid silica. Dissolved AI and Fe
temperature silica polymorphs, o-crls-
tobalite and quartz, are respectively
chemistry and kinetics of the dissolu-
tion and precipitation processes of
( adsorb to the opal-A surface and sup- one and two orders of magnitude lower silica , including polymerization . In
press its solubility and dissolution rate than those of opal-A (Figure 7a). How- solutions of pH < 9, dissolved silicon
c (lIer, 1955, 1973; Lewin, 1961). Also , ever, for opal·CT no thermodynamic is present predominantly in the form

c ageing of the biogenic siliceous tests af-


fects solubility through changes in sur-
data exist.
Silica solubilities bear great import for
of undissociated silicic acid H4Si04
(orthosilicic or monomeric silicic acid).
c face area and crystallite size in the the diagenetic transformations of the The dissolution of solid silica can be


c (0) (b)
c -1.0 ,...---r---r--,.---,----,---r--....,...~ 5000

_ -1.5
-
~
tT
-2.0
2000
1000
500_
N

eno -2.5 200 Q. a.


r: E -3.0
0'
o
100'1;
50 ~
o
-0"
220 IIEE---_

-
t\I
.. -3.5 20 en o
~
0' -4.0
10 en 10
o 5 ~
r:
-45L...-....1--J-_'----'----'-_-'----'---=- 2
.0 100 200 300 400
Temperature (OC) o 50 100 150 200 250
Specific surface area m~g

(c) (d)
o
r
- -05,..,...,...,.."""'"'''''"""''................__.........,...,.-r'ln'''ft'''""'I
-; -1.0
c
;;" -I. 5
o -2.0
Cf) -2.5 100--'-'
E
0' -3.0
.2 -3.5
n
- -4.0
~
g-4.5 0 0.5 1.0 1.5 2.0 2.5 3.0 ' 3.5 4.0 4.5
Pressure (Kb)

Figure 7 Solubility diagrams for various silica phases as a function of (8) temperature (from Williams and Crerar, 1985; modified after Walther and
Helgeson, 1977);(b) specific surface area (from Williams et al., 1985); (c) pressure (for quartz at various temperatures between 25° and BOOOC (from
Williams and Crerar, 1985; modified after Walther and Helgeson, 1977); and (d) pH (from Williams and Crerar, 1985; after Volosov et al., 1972).
c
234 Diagenesis Geoscience Canada Reprint Series 4 (
C
written as persist in undersaturated solutions at diffract visible light (in the same manner
C
Si02 (s) + H20 = H4Si04 (aq) . temperatures below 130°C, although crystal lattices diffract X-rays) and to C
At equilibrium, the solubility product, under such conditions they will gradu- produce the iridescent diffraction col-
ally de polymerize (e.g., Krauskopf, ours of gem opals. These spheres con-
(
Ksp , thus approximates the activity
1956). At concentrations below opal-CT sist of several concentric shells of pri-
a(H4Si04 ) . In solutions of pH> 9, ortho-
saturation, monomeric silicic acid is the mary smaller spheres with diameters
C
silicic acid dissociates (Figure 7d), in a
first step into only form present. On the other hand, if ranging from 100to 500.8. depending on C
supersaturation persists, high-molecu- the opal type (Figure 8b). Uniform size
H4Si04 (aq) -+ H3Si04" + H + ,
lar-weight polymers (with molecular of the primary spheres apparently is
(
and for higher pH values (above 13)in a
second dissociation step into
weights up to 10,000) form. Such poly-
mers havecolloidal dimensions (greater
achieved by the dissolution of smaller
polymers and redeposition of the dis-
C
H3Si04" -+ H2SiO~- + H+ . than 50.8.) and may remain suspended solved silica on the larger ones (Darragh C
These dissociations raise the solubility as sols as long as pH remains relatively et a/., 1976).
significantly, because the total dis - high and salinity low. Otherwise, they Opal-CT: Ultrastructure. C
solved silicon concentration is the sum will form cross-links with neighbors and
n
The "CT in opal-CT stands for cristo- (
of the dissoc iated and undissociated coagulate into gels (Figure 8a). balite/tridymite (Jones and Segnit,
species. Silica polymers display a negative 1971) and denotes a modification of opal C
In supersaturated solutions, dis- surface charge, which results in a point which has structural characteristics of
solved silicon polymerizes forming first of zero charge (PZC,i.e. ,the pH atwhich both o-crlstoballte and a-tridymite. C
oligomers (dimers, tetramers and ring the residual surface chargedisappears)
as low as 2±0.5 (Parks, 1965). Silica
Opal-CT is thus the low-temperature
form (a-form) of cristobalite/tridymite
C
structures) and later higher-molecular-
weight polymers as siloxane bonds (Si- colloids thus repel each other unless the formerly called lussatite (Mallard, C
surface charge is neutralized by other 1890).In opal-CT,cristobalite alternates
O-Si) develop through combination of
silanol (-Si-OH) groups: ions in solution, such as metal hydrox- randomly with unidimensionally dis-
C
ides. Interestingly, the hydroxide most ordered tridymite layers. On X-raypow- (
commonly usedfor silica precipitation in der diagrams the main diffraction peak
industrial applications, Mg(OH)2 (IIer, of opal-CT is a doublet at 4.1 and 4.3.8. C
1979),is also thought to be instrumental (Figures 68 to 61). Wise et al. (1972)
in the nucleation of opal-CT, as dis- using the scanning electron micro-
C
cussed below. scope (SEM) first observed the occur- C
The ultrastructure of precious opal rence of opal-CT in the form of small
(silanol) (siloxane)
shows a hexagonal or cubic closest spheres less than 5/Lm in diameter
(
Williams and Crerar (1985) emphasize
the fact that low-molecular-weight oligo-
packing of opal-A spheres that are
remarkably uniform in size (lIer, 1979).
in deep-sea drilling samples . These
spheres, which consist of an inter-
C
mers also contribute to the total sol- Apparently, they are deposited from col- penetrative growth of tiny cristobalitel C
ubility in solutions at or near opal-A sat- loidal particle suspensions of uniform tridymite blades, were called opal-CT
uration, contrary to the assumption in size that grow in supersaturated solu- lepispheres (Figure 9a) by Weaver and C
most previous experimental work that
all dissolved silicon is monomeric in
tions in the absence of natural coag-
ulants. The sphere diameter is in the
Wise (1972). On high-resolution SEM
photos, lepispheres in their incipient
C
such solutions. Oligomers may even appropriate size range (0.17-0.38JLm) to growth stage show sets of subparallel C
E
C
C
C
C
c
e
Three-
c
Dimensional l
Gel Networks
C
(
Figure 8 (8) Polymerization behaviour of dissolved silicon as a function of pH and ionic strength of the solution. (From Williams and Crerar,
1985). (b) Formation of precious opal by deposition oflarge spheres of opa/-A of uniform size in a hexagonally or cubically closest packed layer.
C
Large spheres consist of concentric shells of smaller primary spheres. (From Williams and Crerar, 1985; after Darragh et al., 1976). (

(.
Diagenesis of Biogenic Siliceous Sediments 235

r> .

c
c
c
r
(
c

[TOOjcrist .

----~
/

r:

0
0
r
C d
0,
0
0
0
r

JI
r:
~
r
'-
r:
Cl

'-.J

'---
r:
'-..-'

Figure 9 (a) Small opa/-CT lep ispheres (2-3p.min diameter) growing on euhedral calcite crystals in a cav ity in partially silicified Maestrich tian
chalk, DSDP 14-144-3-2, 103·104 cm. (b) Opa/-CT blades of a "juvenile" lepisphere displaying twinning angle of 70° corresponding to the
intersection angle of the faces of a cr istobalite octahedron as sho wn in (c) and (d). (From v. Rad et a l., 19 77). (e) Composite lepisphere SOp'm in
diameter which resulted from coalescence ofnumerous individuallepispheres, DSDP 12-117A-2cc. (From Florke et al., 1976). (1) Sieve structure
of diatom trustute. (SEM photos in Figures 9a,b,e,f courtesy U. v. Rad)
(
236 Diagenesis Geoscience Canada Reprint Series 4 (
r
opal-CT blades which penetrate each lepispheres in Paleozoic cherts which will be shown later, both the 4.11 and
C
other at angles between 70 and 71 0. have been portrayed in the literature 4.04A peaks have also been attributed (
Individual blades are 2-51Lm long and (e.g., Jones and Knauth, 1979;Meyers, to opal-CT at various stages of burial
0.05-0.1ILm thick, and display ragged or 1977) are invariably too large for gen- maturation (Murata and Larson, 1975). C
rounded edges (Figure 9b). The pene-
tration angle corresponds to the angle
uine lephispheres, unless they are
aggregates.
The justification given by Tada and
lijima (1983) for distinguishing a disor-
c
of 70°32' at which equivalent faces of a Low-temperature Tridymite and dered tridymite from 4.11 A-opal-CT is r-'"
cristobalite octahedron intersect one
another (Figures 9c,d). Florke et al.
Cristobalite as Separate,
Distinct Mineralogic Phases.
that it did not recrystallize to a 4.04A·
phase upon heating (for 11 days to e
(1976)give a plausible crystallographic
interpretation for the peculiar tw inning
The occurrence, under special geologic
conditions, of low-temperature tridy-
1100°C)contrary to what was expected.
In nature, this low-temperature tridy-
c
behavior of opal-CT in the lepispheres, mite and cristobalite as separate miner- mite is observed as a pore-filling c
which appears to be dictated by crystal
growth kinetics. At more advanced
alogic phases distinct from opal-CTwas
proposed by Tadaand lijima(1983). The
cement precipitated from groundwater
or hydrothermal solutions in silicic vol- c
growth stages, the octahedral skel- disordered low-temperature tridymite canic rocks. The low-temperature a-
c
etons will coalesce to form lepispheres.
The diameter of individual lepispheres
(a-tridymite) is characterized by a rela-
tively broad diffraction peak at 4.11 A on
cristobalite is also generally associated
with volcanic and silicic volcaniclastic c
usually does not exceed the length of
the blades (about 51Lm) of which they
X-ray powder diffractograms obtained
from mixtures of a-tridymite, o-cris-
rocks. In deep-sea sediments, it has
been reported from volcanogenic sedi- c
are composed. Larger lepispheres are tobalite and opal-CT. On the same dif- ments overlying basalt in the West c
almost invariably aggregate forms (Fig-
ure se: see also Carver, 1980, figs. 1C,
fractograms, the better ordered o-cns-
tobalite (also called opal-C) produces a
Pacific (Lau Basin, Griffin et al.• 1972)
and Central Pacific (Zemmels and c
1D, 3A, 3B). Relics of former opal-CT sharper diffraction peak at 4.04A. As Cook, 1973).
c
Si02 (mM) Si02 (mM) c
0.0 0 .2 0.4 0.6 o.e 1.0 1.2 1.4 1 .6 i.e 2.0 0 .0 0 .2 0.4 0.6 0.8 1 .0 1 .2 1.4 1.6 1.8 2.0 c
c
100 100 c
(
200
200
c
c
300
300
c
E 400
c
E 400 c
..c 500 c
-C 500
...j....l
...j....l
0.. c
0.
0
GJ 600 c
0
ill 600
1 L81S552 c
700 x L72S516
lie L66S493 c
700 }{ L63S471
y L63S469
z L60S458
c
800
BOO
x L48S405
... L43S387
e L41S369
e
(
't L65S485 900 x L38S348
e L58S446 + L38S338
900 x L38S346 f. L31S299 L
+ L38S345 o L25S241
A L38S343
1000 l!l L24S238 C
e L38S336 (
1000 I!I L25S239

C
Figure 10 Concentration of dissolved silicon in pore-water profiles of DSDP holes. (L, DSDP leg; S, DSDP site). C
C
(
(
r Diagenesis of Biogenic Siliceous Sediments 237
r
C NATURE OF THE the first porcelanite nodules from this observed. Its presence, however, may
C TRANSFORMATION MECHANISMS depth. Below this depth, a less pro- explain some of the fluctuations seen in
Opal-A to Opal-CT Transformation. nounced second maximum may be ob- the concentration-depth profiles of dis-
C Only a small percentage of the pleni- served in sufficiently deep holes, which solved silica (Figure 10).
Confirmation of the Opal-A to Opal-CT
C tude of biogenic silica (opal-A) pro-
duced by planktonic organisms in the
probably corresponds to the dissolution
of opal-CT and the subsequent repre- Transformation as Dissolution-
o surface ocean reaches the sea floor.
Only a fraction of this escapes dissolu-
cipitation as quartz described in the
next section.
Reprecipitation Mechanism.
The discovery of the opal-CT lepi-
( tion during the first metres of burial. Continued dissolution of opal-A in the spheres with the euhedral crystal
c Even this very small proportion of solu-
tion-resistant species will ultimately
sediment during burial is the result of
slowly increasing temperature and
shapes of the cristobalite/tridymite
blades by Wise et al. (1972), Weaver
c· undergo dissolution at greater sub-bot- pressure. Siliceous tests of diatoms and and Wise (1972) and Berger and v. Rad
c tom depths. The effects of progressive
dissolution have been documented
Radiolaria have large specific surface
areas ranging from several tens to 450
(1972) provided the first proof that the
recrystallization of siliceous oozes to
o by systematic SEM studies of diatom m2'g.1 (Kastner et al., 1977),compared porcelanite occurs through a dissolu-

o oozes (e.g., Hein et al., 1978).Breakage


of partially dissolved diatom valves
with 0.1 m2 • g-1 of crushed quartz in the 3
to 5 phi (25-75JLm) size range (VanLier et
tion-reprecipitation mechanism. Lepi-
spheres develop only where crystalliza-
o accompanies and enhances dissolu-
tion, culminating in the complete de-
al., 1960). The sieve structure of the
porous test walls of these organisms
tion takes place in open pore spaces
such as the cavities of microfossils.
o struction of the tests. Dissolved silicon
profiles from DSDP holes in the pelagic
(Figure 9f) is only partly responsible for
these large specific surface areas. As
More commonly, a densely felted mass
of opal-CTforms which impregnatesthe
o realm reflect the dissolution of solid Hurd et al. (1979) have shown, it is sediment andlor replacesother mineral
o silica particles in the subsurface. These
profiles show consistent increases
ultimately the size of the small opal-A
domains (2.5-4.5'&' diameter)in the tests
phases. The latter process may involve
pseudomorphic replacement of opal-A
o in dissolved silicon with sub-bottom which causes the high specific surface by opal-CT in radiolarian tests which

o depth, not uncommonly exceeding


1 mM (or 60 ppm) at a few 100 m below
areas. Surface area can significantly
affect solubility. When the surface area
perfectly preserves the shape of the
shell (Figure 11). The process is still a
o the sea floor. Concentrations may fluc-
tuate considerably with depth, but these
to volume ratio of a substance becomes
large, small changes in pressure and
dissolution-reprecipitation mecha-
nism, which probably proceeds on a
fluctuations are generally superim- temperature may then markedly influ- grain-by-grainbasiswith local precipita-
posed on an overall trend of downward ence its solubility. Suppression of solu- tion immediately following dissolution.
increasing silica concentrations (Figure tion inhibiting factors such as the re- The presence of a matrix of organic
o 10).In many holes, however,the gradual
downward increase is followed by
moval of protective coatings of organ-
ic matter may further increase sol-
matter, which is negligibly affected by
dissolution, may serve as a template
I""'""
an abrupt decrease below a certain ubility. This explains the continuation of which helps preserve the original shape

o depth(e.g., DSDPsite495,Harrisonetal.,
1982; site 570, Hesse et al., 1985) con-
opal-A dissolution during burial, even
though up to 99% of the original opal
of the shell. The process may be similar
to the silicification mechanism in ooids
0, sistent with reprecipitation as opal- from the surface water may have al- (Hesse, 1987), or to the petrifaction of
CT. In the examples mentioned, this ready been dissolved during settling wood. Where Radiolaria occur embed-
D is substantiated by the recovery of and initial burial. ded in lutitic pelagic limestone, an opal-
o In contrast with the earlier dissolu-
tion, dissolution during sediment burial
CT replaced test may simply represent
a cast of the former opal-A shell. Con-
o occu rs in a more or lessclosed system in
which concentration levels may reach
servation of the original shape during
the replacementprocesscannotbeused
G supersaturation before opal-A dissolu- as evidence for a solid-state reaction in
r
tion has gone to completion. In this the opal-A to opal-CT transformation.
\-
case, dissolution will be interrupted by Opal-CT to Quartz Transformation.
o
r
reprecipitation of a less soluble non-
biogenic opal-A called opal-A', which
The opal-CT to quartz transformation
was assumed to be a solid-state mecha-
forms overgrowths on partially dis- nism by Ernst and Calvert (1969) and
solved siliceous tests. (Hein et al., 1978). Heath and Moberly (1971). However,
Crystallite size calculated from X-ray morphological evidence from scanning
diffraction data for opal-A' is larger electron microscopy (Stein and Kirk-
(20-27.&.) than for biogenic opal-A patrick, 1976) makes it more likely that
(12-16'&'). InindividualDSDPholes,opal-A" this step is also a dissolution-repreci-
r:
overgrowths have been found to occur pitation reaction, like the opal-Ato opal-
'-,'
only over a narrow stratigraphic range CT transformation. In their hydrother-
Figure 11 Radiolarian test replaced by of a few metres. This indicates that they mal experiments, Ernst and Calvert
opal-CT,DSDP41-366-23-1, 42-44 em. (From redissolve with the remaining opal-A (1969) heated opal-CT in distilled water
Riech andv. Rad, 1979; SEM photo, courtesy shortly after formation (Hein et al., to temperatures of 300°, 400°, and
U. v. Rad). 1978). Opal-A' is therefore rarely 500°C under 2 kbar pressure. 9uartz
C
238 Diagenesis Geoscience Canada Reprint Series 4 r
c
formed in each experiment. At 500°C areato the left of point 3 in the diagram, with opal-A of any specific surface area
c
the conversion was complete after 30 as well as with respect to any quartz . is too high for quartz to form directly c
hours, at 400°C after 300 hours (12.5
days), and at 300°C after 5000 hours (7
The nucleation and growth ratesof opal-
CT are slower than those of any opal-A,
from the dissolution of opal-A. At such
high silicon concentrations the faces of c
months). For a given temperature the
conversion rate seemed to be constant.
and those of quartz are slower than
those of opal-CT, because opal-CT and
any embryonic quartz crystal would be
crowded by silanol groups which would
c
The concentration of the reactant opal-
CT had decreased during the experi-
quartz are more highly ordered forms of
solid silica than opal-A. Under these
not have time to be properly fitted into
the crystal lattice. Quartz growth will
c
ment in a more or less linear fashion with assumptions, an opal-A' with a surface be blocked and a less "well-ordered "
(
time. On the basis of general reaction-
rate laws, Ernst and Calvert concluded
area lower than that of opal-A will pre-
cipitate and the solution will evolve
phase, opal-CT, will form instead. No
precise thermodynamic data exist
c
that the reaction was of zero order with along the pathway from points 1 to 2 for this phase. Quartz crystallization c
respect to the number of participating
reactants; it had to be a solid-state
shown in Figure 7b. This process is
called "Ostwald ripening" (lIer, 1979;
is only possible when the "equilibrium
solubility" of opal-CT has been low-
c
reaction. Williams et al., 1985). Near point 2, the ered sufficiently through Ostwald c
Stein and Kirkpatrick (1976)re-exam-
ined the reaction products of these
effect of surface area on opal-A sol-
ubility becomes negligible. Atthis point,
ripening. Opal-CT is a classical exam-
ple for Ostwald's step ruIewhich states c
experiments under the SEM and found
fibrous and euhedral prismatic quartz
the solid silica phase with the next lower
solubility, t.e., opal-CT may appear.
that the transformation of an unstable
to a stable mineral phase (at earth sur-
c
crystals among the reacted material Opal-CT is preferent ially precipitated face conditions) often requires one or c
clearly requiring a dissolved phase for
crystallization. A re-evaluation of the
overquartz, because of its higher nucle-
ation and growth rates.
more intermediate metastable phases.
This is an immediate consequence of c
experimental data in the light of nuclea-
tion and growth theory (Christian, 1965;
The effects of reaction kinetics are
informatively displayed by the Williams
the crystallization kinetics (Morse and
Casey 1988). Ostwald's rule is the
c
Nielsen, 1964)showed that a sigmoidal et al. (1985)model. Their discussion will answer to the earlier question concern- c
curve with slower reaction rates at the
beginning and end of the conversion
be carried one step further considering
the relationship between the dissolu-
ing the requirement of intermediate
metastable phases such as opal-A' or c
process would approximate the rate
data better than the straight-line plots of
tion rate of opal-A and nucleation and
growth rates of opal-CT. Depending on
opal-CT. However, under special cir-
cumstances (see section on absence
c
Ernst and Calvert (1969). the mutual relationship of these rates, of opal -CT) quartz may precipitate c
The Opal-A to Opa/-CT and Opa/-cT
to Quartz Transformations as
further evolution of the solution will fol-
low pathways from points 2 to 4 either
directly from solutions whose silicon
was derived from opal-A dissolution c
Examples of Ostwald Processes.
Recognition of inorganically precipi-
along curve " a" (fast nucleation rate) or
curve "b" (slow nucleation rate). In the
but had not reached opal-A equilibrium
concentration (or even the lower opal-
c
tated opal-A' by Heath (1969) and Hein first case, rapid nucleation (relative to CT concentration). c
et al. (1978) demonstrates that the opal-
A to opal-CT transformation is not a
growth) leads to relatively large specific
surface area because the nuclei are
Loweringtheequilibriumsolubilityfor
dissolved silicon through Ostwald
c
single-step process. Rather, it involves
a series of dissolution-reprecipitation
small and numerous. Silica concentra-
tion will drop off and the surface area of
ripening of the opal-CT phase also
counterbalances a solubility increase
c
react ions as postulated theoretically the newly formed opal-CT decrease with rising temperature during burial. c
by the model of Williams et al. (1985).
This model is based on surface-area
(curve 2-4a), only when the silica re-
moval rate exceeds the dissolution rate
This is a prerequisite for quartz pre-
cipitation which would not occur if opal-
c
effects (Figure 7b) and is equally applic- of the remaining opal-A. It, on the other CT solubility was raised substantially c
able to the opal-CT to quartz transfor-
mation.
hand, the growth rate of opal-CT ex-
ceeds the nucleation rate early in the
with temperature. A high-surface area
opal-CT at 50°C has a theoretical sol- c
The hypothetical Si02-H 20 system
used is a closed system at constant
process, then the fluid should evolve
along pathway 2-4b. Analogous consid-
ubilityof 130ppm.Thesolubilityof alow-
surface area opal-CT at 110°Cis about
c
temperature, pressure, pH and consists erations should apply to the opal-CT to 150 ppm (Fournier, 1973), only slightly c
of the pure reactants. In this system,
opal-A of a diatom species with a spe-
quartz transformation discussed in a
subsequent section, although the struc-
higher than that of the high-surface
area opal-CT at 50°C. A solution "in c
cific surface area, say of 250 m2.g '1,
(i.e ., Thalassiosira decipiens, Figure
tural reorganization within the opal-CT
preceding this transformation is inter-
equilibrium" with "ordered" (low-sur-
facearea) opal-CTat 110°C,is therefore
e
7b), will have a solubility of about 100 preted as a solid-state reaction by some super-saturated only 1.5 times with c..
ppm. Ifdissolution ofthe frustules of this authors. respect to chalcedony or cryptocrystal-
species is fast relative to nucleation and The relationship between specific line quartz. A solution "in equilibrium" l
growth of other new silica phases, then surface area and solubility schemati- with a high-surface-area (or " disor- C
the solution will soon become super- cally shown in Figure 7b also explains dered") opal-CT at 110°C, on the other
saturated with respect to opal-A of a why opal-CT is required as an inter- hand,would havea solubility of 290 ppm C
lower surface area (i.e., opal-A'). The mediate metastable phase in the se- (Fournier, 1973) or nearly 3 times the
solution is also supersaturated with quence of diagenetic silica transforma- equilibrium solubility of chalcedony.
C
respect to opal-CT of any given surface tions. Silicon solubility in equilibrium Sincethe growth of a new ("more highly C
L
C
(
C Diagenesis of Biogenic Siliceous Sediments 239
(
C ordered") silica phase such as chal- state reactions during diagenesis. This secondary cristobalite peaks at 3.1 and
C cedony or quartz is favoured by low study revealed characteristic changes 2.8'&' also appear with increasing burial
supersaturation, the " ordering" process in the main diffraction peak of opal-CT approximately in the middle of the opal-
C' during burial of opal-CT operates toward (4.1'&') with progressive burial diagene- CT stage. While the shift in the d-spac-
( this end and ultimately facilitates quartz sis.ln contrast to Tada and lijima (1983), ing of the (101) peak is relatively rapid at
precipitation. this peak is usually attributed to the (101) the top and bottom of the opal-CT zone
o Crystallographic Structural Changes diffraction of a-cristobalite. In siliceous in the TemblorRange, it progresses very

c of Opal-CT and Quartz in the


Porcelanite and Quartz-chert Stages.
rocks of the Monterey Formation in the
Temblor Range of California, a distinct
slowly in the middle stages (Figure 12).
Nevertheless , it does proceed continu-
( Sharpening and shift ofthe opal-CT shift of this peak from 4.11 to 4.04.&. ously over the entire burial range of
(101) reflection. The important find- is observed with increasing burial (Fig- the opal-CT zone. In contrast, Pisciotto
( ing of a dissolution-precipitation step in ure 6). (Slow scanning at a rate of (1981) found the shift to become more
the opal-CT to quartz conversion by 0.5°29 ' min-' permitted measurement rapid in the Santa Maria ValleyofCalifor-
C Steinand Kirkpatrick in 1976did notclose of the peak position with a precision nia with increasing burial depth, starting
o the discussion about the nature of the
transformation mechanism involved
of ± 0.0052'&'). This decrease in the
d-spacing is accompanied by a progres-
in the middle of the opal-CT zone. The
bulk density of the sediments, on the
o in this phase change. A year before, in sive sharpening of the same peak, and a other hand, does not show any systema-

a 1975, Murata and Larson's results of a


high-precision X-ray diffraction study
gradual disappearance of the c-tridy-
mite (001) peak (at 4.32-4.26'&'), which
tic increase over this range of burial
depths (730-2030 m below reference
o gave rise to new speculations about the
possibility of low-temperature solid-
is replaced by the quartz (100)peak (at
the opal-CT to quartz transition). Minor
level). It stays more or less constant
at an average value of 1.16 g'cm-3, but
( increases abruptly to 1.6g .cm-3 over an
o Radiometric '(10f)
age (10 6 yr) cristabalite (angstroms)
Dry bu Ikdensity
(g/cm3 )
80 m thick sediment interval in the opal-
CT to quartz transition zone (Figure 12).
o 4.04 4.06 4.08 4.10 4.12 0.5 1.0 1.5 2.0 2.5 3.0
Oxygen isotope data from the same

o - 0 5? I I I I I I I I I I I I ,I I I
,
burial depths display a similar kind
of behavior. There is no systematic
E
..........
200 ,
\ change within the opal-CT zone (aver-
age value of o,ao = + 29.4%0 relative to
2:
c:::>
- 8? \
\
SMOW), but a significant decrease
by about 5%0 appears within a short dis-
() ~
600 · + I
,
\ tance below the porcelanite/chert
<C boundary. Murata et al. (1977) con-
~ I
a:::
1000 \ Clay cluded from these observations "that
c' c:::>
u-
"shales
the structural ordering of cristobalite,

o 2:
c:::> ,,
\
\
manifested in changes of the d(101)
spacing, occurred through reactions in
o <:..!)
UJ
::c
1400
,, the solid state" within the opal-CT
stage, but involved complete dissolu-
<...:>
~
UJ 1800
, I
tion-reprecipitation at the stage bound-
ary with the quartz zone.
u- As Isaacs at al. (1983) pointed out,
o c:::>
CL
c:::> 2200
\
I
I
I
however, " neither the structure of the
mineral opal-CT nor the mineralogic
( ~ I significance of the d-spacing of opal-
12? I
3= CT are" sufficiently well understood
c:::> I
--.J 14 I to interpret the changes in the structure
UJ 2600 I of opal-CT as an ordering process in
a:l I
15.3 I the strict sense, although this is what
::c I
~
CL
UJ
3000 ,
I

I
most authors assume. For instance,
the sharpen ing of the (101 )-cristobalite

••
C) I peak with increasing burial may reflect
22.5 I growing crystallite size of the opal-CT.
26
3400 The growing crystallite size in turn
may result from gradual dissolution of
smaller crystals and redeposition of the
Figure 12 d(101) spacing of opal-CT in porcelanite (circles) and cherts (triangles) from the
Monterey Formation in Chico Martinez Creek, plotted against depth below the top of the
dissolved silicon on larger ones (an Ost-
Etchegoin Formation. (From Murata and Larson, 1975, fig. 6). Density data : crosses, diatoma- wald ripening process). This may be
ceous shale; open circles, opal-CTporce/anite; half-filledcircles, porcelanite with quartz; filled considered a re-ordering process in a
circles, quartz chert; filled squares, shale; dashed line, densities of normally compacting general, but not in a strict, sense. High-
shales. precision X-ray diffractograms are sen-

r
c
240 Diagenesis Geoscience Canada Reprint Series 4
(
r
sitive enough to depict such minute the opal-CT stage because the isotopic
c
c
70

structural changes, whatever their ratio of growing larger crystals may be


physical cause, and therefore record inherited from dissolving smaller ones. (
these modifications continuously with Density may also change very little
burial. Standard oxygen mass spec- because the morphology of the opal-CT (
trometry or pycnometry methods may blades remains essentially unchanged.
not pick up small, but continuous , These considerations would make the (
changes with progressive burial. Wil- problem amenable to interpretations
liams and Crerar (1985) and Williams based entirely on dissolution-repreci- C
et al. (1985) suggest that some of the pitation reactions. This would eliminate (
seemingly abrupt mineralog ical or geo- the need for solid-state reactions, which
chemical changes at the boundaries of at the low temperatures of diagenesis C
the opal-CT stage may in fact be more are prohibitively slow.
gradual than they appear to be. Some of Crystallinity index of quartz.
C
o ,
6!:-9-------J.,---'"'------:;';----~
68
!

67
these changes occur so slowly that the
less sensitive methods do not see them
Sharpening of the (101) cristobalite
peak with increasing maturation may be
C
before a certain threshold level charac- likened to the improvement in quartz C
teristic of a diagenetic stage boundary crystallinity with progressive diagene-
is reached. Effects will only be seen sis described by Murata and Norman
C

CR Y STAL LINIT Y
INDE X after a significant portion of the rock (1976). The quartz crystallin ity index of C
has undergone transformation. Alter- these authors is based on high-preci-
(
natively, the oxygen-isotope composi- sion XRD measurements at slow scan-
tion may in fact change very little within ning speeds (0.25°20min-1 ) of the high-
C
119'3Z'30' 119'30' C
C
o
,,', h'l I C
o .5 1km
10.0
o 4.11
C
C
"" C
C
7.2
C
5.8
C
C
2.6
C
C
C
1.2
C
< 1.0 C
35'
OS'
35'
OS'
c
Figure 13 (a) X-ray diffractogram showing
e
the quartz quintuplet at about 68 028, and the (
Parameters a and b used to define the quartz
crystallinity index Cl of Murata and Norman
(1976, fig. 2; for explanation see text).
c
(b) Tracings of diffractograms showing 119'3Z' 30' 119'30' (
increasing quartz crystallinity from bottom
to top. Asterisk marks (212) peak at 6Z74 0 Figure 14 d(101)spacing isopleths for opal-CTporcelanite in the TemblorRange southwest c
28 which is used for the determination of of Taft (California) . These provide an example of " isograd " mapp ing in low- to intermediate- (
the index . CuK" radiation (from Murata and grade diagenetic rocks. Note apparent congruency between structural features and diage-
Norman , 1976, fig. 1). netic trends. (From Murata and Randall, 1975). l.
l
l
c
c' Diagenesis of Biogenic Siliceous Sediments 241

c'
e, angle region between 67 and 69% (Cu cherts sensu stricto. Cretaceous quartz fornia generally conform to the geo-
( K", radiation). In this 20 range, moder- cherts in the West Pacific at about logical structures (Figure 14). The
ately to well-crystallized quartz pro- 400 m subsurface depth have crystal- lowest d-spacings (4.05 to 4.04~)
( duces a quintuplet of XRD peaks. Of Iinities generally less than 1 (using a straddle the axes of anticlines. How-
( these the (212) peak at 67.74° measures scaling factor of 1.36, Pisciotto, 1980). ever,as Mizutani (1977)noticed, the dip
the effectsoft he recrystallization ofcryp- Franciscan cherts show considerably of the reconstructed iso-d-spacings in
(' tocrystalline to microcrystalline authi- better crystallinities (Figure 13b), but the cross-sections of Figure 15 is less
genic quartz during diagenesis and reach high values (above 8.0) only in than the structural dip. This probably
c low-grade metamorphism. The quartz metamorphosed rocks (Murata and indicates that structural deformation in
( crystallinity index most probably is a Norman, 1976). the Temblor Range started when opal-
measure of crystal size. It is defined as Opal-CT d(101) spacing and quartz CT maturation was still in progress
c CI = 10Fa/b crystallinity as mapping tools for dia- (Figure 15c). Alternatively, as dis-

c where a is peak height on the high-angle


side, b is the total peak height (as
genetic grade. Variations in the
d(101) parameter of opal-CT have been
cussed below, discordant maturation
levels with respect to tectonic struc-
c- shown in Figure 13a)and F is a scaling
factor which varies with instrumental
used to map regional maturation levels
in relatively low-grade diagenetic rocks
tures could reflect lithological effects
of the host rocks (Isaacs, 1982).
o settings and adjusts the crystallinity
index to a scale of 0 to 10. The crystal-
(Murata and Randall, 1975)comparable
to isograde mapping in higher-grade
Keller et al. (1985) used quartz crys-
tallinityto map diagenetic and metamor-
( linity of authigenic quartz is charac- metamorphic terrains. The contour- phic grade in the Ouachita Mountains of
teristically poor (e.g., 2.0 to 3.2 in the lines of iso-d-spacings in the Monterey Arkansas and Oklahoma and in a con-
Monterey Formation), even in quartz Formation of the Temblor Range of Cali- tact metamorphic aureole on the Isle of
c. Skye, Scotland. Crystallinity was deter-
mined by mean apparent crystal size
measured underthe SEM. Crystal size
o ranged from less than 1 /Lm for crypto-
crystalline, anhedral quartz in nonmeta-
c morphic terrains to more than 100 /Lm
o for polygonal, triple-point euhedral
quartz in tremolite, diopside and forster-
c ite-grade rocks. The contour maps out-

c line the regional structural trends and


depict areas of subsurface igneous
c activity.

J[
A'

:"~lA ~
QUARTZ
b

.~
RATE CONTROLLING FACTORS OF
('
(b) THE DIAGENETIC SILICA
4.01
TRANSFORMATIONS
4.09 Rates of the Opa/-A to Opa/-CT
( 4.11 L...- -'- ,;,.....---J
Transformation in Deep-sea
o Environments: Temperature and

c Time.
Temperature is the dominant rate-deter-
o
("
( C) mining factor for the diagenetic silica
transformations as illustrated by the ex-
periments of Ernst and Calvert (1969)

o for the opal-CT to quartz transformation


(described above). This is also evident
L in the experiments by Kastner et al.
(1977)for the opal-A to opal-CTtransfor-
( mation (described below). The theoreti-
cal basis for this is the Arrhenius equa-
8· Figure 15 (8) Geologic cross-section with reconstructed d(101) spacingprofiles for opa/-CT tion for the rate constant k of a chemical
in the Temblor Range showing near-concordant relationship between folding and maturation reaction
r levels. For location of section A-A' see Figure 14. (From Murata and Randall, 1975). k = A . exp(-Ea/RT)
(b) d(101) spacings of opa/-CT in surface samples along line A-A'. Region marked "quartz"
where Ea is the activation energy, T is
Ir, indicates replacement of porcelanite (opa/-CT) by quartz-chert, where d(101) dropped below
temperature, R is gas constant, and A is
the lower limit of 4.04"- for opal-CT.
c
I'
(c) Schematic representation of discordant structural and maturation patterns. (From
Mizutani, 1977). Dashed lines, d(101) isopleths; continuous lines, bedding. Note that the
a frequency factor. During the diagene-
sis of deep-sea pelagic sediments or
silica-bearing shallow-water sediments,
reconstructed d(101) isolines in (a) dip less steeply than the geologic structures, suggesting
thatopa/-CT maturation was still in progress when tectonic deformation started. Alternatively pressure effects are generally negligi-
'-..- delayed crystallographic changes might indicate lithologic control. ble compared with temperature or other
effects. Pressure is generally hydro-

c
c
242 Diagenesis Geoscience Canada Reprint Series 4 r
c
static in these environments and varies on seismic reflect ion profiles because it plate was still located south of the equa- C
only to a small extent over the .burial
intervals of a few hundred metres in
is associated with the transition from
siliceous ooze to porcelanite, which is a
tor and had first subsided below the CCl
(see section on "pelagic stratigraphy
C
which the first silica transformations major regional lithification event. In the model" p. 229). The "upper opaque C
take place. Northwest Pacific , for example, this layer" on North Pacific seismic profiles
What are the actual in-situ tempera- event is marked by the occurrence of an west of Hawaii thus records adiagenetic C
tures at which the opal-A conversion to
opal-CT takes place? Downhole tem-
"opaque" seismic reflector in the sub-
surface. It first appears at the meridian
history that required an activation time
of at least 15m.y. before it produced bulk
C
perature measurements at DSDP sites of Hawaii (at approximately 155°W, Fig- physical changes . This illustrates the C
184 and 185 (leg 19) in the Bering Sea ure 17) in mid-Tertiary siliceous sedi- importance of the factor time, which
give temperatures of 35°-51°C at ments (15-20 m.y. old) which rest on 90 may play the major role in diagenesis, if C
500-600 m sub-bottom depths in the
diatomaceous sediments where the
m.y. old Upper Cretaceous oceanic
crust. The reflector increases in thick-
temperatures are low.
Host-rock Lithology as
C
bulk change occurs from opal-A to opal- ness westward from less than 20 m to Rate-controlling Factor. C
CT (Hein et al., 1978). In the Temblor 200-300 m in the West Pacific. As In addition to temperature and time,
Range of California, Murata et al. (1977) numerous drill holes have shown (e.g., there are other factors which may pro- C
obtained oxygen isotopic temperatures DSDP legs 7, 16, 17, 20, 32, 55, 61, 62,
89), the thickness of the reflector repre-
mote or retard the diagenesis of sili-
ceous sediments. Since Bramlette 's
C
for opal-CT from porcelanites of the
Monterey Formation in the range of sents the combined thickness of both (1946) classical work on the Monterey C
41 0·56°C (mean 48°C). They used the siliceous rocks and pelagic limestones. Format ion numerous exceptions from
fractionation factors of Clayton et al. The "opaque layer" can be deciphered the general maturation sequence "sil i-
C
(1972) and labeyrie (1974) assuming a on seismic profiles as a distinct interval ceous ooze -+ porcelanite -+ quartz (
/)1110 of 0%0 (SMOW) for the pore water because it is underlain by a "lower seis- chert " have been recognized . For ex-
from which the opal-Of precipitated. At mically transparent layer" consisting of ample , in the Monterey Formation, par- C
a nearby locality, an interstitial water
/)'B() of + 3.7%0 had to be assumed to
older, less brittle and relatively poorly
consolidated clayey sediments. The lat-
celanite and/or quartz chert beds oc-
cur within the zone of non-recrystal-
C
obtain the same range of temperatures. ter correspond to the lower horizon of lized diatomaceous mudstone and dia- C
These estimates correspond well with brown abyssal clay(-stone) that formed tomite , and chert layers occur within the
a temperature of 50°C calculated on when the northern part of the Pacific porcelan ite zone. Apparently, the dia- C
the basis of geothermal gradients by the
I
C
same authors for the marine sect ion of TERTIARY I CRETACEOUS J U R.
the Temblor Range where the transfor- 20 60 100 11.0 160m.y. C
mation to opal-CT allegedly took place .~!:~::~::~::~::~::
at a sub-surface depth of 700 m. A con- .......................
... ... ... ... ... ... ...
t'.t-,:.... :.... :: ••: ••••:.... :....: C
.....................
....-.... .-.... ...
......................... ... .-.... .-.. C
siderably lower range of temperatures
.......................-.....
. .-.-CT ... - •••:: ••:: ••.-...
(9°-27°C) was estimated by Pisciotto
(1981). This range applies strictly to the ..opal- C
.-.-................._. -.-..:.:..... :..•..
?~

-.- .. .-.....-.--....
top of the opal-CT zone (defined as the ~.:

depth where opal-CT exceeds 5 weight :I:


_
...-.....-.....
-.-...
................. C
..:---::.....:---•........ - .
~
percent (wt. %)) in the Monterey Forma- ~
_
C
tion of the Santa Maria Valley and is an UJ
~.: ::..:::..:::.
absolute minimum range. It is based on
°80
..J
..•:?'.:.••.:..•.:..•.
..............
••• ' • • • •• • • • • c C

)~~~~l~~~~~
000(
detailed considerations of the thermal
and subs idence history of the region. IX:
~
l
Opal-CT formation started about 2 mil- ell
C
lion years (m.y.) after deposition and
reached a peak after 4 to 10 m.y. (the
!1200
II::.::'::.:.:'::.::.••:•.•
. , ' .
••• " ~ ~titk'
I - : •• : .... :t::-.::•• ::•• ::
. li!.: •• ::••:••••::.•::••::.•
':'::••:'::-,:.::-,:'::-,:'::.•:'::••::'
C
shorter time corresponding to higher C
heat flow).
In the pelagic realm away from the
•..
:;::.:.: :::.:: ::.::::.::::.::::.:: ::.:: :••::r, •• • ~... - -- ::.::::.: :::.:::.
::.::_.::.::::.::::.:: _ -..
•::.:.:.:.:.:.:·:·:6:.:-:·:.:.:·:·:.:.:-:·:.:.:·:·:.:.:·:·:.:.:-:.:.:.:.:-:.:.:-:.:.:.:.:.:.::.:-:::.:.:::.:.:::-:.:::.:.:::.:.:: :-:.::~ c
1600
mid-ocean ridges, the transformation
occurs at shallow subsurface depths of
m
e
a few hundred metres, where tempera- ~ opal-A _ opal-CT(porcellanites) k~~~:::}:·:] quartz (cherts) c
ture rarely exceeds 20° -30°C. At these
low temperatures, the transformations
are very slow and the opal-A to opal-CT
A opal-A (rare opal-eTl
B opal-A. opal- CT (access. quartz)
E quartz
A l'OU"lI opol-CT in CSiotom. • .cs lInclion Oeeonl
c
conversion takes some 10 m.y. to go to C opal-A, opal-CT. quartz & l'OUng opol-CT in oll•••CS o.hn I Allontte oe.onl C
completion. For temperatures well be- o opal-CT,quartz l
low 30°C (Figure 16), the conversion
would take up to 30 or 50 m.y. The trans- Figure 16 Age/burial fields for occurrences of opal-A , opa/-CT and authigenic quartz in drill- l
formation can be traced regionally holes of the Deep Sea Drilling Project. (From v. Rad, 1979; after Riech and v. Rad, 1979).
C
(

C
(
c Diagenesis of Biogenic Siliceous Sediments 243
(
c genetic reactions leading to the silica presence of either calcareous ooze or 4. In each of the experiments in which
c transformations proceed faster in cer-
tain horizons than in adjacent ones. In
montmorillonitic clay. The main results
of these experiments can be sum-
opal-CT crystallization occurred , the
concentration of Mg2+ and (OH)- was
( other cases, the trans ition to quartz marized as follows : lowered in the ratio 1:2, parallel with
( seemed to have occurred directly from 1. In all experiments at 150°C, but not in the decrease in the concentration of dis-
opal-A without an intermediate opal-CT all room-temperature experiments, cor- solved silicon .
( stage (e.g., Lancelot , 1973). rosion of the siliceous tests took place 5. Newly formed embryonic opal-CT
As observed during early legs of the after periods of one day to one month. lepispheres always contained trace
( DSDP (e.g., v. Rad and Rosch, 1972; 2. After 2 to 3 months, precipitation of amounts of Mg.
( Lancelot, 1973; Keene, 1975), lithology opal-CT lepispheres was observed, but 6. In the absence of Mg (e.g., in experi-
of the host rocks has a distinct influence only in the experiments with seawater in ments with art ificial seawater lacking
o on silica transformations . For example , the presence of calcite. In these experi- Mg), no opal-CT crystall ization was

o in clayey sediment sections, silica matu-


ration had reached the opal-C'T stage of
ments, embryonic opal-CT lepispheres
could be detected after only one day.
observed during the experiment, even
though calcite was present.
o porcelanite, whereas in accompanying
calcareous sediments of the same age
Precipitation of the lepispheres occur-
red preferentially on the surfaces of
7. In experiments with initial borate
alkalinity instead of bicarbonate alka-
o and thermal maturation level, quartz foraminifera. linity, opal-CT lepispheres formed in the

o chert had formed. This led to specula-


tions that, if the host rock is calcareous,
3. In the presence of calcite, the con-
centration of dissolved silicon de-
same manner as in the presence of bi-
carbonate.This indicatesthat it isthe hy-
o opal-A might convert directly to quartz
(quartz-prec ipitation hypothesis of Lan-
creased compared with those without
calcareous ooze, in which no opal-CT
droxyl ion which is involved in the trans-
formation and not the bicarbonate ion.
o celot, 1973) without the intermediate precipitation was observed. 8. In experiments with montrnorillonlttc

o opal-CT stage.
Experiments by Kastner et a/. (1977)
Particular attention was paid in the
experiments on the effects of Mg(OHb
clays, dissolution of siliceous tests took
place, but no reprecipitation of opal-CT
o provided insight into the role of host- for the precipitation process because of occurred. However, small amounts of an

o rock lithology and related solution


chemistry for the opal-A to opal-CT
the known role of magnesium hydroxide
as a coagulant in silica precipitation.
Mg-rich clay formed.
The results highlighted the signifi -
o transformation. In these hydrothermal
experiments, diatom frustules and ra-
Apparently, the presence both of Mg-
ions and hydroxyl-groups is essential
cance of a magnesium hydroxide com-
pound (MHC). This compound, MHC,
o diolarian tests were reacted with sea-
water or distilled water at 150°C in the
for opal-CT crystallization, as shown by
further results of Kastner et a/. (1977):
attracts silanol groups with their high
negative surface charge and causes

120 ' 150' 180' 120' 90'

Opaque layer th ickne..


o 60'
~ 20-200 meters

o ~ 2oo-JOO meters

o ~.~
>300 meters

o
o
o
JO' !!l...---+---.~.&

120' 150'

Figure 17 Thickness of seismic-stratigraphic units in the Pacific . (From Wyllie, 1971; after Ewing et aI., 1968). Isopach lines for upper
transparent layer in tenths of seconds reflection time (two-way travel time, i.e., each contour represents approximately 100metres).
c
244 Diagenesis Geoscience Canada Reprint Series 4 c
c
them to precipitate and nucleate as the formation of the magnesium-hydro- periods of 1 to 30 days (Figure 18). In c
opal-CT lepispheres. The MHC has
been postulated to be the mineral
xide nuclei. Consequently, no opal-CT
formed during the duration of the
all experiments , Mg and (OH) concen-
trationsdecreased in the 1:2ratio estab-
c
sepiolite (Kent and Kastner, 1985).Opal- experiments (up to 6 months) . lished previously, and opal-CT lep- c
CT precipitation apparently is more
rapid than sepiolite growth once the
Opal-CT Precipitation as
Rate-limiting Factor.
ispheres or embryonic lepispheres
formed. This confirmed that the MHC c
nuclei have formed, therefore opal-CT Extending these hydrothermal experi- serves to nucleate the opal-CT. In c
outgrows sepiolite . The role of calcium
carbonate, which also dissolves in the
ments, Kastner and Gieskes (1983)
determined the rate-limiting steps in
experiments with low-surface area sil-
ica (i.e., Eocene Radiolaria with a spe- c
process, is thought to resupply alkali-
nity consumed in the formation of the
the dissolution-reprecipitation process.
The overall reaction rate is a function of
cific surface area of 5.3 m2'g-') , the
opal-A dissolut ion rate apparently was
c
nuclei. Seawater supplies the neces- the rates of dissolution, nucleation, and the rate-controlling step at tempera- c
sary Mg. When the (OH)-groups have
been exhausted, the rate of nucleus for-
growth of the silica phases involved.
Which one of these mechanisms will be
tures of 50 0 , 75 0 , and 100°C. At these
temperatures, the concentration of dis- c
mation drops and the existing opal-CT
embryos grow to well-developed lep-
the rate-limiting factor depends on spe-
cific chemical and physical conditions.
solved silicon remained below the equi-
librium solubility of l3-cristobalite. Sol-
c
ispheres, provided continued opal-A Amorphous silica of varying specific sur- ubility data are only available for this c
dissolution supplies the required dis-
solved silicon. In experiments with moot-
face area was placed in aqueous solu-
tions of MgCI2 (0.03M) and NaHC03
phase which most closely approximates
a " poorly ordered opal-CT". Nuclei for- c
morillonitic clays, the clay minerals
compete for the Mg and thus prevent
(0.03M) and heated to temperatures of
50 0 , 75 0 , 1000 , 1250 , and 150°C for
mation and growth of opal-CT appar-
ently kept pace with opal-A dissolution
c
c
~
::L
~
<, c
o<t
.-
~
E E
0-
41
0
<t
c
(J)
-,9 C' ~
(J)
¢ -A C' ~
c
a
.-
<t
d ~
:J: ~ <2: :J: <2:
c
1500
.------.. 31 36 6000 ..........--. -,9 25 30
3000 +++ -+-+
' 000

( -.
- A.- 30
__ - - +
. . ... 0 __
30
c
1000
Q.
+
-+r+ •
--+-
29 34 4000 20 20 ?OOO 20 20
c
500
)(.
27 32 2000
+,,+-+ +-
15 10 1000 10 10 c

I· 0_0_
50·C
0-
\0""0-0 l25·C
0-
10 0
o L..-_---.1.._ _-'-_---'-'
50'C
c
0 25 30 0
e b A c
3000
o
b
......--.-
-,8
F 32 29
• __ e ~ . -
A
25 30 4000
,~--.
Q•• _·T_+~...!!+_
.- 30 30
c
10,000
c
/~
'0 • \
20 20
20 20
2000 28 25
I" -,9 °'°'0 - 0 - - - - _ 0 -
. (
'+ I 2000
~ 5000
~~:
10 10
1000 24 21
150·C
+-
15 10
75·C c
0
75·C
20 17
0 10
0
20 30
10 0 OL..----'---.L..--~
c
c
-A DAYS
c
c
5000
.-.- -.e.- 30 30 1)000
~ .....-.-----;
- A. 30 15 c
3000 26 20 A Opal-A 4000 o'+,+-+ + 20 10 c
1000
'+ 0
22 10
,9 I3-Cristobalite '°'°_0- 0 - 10
e
' " - 0- - 0-
+----+ 100·C
• H4S i04 2000
100·C
5

~+18 0 + Mg
00 10 20 30 0 Alkalinity o 10 20 30
DAYS DAYS

Figure 18 Changes in dissolved silicon, magnesium and alkalinity as a function of time and Figure 19 Changes as in Figure 18, how-
temperature in hydrothermal experiments with Eocene Radiolaria (specific surface area of 5.3 ever for Ludox silica (specific surface area of
mr- g-1). -+{3 solubility of a-cristobalite; -+A solubility of opal-A. (From Kastner and Gieskes, 61.5 m 2 .g-1). (From Kastner and Gieskes,
1983, fig . 1). 1983, fig. 2).
c
c
C
r
'-. Diagenesis of Biogenic Siliceous Sediments 245
C'
C at these temperatures . At 125° and isotope data and heat-flow considera- duced d(101)spacing of the initial opal-
C 150°C, however, opal-CT precipitation
became the rate-limiting step after a few
tions (Murata et a/., 1977; Murata and
Larson, 1975; Pisciotto, 1981). The
CT inclayey host sediments. Inthe Monte·
rey Formation, Isaacs (1982) observed
( days , because the concentration of dis- actual temperature at which the trans- that the first opal-CT to appear in a
( solved silicon rose above the equilib- formation occurs at a particular locality progressive burial sequence has a
rium solubility of ,s-cristobalite (Figure is a complex function of many factors, d(101) spacing which varies inversely
r 18). In experiments with higher-surface
area silica (i.e., Ludox silica with a spe-
including the previous opal-CT matura-
tion history. Pisciotto's (1981) tempera-
with detrital mineral content of the host
sediment (Figure 20). This observation
cific surface area of 61.5 m2 • g"), the ture estimates for the base of the opal- confirms the results of Murata and lar-
same behaviour was found at all tem- CT zone in the Monterey Formation son (1975) from the Chico Martinez
peratures studied: ,s-cristobalite sol- (35°-61°C), are also considerably lower Creek study which showed that, at any
ubility was rapidly exceeded; but opal- than those of other authors as they were given burial depth, the opal-CT d-spac-
A equilibrium solubility concentrations for the top of this zone. ing in (detritus-rich) porcelanite is 0.004
were not attained. This again indicated As discussed previously, opal-CT pre- to 0.015,a, smaller than in associated
o that opal-CT precipitation was the rate-
limiting. process (Figure 19). These
cipitation is the rate-limiting factor in the
opal-A to opal-CT conversion, when dis-
(detritus-poor) quartz chert (Figure 12).
This indicates retardation of opal·CT
o experiments also clearly illustrate the solution of immature, high-surface area nucleation in clayey sediments because

o dominant role of temperature as rate-


controlling factor in the conversion of
opal-A is involved. Under such condi-
tions, the concentration of silicon in solu-
of the competition for MHC by clay min-
erals, consistent with the results of
o opal-A to opal-CT.
The Opa/·CT to Quartz Trans-
tion will eventually approach the theoreti-
cal equilibrium solubility value for opal-
Kastner et a/. (1977). Furthermore, it
indicates delayed growth of opal-CT
formation: Temperature and Rate. CT,which is a function ofthe surface area until silicon solubilities "in equilibrium"
Temperature estimates range from 55° ofthis phase for a giventemperature (see with a lower surface area opal-Of (of a
to 110°Cfor the opal-CT to quartz trans- section on Ostwald processes). d-spacing of 4.08,a, or less) are encoun-
formation in the Monterey Formation. Lowered silicon concentrations are tered . Such reduced silicon concen-
These estimates are based on oxygen also required to understand the re- trations in clay-rich host sediments can
be accomplished most easily by adsorp-
RELATIVE DETRITAL MINERAL CONTENT, tion of silica on detrital minerals (Siever
WEIGHT % and Woodford, 1973). Lowered silicon
concentrations can also be achieved by
70 50 30 10 the neoformation of silica-rich clay min-
erals, provided their nucleation and
growth rates are faster than those of the
w silica phases that could potentially
a:
Opal-A ::> form. These and other possible sce-
....
<t narios are discussed in more detail by
a: Williams et st. (1985).
w
c, One would expect from the previous
~ discussion that the detrital mineral con-
w
.... tent , while retarding the opal-A to opal-
Cl CT transformation, would actuallyen-
Z hance the opal-CT to quartz transfor-
(/)
mation . The findings of Isaacs (1982)
<t
W summarized in Figure 20 suggest that
a: this is actually the case. In sediments
u
z with more than 70% detrital minerals
the initial opal-CT has a d(101) spacing
of 4.08,a, or less. In these sediments, the
transformation to quartz should occur
earlier than in sediments with less than
Quartz 30% detrital minerals with an initial
d(101)spacing of 4.11,a,. This is because
reduction of the opal-CT d-spacing to
values below 4.07,a, (4.09,a, in certain
Cretaceous cherts from the West Paci-
30 50 70 90 fic ; Pisciotto, 1980) is a prerequis ite for
RELATIVE SILICA CONTENT, WEIGHT % quartz precipitation. Such an inference,
however, is at variance with the earlier
Figure 20 Schematic summary of the role of host rock composition and temperature as observation (i.e., Lancelot, 1973) that
controlling factors in the opet-cr maturation sequence. The initial d(101)spacing of opal-CThas the silica maturation sequence seems
been shown to vary inversely with detrital content (from Isaacs et aI., 1983; after Isaacs, 1982). to be accelerated in calcareous host
c
246 Diagenesis Geoscience Canada Reprint Series 4 c
c
rocks, which leads to the relatively early transition to quartz. In contrast, in the quartz is opposite to that of opal-CT. c
formation of quartz chert. Santa Maria basin, quartz formation Opal-CT crystallization is promoted c
The ent ire silica maturation se-
quence in clayey sediments is delayed
seemed to be slowed down because it
occurred at higher temperatures in por-
in the presence of Mg2+ (and high
alkalinity). c
by the initial retardation of the opal-A to
opal-O'f transformation. The ambiguity
celanite than in chert.
Absence of Opal-CT as
Summary: The "Stability" Fields of
the Various Silica Phases in Deep-sea c
between the conclusions of Isaacs
(1982)and those of Lancelot (1973)may
an Intermediate Metastable Phase.
It seems unlikely that the opal-CT stage
Diagenetic Environments.
The distribution of the various silica
c
be resolved, if it is assumed that the can be bypassed entirely in the normal phases in oceanic sediment sequences c
delay cannot be compensated for by
later acceleration due to an abbreviated
diagenetic silica maturation process,
except under special conditions. The
has been summarized by Riech and v.
Rad (1979) on the basis of available
c
opal-CT stage. Although the opal-CT reasons why the diagenetic evolution DSDP data (Figure 16).There is consid- c
stage may in fact last longer in carbon-
ates than in clay-rich siliceous sedi-
path opal-A --+ opal-CT --+ quartz is
observed in most situations have been
erable overlap on this depth/age graph
between the fields for the three main c
ments, (contrary to Lancelot's (1973)
assumption), this may be outweighed
outlined in the previous section on reac-
tion kinetics and Ostwald's step-rule.
silica phases.
Opal-A has been found in sediments
c
by a considerably earlier initiation of the Rareexceptions seem to be restricted to as old as 85 Ma (Late Cretaceous), but c
transformation sequence in carbonates .
The field relationship between detri-
micro-environments such as the cav-
ities of foraminifera (e.g., Keene, 1975)
only at shallow subsurface depths. With
increasing depth (and temperature) its c
tal content and opal-CT transforma-
tion rates, reported by Isaacs (1982)
or Radiolaria in calcareous sediments.
These are often filled with chalcedony,
maximum survival time is shortened
significantly. For example, at 1,000 m
c
from the Santa Barbara coast, is not while the host rocks are calcareous subsurface depth, opal-A is normally no c
observed everywhere in the Monterey
Formation. Pisciotto (1981), for exam-
opal-CT rocks or diatomaceous (opal-A)
shales (Isaacs , 1982). This indicates
longer present in sediments older than
about 20 Ma. c
ple, found the appearance of opal-CT as anomalously early quartz (i.e., chal - Opal-CT takes a minimum of about 10 c
well as quartz at lower temperatures in
the Santa Barbara basin to be associ-
cedony) precipitation. Precipitation of
the chalcedony occurred in spherical
m.y. to first appear, requiring elevated
heat-flow.Otherwise its formation takes c
ated with lower detritus contents. In the
most recent study of the problem, the
open cavities indicating limited over-
burden weight and very shallow burial.
even longer. Exceptionally young opal-
CT has been observed by Weaver and
c
role of organic matter for the transfor- This chalcedony does not appear to Wise (1973) in Pliocene sediments (less c
mation reactions was investigated (Hin-
man, 1987). Results suggest that in
have had an opal-CT precursor in the
cavities, because elsewhere in the host
than 5 Ma), where it occurred adjacent
to igneous dykes and sills. On the other c
organic-matter rich sediments the rate
of silica diagenesis should be reduced.
rock opal-CT is still present which shows
nosign thatthe transformation to quartz
hand, opal-CT may still persist in sedi-
ments 100 to 120 m.y. old. Little new
c
Organic acids released byorganic-mat- has started. Most likely, the chalcedony opal-CT forms, however, in pre-Tertiary c
ter maturation would dissociate and
lower the pH thereby reducing carbon-
formed directly from opal-A, possibly
because the concentration of dissolved
sediments (i.e., sediments olderthan 65
Ma), because very little source material c
ate alkalinity. This in turn would slow
down the transformations by decreas-
silicon in the microenvironment of
the cavities, for some unknown reason,
(opal-A) is left in those sediments. With
age and increasing burial, opal-CT
c
ing the silica polymerization rate. remained below a-cristobalite equi- undergoes the progressive crystallo- c
Although lowering of the pH will pro-
mote carbonate dissolution and thus
librium solubility during the early stage
of opal-A dissolution. Among the mech-
graphic structural changes in the d(101)
spacing described earlier. No opal-CT c
buffer the pH, this effect may be nul-
lified, if little carbonate is available or
anisms to maintain low silica con-
centrations in pelagic carbonates dis-
has been found in pre-Cretaceous sedi-
ments (older than 144 Ma).
c
accessible for dissolution . In this case, cussed by Williams et at. (1985), the In Figure 16,the quartz field overlaps c
no effect of carbonate content on the
silica transformation rates may be seen.
early precipitation of calcium zeolites is
a possibility. It seems that as of yet no
the opal-CT field, and to a slight degree
the opal-A field. This overlap illustrates c
as in Isaacs' (1982) study. The initial specific studies have been directed at
this problem . The early diagenetic sta-
how local variations in heat flow, pore c
opal-CT formed in organic-matter rich
sediments should have a lower d(101) bilization of Radio/aria by chalcedony
fluid Chemistry, host-rock lithology and
other factors can affect the rate of c
spacing because of a slower nucleation
and growth rate under decreased car-
might be the key for the occurrence of
Jurassic radiolarites as ribbon cherts
the diagenetic transformations . Quartz
cherts need a minimum of 30 to 40 m.y.
e
bonate alkalinity. In so far as organ ic- which appear to be absent or scarce in to form at burial depths of 500 m or c
matter content may be positively corre-
lated with detrital mineral content, Hin-
younger, diatom-dominated siliceous
sediments.
more, and considerably longer at shal-
lower depths . Genuine quartz cherts, c
man's (1987)results are in accordance
with Isaacs' findings . However, Hinman
Hinman (1987) suggested that direct
quartz precipitation may be possible in
consequently, are rare in Cenozoic
pelagicsediments, but becomepredomi-
c
(1987)did not find evidence that an ini- the absence of Mg2+ , if sufficient alkali-
nity is available. Mg2+ ions in solution
nant in Lower Cretaceous and older sili- c
tially lower d(101) spacing of opal-CT in
organic-matter and detritus-rich sedi- appear to have an inhibiting effect on
ceous rocks. They are the exclusive
lithology of siliceous sediments in the c
ments also accelerates the subsequent quartz precipitation. This behaviour of Paleozoic and Precambrian.
<..
(
(
(
r Diagenesis of Biogenic Siliceous Sediments 247
r

PHYSICAL DIAGENESIS OF Iithified or semi-lithified while others are the microquartz seems to have recrys-
c SILICEOUS SEDIMENTS not. Shaking during an earthquake may tallized in place from opal-CT. The
The treatment of the diagenesis of sili- rupture the lithified layers and cause folded dyke in Figure 21 a behaved as a
(J ceous sediments would be incomplete injection of unlithified sediment into the more competent layer, while the sur-
( without a discussion of phenomena of fractures from adjacent uncemented rounding host sediment was still under-
phys ical diagenesis in cherts. A step- layers (see numerous illustrations in going compaction. Steinitz (1970) and
wise compaction history is character- Snyder et a/., 1983), part icularly if these Snyder et at. (1983)invoke similar mech-
c ist ic of siliceous sediments during bur-
ial, which contrasts with the more grad-
had been overpressured. The opal-A to
opal-CT and the opal-CTto quartz trans-
anisms of dyke and vein formation.
Paris et at. (1985) ascribe chert breccias
/ ual compaction history of argillaceous formations are dehydration reactions. and veins in the Archean Barberton

c sediments. This is implicit in the con-


stant bulk density of Figure 12 for the
They may generate excess pore pres-
sure and cause hydraulic fracturing .
greenstone belt in South Africa to the
injection of hot, high-pressure hydro-
opal-CT stage and reflects the rap id The examples shown in Figure 21 are thermal fluids related to volcanism.
crystallographic changes associated Cretaceous radiolarian porcelanites Some chert breccias, however, are of
o with the phase changes at the stage from the West Pacific east of the Mar- normal epigenetic, synsedimentary

c boundaries.
Other diagenetic features character-
ianas deep-sea trench/island arc. The
dykes probably reflect seismic activity
origin, such as the ones in the Bur-
lington Limestone of Missouri. Accord-
o istic of chert formations are dykes,
diapirs, and breccias that have long
assoc iated with the Marianas subduc-
tion zone . The brittle host sediment is
ing to Carozzi and Gerbe r (1978), these
formed due to storm action on a Missis-
c been described in the literature (e.g., porcelanite consisting predominantly
of opal-CT with chalcedony-filled
sippian carbonate flat. They provide
Taliaferro, 1934).They attest to differen- evidence for the early-diagenetic origin
tial compaction and variable rates of radiolarians. The fractures and dykes of some chert-nodules in limestones,
o silica recrystallization and cementa-
tion. In a given sequence of siliceous
contain porcelanite fragments and fine-
grained opal-CT sediment cemented by
which will be discussed in more detail in
the accompanying paper.
o sediments, some layers may already be microquartz and chalcedony. Some of
o
o
J

r-...
~

o
V

o
o
o
o

C)
o
r

Figure 21 (a) (left) Folded chert dyke in Lower Cretaceous radiolarian porcelanite, West Pacific . Porcelanite fragments in the dyke are
cemented by microquartz and chalcedony which enclose considerable amounts of opal-CT sediment , except where the cement is very light-
coloured (especially at the dyke margins). Folding of the microdyke was caused by differential compaction. The pure chalcedonic cement at
the dyke margin was probably precipitated into pore space that was generated by shrinkage of the host sediment during ongoing compaction
and was probably the latest cement phase . Height of thin-section approximately 2 em. DSDP site 20-198A, sample scc .nt.
(b) (right) Multiple fractures filled with injected opal-CT sediment and fragments which were cemented by microquartz and chalcedony.
Marg ins and ends of the finer fractures are light coloured and consist almost entirely of microquartz or chalcedony cement which probably
was the last cement. Height of section approximately 2.5 cm. DSDP site 20-198A. sample Scc, #4.
c
248 Diagenesis Geoscience Canada Reprint Series 4 c
c
CONCLUSIONS does not seem to have been studied. Berger, W.H., 1970, Biogenous deep-sea
c
The century-old chert problem has been What is the chemical significance of sediments: fractionation by deep-sea c
resolved as a result of chemical ocean-
ographic and sedimentological studies
organic matter in affecting the rates of
silica transformations? What is the role
circulation: Geological Society of Amer-
ica, Bulletin, v. 81, p. 1385-140t c
made possible largely due to drilling
in the deep oceans. Siliceous pelagic
of trace elements forthe transformation
rates, and what is the role of some of the
Berger, W.H. and Winterer, E.L., 1974, Plate
stratigraphy and the fluctuating carbon- c
sediments which coverwide areas ofthe major seawater constituents besides
ate line, in HsO, K. and Jenkyns, H.C.,
eds., Pelagic Sediments on Land and c
deep-sea floor do not originate directly
from submarine volcanic and hydro-
Mg and alkalinity, such as sulphate?
The influence of host-rock lithology on
underthe Sea: International Association
of Sedimentologists, Special Publica-
c
thermal activity. Chemical precipita- the diagenetic silica transformations tion, v. 1, p. 11-48. c
tion as a silica gel or silica extraction
by deep-water radiolarians (Davis, 1918)
also requires further study. Results of
Isaacs (1982) suggest that detrital con-
Bossellini, A. and Winterer, E.L., 1975,
Pelagic limestone and radiolarite of the c
do not contribute significantly to the
formation of Phanerozoic siliceous sedi-
tent accelerates the opal-CT to quartz
transformation while it has a retarding
Tethyan Mesozoic: A genetic model:
Geology, v. 3, p. 279-282. c
ments. The silicon supplied from various effect on the opal-A to opal-CT transfor- Bramlette, M.N., 1946,The MontereyForma-
tion of California and the origin of its sili- c
sources is involved in an ocean-wide
cycle. Siliceous organisms extract sili-
con from nutrient-rich surface waters in
mation (Kastner et a/., 1977). However,
the overall maturation seems to be
faster in carbonates than in clayey sedi-
ceous rocks: United States Geological
Survey, Professional Paper 212, 55 p.
c
regions of oceanic upwelling. A small ments (Lancelot, 1973).
Calvert, S.E., 1966a,Accumulation of diato-
maceous silica in the sediments of the
.C
fraction (less than 10%)of this biogenic These are challenging questions for Gulf of California: Geological Society of C
silica is removed by sedimentation, the further research on silica diagenesis America, Bulletin, v. 77, p. 569-596.
remainder stays in the cycle being re- which have direct applications in petro- Calvert, S.E., 1966b, Origin of diatom-rich C
sediments from the Gulf of California:
dissolved during settling and exposure
on the ocean floor. Dissolved silicon is
leum exploration and basin analysis.
Journal of Geology, v. 74, p. 546-565. C
re-used by organisms up to a 100times ACKNOWLEDGEMENTS Calvert, S.E., 1968, Silica balance in the (
ocean and diagenesis: Nature, v. 219,
for shell construction. Funding forthis review and the author's
Porcelanites and cherts under the research on silica diagenesis came
p.919-920.
Calvert, S.E., 1983,Sedimentarygeochem-
C
ocean floors, which represent an essen-
tial element of the pelagic stratigraphy,
from the Natural Sciences and Engi-
neering Research Council of Canada.
istry of silicon , in Aston, S.R., ed., Silicon C
Geochemistry and Biogeochemistry:
develop from the biogenic siliceous Valuable critical comments streamlin- Academic Press, New York, p. 143-186. C
oozes through a two-stage diagenetic ing the manuscript were provided by S. Carver, R.E., 1980,Petrology of Paleocene-
transformation involving the transition Calvert, E. McBride, A. Mucci and espe- Eocene and Miocene opaline sedi- C
from opal-A to opal-CT and the transi-
tion from opal-CT to quartz. Both trans-
ciallyT. Barrett and E. Burton. U. v. Rad
made available the originals for most of
ments, southeastern Atlantic coastal
plain: Joural of Sedimentary Petrology,
C
formations are dissolution/reprecipita- the photomicrographs included in this v. 50, p. 569-582.
Cavaroc, Wo, Jr. and Ferm, J.C., 1968, Sili-
C
tion processes. Radiolarian cherts of review. R. Yates helped with the photog-
ophiolite sequences are ancient equiv- raphy and drafting. Their support is
ceous spiculitesas shoreline indicatorsin C
deltaic sequences: Geological Society of
alents of these deep-sea cherts trans-
ferred to orogenic belts by obduction
gratefully acknowledged. America, Bulletin, v. 79, p. 263-271. C
Chipping, D.H., 1971, Paleoenvironmental
(tectonic accretion during subduction or REFERENCES significance of chert in the Franciscan C
collision) along active margins. Occur-
rence of these Mesozoic and older ra- General
Formation of western California: Geo-
logical Society of America, Bulletin,
E
diolarites as ribbon cherts, which seem These cover the sections Introduction,
Sources of non-detrital silica in siliceous
v. 82, p. 1707-1712.
Dapples, E.C., 1967, Silica as an agent in
C
to be absent in Cenozoic deposits, may
be related to the early diagenetic pre- sediments, Biogenic siliceous oozes,
Pelagic stratigraphy, Formation of bed-
diagenesis, in Larsen, G. and Chilingar, C
G.V., eds., Diagenesis in Sediments:
cipitation of chalcedony in Radiolaria.
Solving the principal aspects of the
ded chert, Shallow water chert, and Developments in Sedimentology, v. 8, C
Conclusions. p.323-342.
chert problem has also brought into Baltuck, M., 1983, Some sedimentary and DeMaster, D.J., 1981, The supply and accu- C
focus some unresolved detailed ques-
tions of silica diagenesis. What is the
diagenetic signatures in the formation
of bedded radiolarite, in lijima, A., Hein,
mulation of silica in the marine environ-
ment: Geochimica et Cosmochemica
c
mineralogic significance of the change
in the d(101)spacing of opal-CT during
J.R. and Siever, R., eds., Siliceous
Deposits in the Pacific Region: De-
Acta, v. 45, p. 1715-1732.
Diersche, V., 1980, Die Radiolarite des
e
progressive burial diagenesis? Why is velopments in Sedimentology, v. 36, Oberjura im Mittelabschnitt der Nord-
<--
p.299-315.
there little or no change in the isotopic
composition of opal-CT during burial Barrett, T.J., 1981, Chemistry and miner-
alogy of Jurassic bedded chert overlying
lichen Kalkalpen: Geotektonische For-
schungen, v. 58, 217 p.
Edmond, J.M., Measures, C., McDuff, R.E.,
c
although recrystallization reactions
seem to occur throughout the opal-CT
ophiolites in the North Apennines, Italy: Chan, L.H., Collier,R., Grant, B., Gordon, C
Chemical Geology, v. 34, p. 289-317. L.1. and Corliss, J.B., 1979a,Ridge crest
stage and are not restricted to the stage Bates, R.L. and Jackson, J.A., 1980, Glos- hydrothermal activity and the balancesof l
boundaries. The same question may be
raised for the opal-A and the quartz-
sary of Geology, Second Edition: Ameri-
can Geological Institute, Falls Church,
the major and minor elements in the
ocean: The Galapagos data: Earth and
C
chert stages of silica diagenesis, but Virginia, 749 p. Planetary Science Letters, v. 46, p. 1-18. C

c
r
,r Diagenesis of Biogenic Siliceous Sediments 249
r:
r
'-

c Edmond, J.M., Jacobs, S.S., Gordon, A.L.,


Mantyla, A.W. and Weiss, R.F., 1979b,
Water column anomalies in dissolved
Imoto, N., Shimizu, D., Shiki, T. and
Yoshida, M., 1974, Sole markings ob-
served in bedded cherts from the Tarnba
Sano, H., 1983, Bedded cherts associated
with greenstones in the Sawadani and
Shimantogawa Groups, Southwest
C' silica over opaline pelagic sediments belt, Southwest Japan: Kyoto University Japan, in lijima, A., Hein, J.R. and
and the origin of the deep silica max- of Education, Bulletin, v. B44, p. 19-26 Siever, R., eds., Silicous Deposits in
( imum: Journal of Geophysical Re- (in Japanese). the Pacific Region: Developments in
o search, v. 84 (C12), p. 7809-7826.
Folk, R.L.andMcBride,EE, 1978, Radiolarites
Isaacs, C.M., 1982, Influence of rock com-
position on kinetics of silica phase
Sedimentology, v. 36, p. 427-440.
Schmid, E, 1986, Flint stratigraphy and its
o and their relation to subjacent "oceanic
crust" in Liguria, Italy:Journal of Sedimen-
changes in the Monterey Formation,
Santa Barbara area, California: Geol-
relationship to archeology, in Sieveking,
G. deG.and Hart, M.B.,eds., TheScien-
( tary Petrology, v. 48, p. 1069-110t ogy, v. 10, p. 304-308. tific Study of Flint and Chert: Cambridge
Garrels, R.M., 1987, A model for the depo- Isaacs, C. M., 1984,The Monterey - key to University Press, p. 1-5.
sition of the microbanded Precambrian offshore California boom: Oil and Gas Steinberg, M., Bonnot-Coutois, C. and Tlig,
iron formations: American Journal of Journal, v. 82, p. 75-81. S., 1983, Geochemical contribution to
Science, v. 287, p. 81-96. Isaacs, C.M., Pisciotto, K.A. and Garrison, the understanding of bedded chert, in
o Gibson, T.G. and Towe, K.M., 1971, Eocene
volcanism and the origin of the horizon
R.E., 1983,Facies and diagenesis ofthe
Miocene Monterey Formation, Califor-
Iijima, A., Hein, J.R. and Siever, R., eds.,
Siliceous Deposits in the Pacific Region:
A: Science, v. 172, p. 154-154. nia: A summary, in lijima, A., Hein, J.R. Developments in Sedimentology, v. 36,
Goldstein, A., Jr., 1959, Cherts and and Siever, R., eds., Siliceous Deposits p.193-210.
novaculites of Ouachita facies, in Ire- in the Pacific Region: Developments in Steinmann, G., 1906, Geologische Beo-
land, H.A., ed., Silica in Sediments: Sedimentology, v. 36, p. 247-282. bachtungen in den Alpen. II: Die
J Society of Economic Paleontologists, Jenkyns, H.C. and Winterer, EL., 1982, Pa- Schardtsche Oberfaltungstheorie und
Special Publication No. 7, p. 135-149. laeoceanography of Mesozoic ribbon die geologische Bedeutung der Tief-
Griffin, J., 1980, The effect of pressure on the radiolarites: Earth and Planetary Sci- seeabsatze und der ophiolitischen
solubility of 11 silicates in seawater ence Letters, v. 60, p. 351-375. Massenge steine: Berichte der Natur-
at 20°C, pH 8, unpublished Master of Jones, D.L. and Murchey, B., 1986, Geo- forschenden Gesellschaft Freiburg,
Science thesis, University of Hawaii, logic significance of Paleozoic and v. 16, p. 18-67.
Honolulu. Mesozoic radiolarian chert: Annual Re- Steinmann, G., 1927, Die ophiolithischen
Heath, G.R., 1969, Mineralogy of Cenozoic views of Earth and Planetary Sciences, Zonen in den Mediterranen Kettenge-
deep-sea sediments from the equatorial v. 14, p. 455-492. birgen: Congres Geologique Interna-
Pacific Ocean: Geological Society of Kastner, M., Keene, J.B. and Gieskes, J.M., tional, Comptes Rendues, 14e session,
America, Bulletin, v. 80, p. 1997-2018. 1977, Diagenesis of siliceous oozes. I. Madrid, 1926, v. 2, p. 637-668.
Heath, G.R., 1974, Dissolved silica and Chemical controls on the rate of opal-A Weaver,C.E. and Beck, K.C., 1977, Miocene
deep-sea sediments, in Hay, W.W., ed., to opal-CT transformation - an experi- of the S.E United States: a model for
Studies in Paleo-oceanography, Society mental study: Geochimica et Cosmo- chemical sedimentation in a peri-marine
J
of Economic Paleontologists and Miner- chimica Acta, v. 41, p. 1041-1059. environment: Sedimentary Geology,
alogists, Special Publication, v.20, Lancelot, Y.,1973,Chert and silica diagene- v. 17, p. 1-234.
p.77-93. sis in sediments from the central Pacific, Weaver, EM. and Wise, SW., 1974, Opaline
Hein, J.R. and Karl, S.M., 1983, Com- in Winterer, E.L., Ewing, J.1. et et., Initial sediments of the southeastern coastal
parisons between open-ocean and con- Reports ofthe Deep Sea Drilling Project, plain and horizon A: Biogenic origin: Sci-
tinental margin chert sequences, in v. 17, p. 377-405: United States Govern- ence, v. 184, p. 899-90t
Iijima, A., Hein, J.R. and Siever, R., ment Printing Office, Washington, D.C. Wenk, E, 1949, Die Assoziation von Radio-
eds., Siliceous Deposits in the Pacific Re- Lane, N.G., 1981, A nearshore sponge spic- larienhornsteinen mit ophiolithischen
gion: Developments in Sedimentology, ule mat from the Pennsylvanian of west- Erstarrungsgesteinen als petrogenet-
v. 36, p. 25-43. central Indiana: Journal of Sedimentary isches Problem: Experientia, v. 5, p.
Hesse, R., 1990,Silica diagenesis: Origin of Petrology, v. 51, p. 197-202. 226-232.
inorganic and replacement cherts, in McBride, E.E and Folk, R.L., 1979, Features Wermund, E.G. and Moiola, R.J., 1966,
Mcllreath, LA. and Morrow, D.W., eds., and origin of Italian Jurassic radiolarites Opal, zeolites, and clays in an Eocene
Diagenesis: Geological Association of deposited on continental crust: Journal of neritic bar sand: Journal of Sedimentary
Canada, Geoscience Canada Reprint Sedimentary Petrology, v. 49, p. 837-868. Petrology, v. 36, p. 248-253.
Series 4, p. 253-275. Mizutani, S. and Shibata, K., 1983,Diagene- Wise, S.W.andWeaver, F.M.,1973,Originof
Hesse, R., Foreman, H.P., Forristall, G.Z., sis of Jurassic siliceous shale in central cristobalite-rich Tertiary sediments in
Heezen. B.C., Hekel, H., Hoskins, R.H., Japan, in lijima, A., Hein, J.R. and the Atlantic and Gulf Coastal Plains: Gulf
Jones, EJ.W., Kaneps, A.G., Krashen- Siever, R., eds., Siliceous Deposits in Coast Association of Geological Soci-
ninikov, VA, MacGregor, I. and Okada, the Pacific Region: Developments in eties, Transactions, v. 23, p. 305-323.
""\
H., 1974, Walther's facies rule in pelagic Sedimentology, v. 36, p. 283-298.
J
realm, a large-scale example from the Nisbet, E.G. and Price, I., 1974, Siliceous Stages of Burial Diagenesis in Biogenic
r:
Mesozoic-Cenozoic Pacific: Zeitschrift turbidites: bedded cherts as redepos- Siliceous Sediments - Characteristics of
der Deutschen Geologischen Gesell- ited ocean ridge-derived sediments, in the Silica Phases in Siliceous Sediments
schaft, v. 125, p. 151-172. Hsu, K. andJenkyns, H.C., eds., Pelagic
Hurd, D.C., 1973, Interactions of biogenic Sediments on Land and under the Sea: Bramlette, M.N., 1946,The MontereyForma-
opal, sedimentand seawater in the central International Association of Sedimen- tion of California and the origin of its sili-
Equatorial Pacific: Geochimica et Cos- tologists, Special PUblication, v. 1, ceous rocks: United States Geological
mochimica Acta, v. 37, p. 2257-2282. p.351-366. Survey, Professional Paper 212, 55 p.
Hurd, D.C.,1983,Physicaland chemical prop- Robertson, A.H.E, 1977, The origin and dia- Calvert, S.E, 1971, Composition and origin
erties of siliceous skeletons, in Aston, genesis of cherts from Cyprus: Sedi- of North Atlantic deep sea cherts: Con-
S.R., ed., Silicon Geochemistry and Bio- mentology, v. 24, p. 11-30. tributions to Mineralogy and P~trology,
geochemistry:AcademicPress,NewYork, v. 33, p. 273-288.
p.187-244.
c
250 Diagenesis Geoscience Canada Reprint Series 4 c
c
Carver, R.E., 1980, Petrology of Paleocene- Parks, GA, 1965, The isoelectric points of Nature of the Diagenetic Transformation
c
Eocene and Miocene opaline sedi- solid oxides, solid hydroxides, and Mechanisms between Different Silica (
ments, southeastern Atlantic Coastal
Plain: Journal of Sedimentary Petrol-
aqueous complex systems: Chemical
Reviews, v. 65, p. 177-198.
Phases and Physical Diagenesis of
Siliceous Sediments c
ogy, v. 50, p. 569-582.
Darragh, P.J., Gaskin, A.J. and Sanders,
Pisciotto, K.A., 1981, Distribution, thermal
histories, isotopic compositions and Berger, W.H. and v. Rad, U., 1972, Creta- c
J.V., 1976, Opals: Scientific American,
v. 264, p. 84-94.
reflection characteristics of siliceous
rocks recovered by the Deep Sea Drilling
ceous and Cenozoic sediments from the
Atlantic Ocean, in Hayes, D.E., Pimm, c
Ernst, WG. and Calvert, S.E., 1969, An
experimental study of the recrystalliza-
Project, in Warme, J.E., Douglas, R.G.
and Winterer, E.L., eds., The Deep Sea
A.C. et al., Initial Reports of the Deep
Sea Drilling Project, v. 14, p 787-954:
c
tion of porcelanite and its bearing on the Drilling Project: A decade of progress: United States Government Printing Off- c
origin of some bedded cherts: American
Journal of Science, v. 267A, p. 114-133.
Society of Economic Paleontologists
and Mineralogists, Special Publication
ice, Washington, D.C.
Bramlette, M.N., 1946, The Monterey For- c
Florke, OW., Hollmann, R., v. Rad, U. and
Rosch, H., 1976, Intergrowth and twin-
32, p. 129-147.
Riech, V. and v. Rad, U., 1979,Silica diagen-
mation of California and the origin of its
siliceous rocks: United States Geologi- c
ning in opal-CT lepispheres: Contribu-
tions to Mineralogy and Petrology, v. 58,
esis in the Atlantic Ocean: Diagenetic
potential and transformations, in Tal-
cal Survey, Professional Paper 212,
55 p. c
p.235-242.
Hurd, D.C. and Theyer, E, 1975,Changes in
wani, M., Hay,Wand Ryan, WB.E, eds.,
Deep Drilling Results in the Atlantic
Carozzi, AV. and Gerber, M.S., 1978,Syn-
sedimentary chert breccia: A Mississip-
c
the physical and chemical properties of Ocean: Continental margins and paleo- pian tempestite: Journal of Sedimentary c
biogenic silica from the central Equato-
rial Pacific. 1.Solubility, specific surface
environment: American Geophysical
Union, Maurice Ewing Series, v.3,
Petrology, v. 48, p. 705-708.
Christian,J.W, 1965,Thetheoryoftransfor- c
area, and solution rate constants of acid-
cleaned samples: Analytical Methods in
p.315-341.
Tada, A. and lijima, A., 1983, Identification
mations in metals and alloys: Pergamon
Press, Oxford, 975 p. c
Oceanography: American Chemical
Society, Advances in Chemistry Series,
of mixtures of opaline silica phases and
its implication for silica diagenesis, in
Clayton, R.N., O'Neil, J.A. and Mayeda,
T.K., 1972, Oxygen isotope exchange c
v. 147, p. 211-230.
lIer, A.K., 1955, The Colloid Chemistry of
lijima,A., Hein,J.R. and Siever, R.,eds.,
Siliceous Deposits in the Pacific Region:
between quartz and water: Journal of
Geophysical Research, v. 77, p. 3057-
c
Silica and Silicates: Cornell University Developments in Sedimentology, v. 36, 3067. c
Press, Ithaca, New York, 324 p.
lIer, R.K., 1973, Effect of adsorbed alumina
p.229-245.
Volosov, A.G., Khodarovskiy, I.L. and
Ewing, J., Ewing, M., Aitken, T.and Ludwig,
W.J., 1968, North Pacific sediment c
on the solubility of amorphous silica in
water: Journal of Colloid and Interface
Ryzhenko, B.N., 1972, Equilibria in the
system Si02-H 20 at elevated temper-
layers measured by seismic profiling, in
Knopoff, L., Drake, C.L. and Hart, P.J., c
Science, v. 43, p. 399-408.
lIer, A.K., 1979, Chemistry of Silica: Wiley-
atures along the lower three-phase
curve: Geochemistry International, v. 9,
eds., The Crust and Upper Mantle of the
Pacific Area: American Geophysical c
Interscience, New York, 866 p.
Isaacs, C.M., Pisciotto, K.A. and Garrison,
p.362-377.
v. Rad, U., Riech, V. and Rosch, H., 1977,
Union, Geophysical Monograph, v. 12,
p.147-173.
c
R.E., 1983, Facies and diagenesis ofthe Silica diagenesis in continental margin Fournier, A.O., 1973, Silica in thermal waters: c
Miocene Monterey Formation, Califor-
nia: A summary, in Iijima, A., Hein, J.R.
sediments off Northwest Africa, in Lan-
celot, Y.,Seibold, E. etel., Initial Reports
Laboratory and field investigations, in
Ingerson, E., ed., International Sym- c
and Siever, A., eds., Siliceous Deposits
in the Pacific Region. Developments in
of the Deep Sea Drilling Project, v. 41,
p. 879-905: United States Government
posium on Hydrogeochemistry and Bio-
geochemistry, Tokyo 1970, Proceedings, c
Sedimentology, v. 36, p. 247-282.
Jones, D.L. and Knauth, L.P.,1979,Oxygen
Printing Office, Washington, D.C.
Walther, J.V. and Helgeson, H.C., 1977, Cal-
v. 1 (Hydrogeochemistry), p. 122-139:
Clarke Co., Washington, D.C. c
isotopic and petrographic evidence
relevant to the origin of the Arkansas
culation of the thermodynamic proper-
ties of aqueous silica and the solubility of
Harrison, WE., Hesse, R., and Gieskes,
J.M., 1982, Relationship between sedi-
c
Novaculite: Journal of Sedimentary quartz and its polymorphs at high pres- mentary facies and interstitial water c
Petrology, v. 49, p. 581-597.
Jones, J.B. and Segnit, E.R., 1971, The
sures and temperatures: American
Journal of Science, v. 277, p. 1315-1351.
chemistry in slope, trench and Cocos
plate sites from the Mid-America Trench c
nature of opal. 1.Nomenclature and con-
stituent phases: Journal of the Geologi-
Weaver, EM. and Wise, S.W, Jr., 1972,
Ultramorphology of deep sea cristobali-
transect, active margin off Guatemala,
Leg 67, DSDP,in Huene, A., Aubouin, J. c
cal Society of Australia, v. 18, p. 57-68.
Krauskopf, K.B., 1956, Dissolution and pre-
tic chert: Nature, v. 237, p. 56-57.
Williams, L.A. and Crerar, D.A., 1985,Silica
et al., Initial Reports of the Deep Sea
Drilling Project, v. 67, p. 603·614:United c
cipitation of silica at low temperatures:
Geochimica et Cosmochimica Acta,
diagenesis, II. General mechanisms:
Journal of Sedimentary Petrology, v. 55,
States Government Printing Office,
Washington, D.C.
c
v. 10, p. 1-26.
Lewin,J., 1961, The dissolution of silica from
p.312-321.
Williams, L.A., Parks, G.A. and Crerar, D.A.,
Heath, G.A., 1969, Mineralogy of Cenozoic
deep-sea sediments from the equatorial
e
diatom walls: Geochimica et Cosmo- 1985,Silica diagenesis, I. Solubility con- Pacific Ocean: Geological Society of (
chimica Acta, v. 21, p. 182-198.
Mallard, M.E., 1890, Sur la lussatite,
nouvelle variete minerale cristallisee de
trols: Journal of Sedimentary Petrology,
v. 55, p. 301-311.
Wise, S.W.,Jr., Buie, B.E and Weaver, EM.,
America, Bulletin, v. 80, p. 1997-2018.
Heath, G.R. and Moberly, R., Jr., 1971,
Cherts from the western Pacific, Leg 7,
c
silice: Bulletin de la Societe franc;:aise de 1972, Chemically precipitated sedimen- Deep Sea Drilling Project, in Winterer,
(.
Mineralogie et Cristallographie, v. 13,
p.63-66.
tary cristobalite and the origin of chert:
Eclogae Geologicae Helvetiae, v. 65,
E.L., Riedel, WR.etal., Initial Reports of
the Deep Sea Drilling Project, v. 7,
c
Meyers, WJ., 1977, Chertification in the p.157-163. p. 991-1007: United States Government c
Mississippian Lake Valley Formation,
Sacramento Mountains, New Mexico:
Sedimentology, v. 24, p. 75-105.
Printing Office, Washington, D.C.
c
(
c
c Diagenesis of Biogenic Siliceous Sediments 251
c
c Hein, J.R., Scholl, DW., Barron, J.A., Jones, Labeyrie, L.D., 1974, New approach to sur- Steinitz, G., 1970, Chert "dike" structures
c M.J.andMiller,J., 1978,Diagenesisof late
Cenozoicdiatomaceousdeposits and for-
face seawater paleotemperatures using
180 /160 ratios in silica of diatom frust-
in Senonian chert beds, southern

r mationofthe bottomsimulating reflectorin ules: Nature, v. 248, p. 40-42.


Negev, Israel: Journal of Sedimentary
Petrology, v. 40, p. 1241-1254.
the southern Bering Sea: Sedimentology, Lancelot, Y.,1973,Chert and silica diagene- Taliaferro, N.L., 1934, Contraction pheno-
v. 25, p. 155-181. sis in sediments from the central Pacific, mena in cherts: Geological Society of
Hesse, R., 1987, Selective and reversible in Winterer, E.L., Ewing, J.1. et et., Initial America, Bulletin, v. 45, p. 189-231.
r~ carbonate-silica replacements in Lower Reports ofthe DeepSea Drilling Project, VanLier, J.A., de Bruyn, P.L. and Overbeek,
r. Cretaceous carbonate-bearing tur-
bidites of the Eastern Alps: Sedimentol-
v. 17, p. 377-405: United States Govern-
ment Printing Office, Washington, D.C.
J.T.G., 1960, The solubility of quartz:
Journal of Physical Chemistry, v. 64,
C ogy, v. 34, p. 1055-1077.
Hesse, R., Lebel, J. and Gieskes, J.M.,
Mizutani, S., 1977, Progressive ordering of
cristobalitic silica in the early stage of
p. 1675-1682.
v. Rad, U., 1979,Si0 2Diagenese in Tiefsee-
C 1985, Interstitial water chemistry of gas diagenesis: Contributions to Mineralogy sedimenten: Geologische Rundschau,
r hydrate bearing sections on the Middle- and Petrology, v. 61, p. 129-140. v. 68, p. 1025-1036.
America Trench Slope, Deep Sea Drill- Morse, J.W.and Casey,W.H., 1988,Ostwald v. Rad, U. and Rosch, H., 1972, Mineralogy
ing Project, Leg84, in Auboin, J., Huene, processes and mineral paragenesis in and origin of clay minerals, silica and
R.V. et al., Initial Reports of the Deep sediments: American Journal of Sci- authigenic silicates in leg 14sediments,
Sea Drilling Project, v. 84, p. 727-737: ence, v. 288, p. 537-560. in Hayes, D.E., Pimm, A.C. et el., Initial
United States Government Printing Of- Murata, K.J., Friedman, I. and Gleason, Reports ofthe Deep Sea Drilling Project,
fice, Washington, D.C. J.D., 1977, Oxygen isotope relations v. 14, p. 727-751: United States Govern-
Hinman, N.W., 1987, Organic and inorganic between diagenetic silica minerals in ment Printing Office, Washington, D.C.
r )
chemical controls on the rates of silica Monterey Shale, Temblor Range, Cal- Weaver, F.M. and Wise, S.w., Jr., 1972.
diagenesis: A comparison of a natural ifornia: American Journal of Science, Ultramorphology of deep sea cristobali-
" t
system with experimental results, un-
published Ph.D. thesis, University of
v. 277, p. 259-272.
Murata, K.J. and Larson, A.A., 1975, Dia-
tic chert: Nature, v. 237, p. 56-57.
Williams, L.A. and Crerar, D.A., 1985,Silica
California, San Diego, 381 p. genesis of Miocene siliceous shales, diagenesis, II. General mechanisms:
Hurd, D.C.,Wenkham,C., Pankratz, H.S.and Temblor Range, California: United Journal of Sedimentary Petrology, v. 55,
Fugate, J., 1979, Variable porosity in sili- States Geological Survey, Journal of p.312-321.
ceous skeletons: Determination and im- Research, v. 3, p. 553-566. C fo Williams, L.A., Parks, G.A. and Crerar, D.A.,
portance: Science, v. 203, p. 1340-1343. Murata, K.J. and Norman, M.B., II, 1976, 1985,Silica diagenesis, I. Solubility con-
lIer, R.K., 1979, Chemistry of Silica: Wiley- An index of crystallinity for quartz: trols: Journal of Sedimentary Petrology,

c Interscience, New York, 866 p.


Isaacs, C.M., 1982, Influence of roc.lU<..om-
American Journal of Science, v. 276,
p. 1120-1130.
v. 55, p. 301-311.
Wise, S.w., Jr., Buie, B.F.and Weaver,F.M.,
position on kinetics of silica phase Nielsen, A.E., 1964, Kinetics of Precipitation: 1972,Chemically precipitated sedimen-
changes in the Monterey Formation, The Macmillan Co., New York, 151 p. tary cristobalite and the origin of chert:
Santa Barbara area, California: Geol- Paris, I., Stanistreet,I.G. and Hughes, M.J., Eclogae Geologicae Helvetiae, v. 65,
ogy, v. 10, p. 304-308. 1985, Cherts of the Barberton green- p. 157-163.
C Kastner, M.andGieskes,J.M., 1983,Opal-A
to opal-CT transformation: A kinetic
stone belt interpreted as products of
submarine exhalative activity: Journal
Wyllie, P.J., 1971, The Dynamic Earth. Text-
book in geosciences: Wiley-Inter-
l study,in Iijima, A., Hein, J.A., and Siever,
R., eds., Siliceous Deposits in the Pacif-
of Geology, v. 93, p. 111-129.
Pisciotto, K.A., 1980,Chert and porcellanite
science, New York, 476 p.
Zemmels, I. and Cook, H.E., 1973, X-ray
ic Region: Developments in Sedimentol- from Deep Sea Drilling Project Site 436, mineralogy from the Central Pacific
ogy, v. 36, p. 211-227. Northwest Pacific, in Langseth, M., Ocean, in Winterer, E.L., Ewing, J.1. et
Kastner, M., Keene, J.B. and Gieskes, J.M., Okada, H. et el., Initial Reports of the el., Initial Reports of the Deep Sea
1977, Diagenesis of siliceous oozes. I. Deep Sea Drilling Project, v. 56/57, Drilling Project, v. 17, p.517-559:
Chemical controls on the rate of opal-A p. 1133-1142: United States Government United States Government Printing Of-
to opal-CT transformation - an experi- Printing Office, Washington, D.C. fice, Washington, D.C.
mental study: Geochimica et Cosmo- Pisciotto, K.A., 1981, Diagenetic trends in
chimica Acta, v. 41, p. 1041-1059. the siliceous facies of the Monterey
Keene, J.B., 1975, Cherts and porcelanites Shale in the Santa Maria region, Califor-
from the North Pacific, DSDP, leg 32, in nia: Sedimentology, v. 28, p. 547-571.
Larsen, R. and Moberly, A. et al., Initial Siever, A. and Woodford, N., 1973,Sorption
C Reports ofthe Deep Sea Drilling Project, of silica by clay minerals: Geochimica et
r'
L
v. 32, p. 429-507: United States Govern- Cosmochimica Acta, v. 37,p. 1851-1880. Originally published in
ment Printing Office, Washington, D.C. Snyder, W.S., Brueckner, H.K. and Schwei- Geoscience Canada v. 15 Number 3
Keller, W.D., Stone, C.G. and Hoersch, kert, A.A., 1983,Deformational styles in (September 1988)
W.D., 1985, Textures of Paleozoic chert the Monterey Formation and other sili-
Revised 1989
and novaculite in the Ouachita Moun- ceous rocks, in Isaacs, C.M. and Gar-
tains of Arkansas and Oklahoma and rison, R., eds., Symposium Volume on
their geological significance: Geologi- Monterey Oilfields: Society of Economic
cal Society of America, Bulletin, v. 96, Paleontologists and Mineralogists,
p. 1353-1363. Pacific Section, Los Angeles, p. 151-170.
Kent, D.B. and Kastner, M., 1985, Mg2+ Stein, C.L. and Kirkpatrick, R.J., 1976,
removalinthe system Mg2+ - amorphous Experimental porcelanite recrystalliza-
Si02 - H20 by adsorption and Mg-hydro- tion kinetics: A nucleation and growth
xysilicate precipitation: Geochimica et model: Journal of Sedimentary Petrol-
Cosmochimica Acta, v. 49, p. 1123-1136. ogy, v. 46, p. 430-435.
c
252 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
c
c
c
<;;
c
c
c
(
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
SEM photomicrograph of authigenic quartz in the Lower Silurian Whirlpool Sandstone Formation of
southeastern Ontario. This quartz crystal has grown from the surface of a detrital quartz grain into
c
a pore space. Fibrous authigenic illite coats the surface of the detrital quartz. Photograph courtesy c
of K.J. O'Shea (Golder Associates Ltd.).
c
c
(
c
C
l
C
l
C
C
r.
C. Origin of Inorganic and Replacement Cherts 253

( :
C and experimental stud ies by Drum up to 12.5 mmoles Si0 2 per gram of air-
c· (1968), Leo and Barghoorn (1976), and
Sigleo (1978) have shown , silicification
dried pulp in 24 hours . From a summary
of the literature and his own work, Stein
c of wood is not a replacement but a per- (1982)concluded that the conversion of

c meation or void-tlllinq process. Dis-


solved silicon has a particular affinity
opal-A through opal-CT to quartz in fos-
sil wood occurs at rates comparable to
c· for the organic molecules making up
the vascular tissue, particularly lignin
those of the silica transformations in
biogenic siliceous oozes. For samples
c and cellulose, with their numerous that have reached the quartz stage ,

c Silica Diagenesis:
exposed functional groups (i.e., hydro-
xyl groups). The mechanism of silica
Stein (1982) demonstrated a progres-
sive increase in the quartz crystallinity
( deposition on wood surfaces involves index with geologic age. The quartzfab-
Origin of Inorganic and hydrogen bonding between the hydro- ric may still show a distinct relationship
( xyl groups in cellulose or lignin and with the original cell structure of the
Replacement Cherts
o those in the silanol molecule. The silicic
acid actually involved in the petrifaction
tissue (Figure 1), indicating that even in
the second transformation step (from
o Reinhard Hesse mechanism may not be monomeric sil- opal-CT to quartz) the organic mole-

o Depanrnent of Geological Sciences


McGill University
icic acid. At the time of bond formation
it may have polymerized to a low-mo-
cules of the remaining wood tissue have
a controlling influence on the distribu-
o 3450 University St.
Montreal, Quebec H3A 2A7
lecular weight polysilicic acid with the
capacity of forming multiple hydrogen
tion of the grain boundaries of the pre-
cipitated quartz. This is not surprising in
o bonds (Leo and Barghoorn, 1976). Min- view of the relatively low temperatures

o INTRODUCTION
Silicification is a common diagenetic
erai parageneses and trace element
data for petrified wood samples and
(less than 110°C) at which the transfor-
mation is assumed to occur (by analogy
o phenomenon in a wide variety of origi-
nally non-siliceous sediments, and its
their host sediments indicate that silica
mineralization takes place within the
with siliceous oozes). The pyrolysis
results of Sigleo (1978)showed that Iig-
c extent ranges from minor to pervasive. chemical and pH range of most surface nin-derived pyrolysates are still present

o Examples of partial and minor silicifi-


cation include: (1) silicification of fossil
waters. According to Sigleo (1978) clay
minerals can co precipitate with silica.
at this step.

o wood; (2) chertification of carbonates


and carbonate-bearing sandstones;
In order to produce silicification, the
aqueous environment ought to be an-
CHERTIFICATION OF CARBONATES
AND CARBONATE-BEARING
c and (3) replacement of evaporites. In all oxic to prevent rapid oxidation, and SANDSTONES

o three examples the sourceofthe silica is


predominantly biogenic. Pervasive
should contain a moderate concentra-
tion of silica (up to 140 ppm) over
Much less is known about the chemical
conditions and temperature of silicifica-
o chertification occurs on the scale of
individual layers, beds or entire forma-
an extended period of time. Ground
waters that have percolated through
tion of ancient carbonate rocks, be-
cause most of the evidence is based on
o tions. It has been described in lacus- volcanic ashes (Murata, 1940), as well thin section and/or geological field ob-

c trine, pedogenic and hydrothermal-


volcanogenic environments. Examples
as other silica-bearing meteoric or for-
mation waters have a high potential for
servations rather than on experimental
or geochemical results. Pore fluid com-
(; are (4) Magadi-type cherts; (5) other the fossilizat ion of wood through silicifi- positions are generally not available for

o lacustrine cherts; (6) silcretes; and (7)


hydrothermal-volcanic cherts. In the
cation.
Although most fossil wood consists of
the solutions which caused silicification
in these rocks . Studies of silicified car-
o last example chertification tends to
affect entire formations. In examples (4)
quartz, the silicification process in-
volves the same maturation sequence
bonates in the past have focussed on (i)
description and analysis of the silica
to (7) the source of the silica is predomi- as in biogenic siliceous oozes, i.e ., opal- fabrics, (ii) relative timing of the sil-
nantly inorganic. A ..... opal-CT ..... quartz (Buurman, 1972; icification process with respectto diage-
Leo and Barghoorn, 1976; Stein, netic events affecting the carbonate
SILICIFICATION OF WOOD 1982). Once silicic acid has per- host sediment, and (iii) general con-
Silicification of plant remains is the most meated the plant cells and replaced straints for the chemical environment of
common among several preservation the cell fluids, it polymerizes, precipi- silicification based on geologic evi-
mechanisms for fossil wood, which in- tates and dehydrates in cell centres and dence as well as on identification of the
clude petrifaction by carbonates, sul- openings between cell walls. These ini- source(s) of the silica. These are mostly
phides, sulphates and phosphates. The tial steps in the petrifaction reactions studies undertaken since the mid-1960s.
sequence of silica phases and their can occur in a matter of days to years, as Extensive earlier literature on the origin
transformations in silicified wood is suggested experimentally by Leo and of nodular chert in carbonate rocks dat-
essentially the same as that in biogenic Barghoorn (1976).The opal-A formed in ing back to the last century contributes
,- siliceous oozes, and therefore forms
the link between silicification of the lat-
the process preserves in remarkable
detail the tissue structure seen in many
little to the foregoing problems due to
the limited understanding of the solu-
ter (dealt with in the previous article: petrified wood samples. According to tion chemistry involved and ofthediage-
Hesse, this volume, p. 227-251) and experiments by Merrill and Spencer netic reaction sequences in carbonates
non-siliceous materials. As analyses (1950), cellulose fibers can absorb and siliceous sediments.
c
254 Diagenesis Geoscience Canada Reprint Series 4 c
c
Chertification of carbonates involves developed in evaporites than in carbon- centre (Figure 2a). Such fabrics charac-
c
the precipitation of pore -filling silica ates. At least some of these different ter ize void-filling cements, but with c
cements as well as the replacement of
carbonate by silica. Both may occur
fabrics may have had opal-A and/or
opal-CT precursors, although generally
quartz they seem not to be restricted to
cements. Replacement of carbonate c
before and/or after, but probably not
during carbonate cementation of the
these phases are not preserved and
their former presence is difficult to
fossils or of an earlier opal-CT phase
(e.g., in fossil wood) may produce the
c
host sediment. The same relationships prove. However, wherever pore fluids same fabric . Replacement fabrics can c
hold for carbonate-bearing sandstone. became highly supersaturated with sil- be distinguished from cement fabrics
The processes of silicification and car- ica during burial, these metastable such as mold infills by the presence of C
bonate cementation seem to be mutu-
ally exclusive with the possible excep-
phases are expected to have preceded
the precipitation of quartz.
carbonate and/or organic matter inclu-
sions in the former (Figure 2b). The term
C
tion of dolomitization. The change-over (a) Equigranu/ar types. "megaquartz", applied toamicroscopic C
from one to the other may occur several (1)Thecommon microcrystalline quartz feature, clearly is a misnomer, regard-
times in the diagenetic history of a sedi- ("microquartz" of Folk and Pittman, less of how well entrenched it may be in C
ment. In early diagenesis. the choice of
which of the two processes will operate
1971) consists of tiny crystals of quartz
(generally less than 5 to 20 microns in
the literature.
(b) Fibrous types.
C
first. appears to depend strongly on diameter) which display an equigranu- (3) The most abundant variety among C
environmental conditions (submarine lar texture with pin-point extinction pat- these is "chalcedony sensu stricto" or
versus meteoric or mixing-zonediagene- tern. If the size of individual crystals is " chalcedonic quartz" or "length-fast
C
sis). During later diagenetic stages host-
rock composition becomes important.
below the resolution of an ordinary light
microscope, this fabric is called crypto-
chalcedony", which are the common
names in use for this mineral, in which
C
Silica Fabrics. crystalline. the elongation of the fibres is perpen- C
The silica occurs in the form of quartz.
which includes equigranular and fibrous
(2) Megaquartz (size range of 20 to
2000 microns or larger) has a mosaic
dicular to the crystallographic c-axis (or
the epsilon vibration direction). Bundles
C
types. Seven different recurring fabrics fabric similar to drusy calcite mosaics, of fibres commonly radiate from a single C
have been recognized (Figure 2). al- commonly displaying a progressive in- point on the substrate from which they
though some of these are more typically crease in crystal size from margin to grow. This radiating pattern is charac- C
C
C
C
C
C
C
C
C
C
C
C
C
C
c
e
(
c
c.
c
Figure 1 Photomicrographs of petrified wood. (8) Well-preserved cell-structure. (b) As in (a) but with crossedpo/arizers. Note that variations
c
in grain size and orientation of quartz crystals are controlled by cell-structure of original tissue . c
c
(
c
c Origin of Inorganic and Replacement Cherts 255

c
c· teristic of chalcedony which typically grains, in a fashion similar to pressure sence of quartzine alone cannot be
c occurs as a vOid-filling cement , e.g., in
the interior of radiolarian tests . It may
fringes in metamorphic rocks (Hesse,
1987). Magnesium dissolved from the
used to establish the former presence of
evaporites that have been dissolved.
c also form replacement fabrics (e.g., dolomite may play asimilar role in nucle- Folk(1975)himself cautioned against an

c· Wilson, 1966). So-called "chalcedonic


overlays" (Wilson, 1966; Figure 2c)
ating this chalcedony by providing mag-
nesium hydroxide nuclei as does the
uncritical application of this criterion
after having observed a number of
( commonly line primary or secondary magnesium-hydroxidecompound (MHC) examples of quartzine-replaced fossils
pores as isopachous rims of chalce- referred to in Hesse (1990b) for opal-CT (echinoderms, brachiopods, bryozoa)
( dony radiating from silicified frame- nucleation. The direct precipitation of in rocks that showed no evidence of

c work grains on the cavity walls. They


often consist of consecutive layers
quartz from dissolved opal-A without an
opal-CT precursor is favored by a lack of
evaporitic conditions. As an alternative,
he suggested Mg-rich fluids as the
c which in plain polarized light produce a Mg according to Hinman (1987). The geochemical environment for carbon-

o brownish color banding that is probably


due to the presence of bands of very
fringing cement, however, forms diage-
neticallytoo late for opal-A to be present
ate replacement by quartzine, an idea
which is supported by the more recent
o small inclusions. They may be followed
by megaquartz, the grain size of which
as a silica source.
(4) In "length-slow chalcedony" or
evidence of Kastner (1980) and Keene
(1983). These authors also concluded
o increases toward the pore centre, and quartzine (the name first proposed that quartzine-precipitating flu ids ought

o locally by spherulitic chalcedony (Fig-


ure 2c).
by Michel-Levy and Munier-Chalmas ,
1892)the elongation of the fibres is par-
to be enriched in sulphate. However,
Brown et al. (1969) and Meyers (1977)
o Parallel, non-radiating chalcedony
fibers occur in "fringing" or "palisade
allel with the crystallographic c-axis.
This fabric occurs in chert nodules
saw no evidence for the presence of
either magnesium or sulphate in fluids
o cement" in high-grade diagenetic or replacing former evaporites, and has causing replacement of calcitic fossils

o low-grade metamorphic calcareous


sandstones that have undergone tec-
been used as evidence for "vanished
evaporites " (Folk and Pittman, 1971).
by spherulitic quartzine (Figure 2e).
(5) Lutecite is a fibrous quartz variety
o tonic deformation (Figure 3a). In these
fringing cements, length-fast chal-
This popular view was challenged by
Kastner (1980) and Keene (1983), who
intermediate between chalcedony
sensu stricto and quartzine with the
o cedony is intimately intergrown with showed that quartzine also occurs in fibre axis inclined about 30° to the

o length-slow chalcedony. The fibres form


in the pressure shadows of rigid, detrital
deep-water pelagic sediments and is
not restricted to shallow-water evapori-
crystallographic c-axis (Figures 2f,4;
Frondel, 1962).
o grains, specifically sugary dolomite tic environments. Therefore, the pre- (6) "Zebraic chalcedony" displays a

o beautifully banded extinction pattern


under crossed polarizers (Figure 3c).

o M 0 R p H 0 L o G y This results from a systematic helical


twisting of the fibre axes about the crys-
0, mosaic
quartz
chalceclonic spherulitic
overlay chalcedony
lutecite
m icrocryst.
granular qtz.
tallographic c-axis (McBride and Folk,

c 1977; Frondel, 1978) as schematically


illustrated in Figure 4. Although zebraic
c chalcedony is commonly associated
with cherts replacing evaporites. it has
o also been described in chert formations

o without any evidence for the former pre-


sence of evaporites (e.g., Simonson,
o w
1987).
(7) "Microflamboyant quartz" has afa-
C) z ...c b bric intermediate between equant and
(
CII fibrous quartz types (Milliken, 1979).
w E Also known as "flamboyant lutecite"
c CII
U
11I
(Folk and Pittman, 1971) or "flamboyant
spectral extinction" (Chowns and Elk-
C 0.
CII ins, 1974), this fabric displays undulose
'-
D extinction caused by composite , fan-
ning crystals whose individual crystal
C Figure 2 Microscopic quartz fabr ics. (From Wilson, 1966).(a) Mosaic drusy quartz display- boundaries are not clearly recogniz-
ing increasing crystal size toward pore centre. (b) Mosaic quartz replacing biogenic carbon- able. Undulose extinction in this case
ate fabric, relics of which are preserved as inclusions. (c) Chalcedonic overlay lining silicified results from crystal growth in domains
serpula tube grading inward through microquartz to mosaic megaquartz. Lower half: cnet-
rather than from grain deformation.
cedonic overlays on silicified grains followed toward pore center by spherulitic chalcedony.
(d) Pore-filling spherulitic chalcedony. (e) Spherulitic chalcedony containing inclusions Megaquartz in evaporite-replaced
'-.
/ of a replaced former aragonite shell. Lower half: Chalcedony spheres supporting silicified chert rarely displays radially undulose
ooid layers. (f) Lutecite partially replacing calcitic shells. (g) Equigranular microcrystalline extinction as a growth phenomenon as
quartz replacing framework grains rimmed by cha/cedonic overlays. well (Milliken , 1979, fig . 3).
,.'
256 Diagenesis Geoscience Canada Reprint Series 4

. d .
\
c· Origin of Inorganic and Replacement Cherts 257
c

c Origin of Quartz Fabrics: Void-filling
Cements versus Replacements.
in itself is not a reliable fabric indicator
for a void-filling mechanism because
although zebraic chalcedony and
quartzine are predominantly replacive
c. Void-filling cement. Of the fabrics
described, only one has been identified
it is also observed in quartz replacing
fossil fragments. In the latter case,
too. However,the occurrence of quartz-
ine (together with chalcedony) in the
( exclusively as a void-filling cement, however, it is riddled with carbonate fringing cements (pressure fringes), as

c i.e.• Wilson's (1966) "chalcedonic over-


lays". Where this cement is followed by
inclusions (Figure 2b). Length-fast
chalcedony occurs predominantly(e.g.,
the name says, suggests a mechanism
involving crystal growth into a pore-
( mosaic megaquartz and/or spherulitic Meyers and James, 1978, p. 107), but space, i.e., cementation. This pore
chalcedony, the latter are unquestiona- not exclusively as a cement. space is opening under tectonic defor-
c bly also of void-filling origin (Wilson, Replacement. Lutecite, on the other mation by the detachment of cement

c 1966; Schmitt and Boyd, 1981). As men-


tioned previously, "drusy megaquartz"
hand, appears to be the only fabric
known exclusively as a replacement,
crystals or matrix grains from rigid
framework grains and is being filled in
c
0
0
0
0
0
C-
O
0
0

c
0
o
0
r ·

r:
~

r--
~

~)
,.
Figure 3 Ca) (opposite page, upper left) Fringing cement ("" palisade cement, p) forming discontinuous rim on microcrystalline, "sugary"
c
r:
dolomite grain in the direction perpendicular to maximum tecton ic stress (N-S). Note absence of fringing cement in the direction parallel to
maximum stress (E-W). Intergrown quartzine and chalcedony fibers are elongated NoS. Fibrous silica cement was followed (or partially
replaced) by fibrous late calcite cement (e) which started to grow from the edge of the detrital dolomite. Lower Cretaceous Gault Formation,
r
Uechtenstein. Height of picture corresponds to 0.5 mm.
(b) (opposite page, upper right) Fringing cement under crossed polarizers, same thin section as in (a).
r: Ce) (opposite page, lower left) Large fans of zebraic chalcedony radiating from sificified framework grains into large pore. Note smooth fan
1..... boundaries (arrows). Centre of pore filled by drusy megaquartz. Length of scale ber » 0.5 mm. Lower Proterozoic Sokoman Formation,
r Quebec. (From Simonson, 1987, fig. 7c; photomicrograph courtesy of 8.M. Simonson).
'-- Cd) (opposite page, lower right) Spherufitic chalcedony cement with isopachous growth bands in sifica-cemented eolian (?) sands from
Steamboat Springs , Nevada. Note smooth interfaces between spherulitic fans (arrows). Scale bar"" 0.05 mm. (From Simonson, 1987, fig. 12c;
'-' photomicrograph courtesy of 8.M. Simonson).
v-:
(e) (above left) Selective sificiflcation of ooid cortex at contact points with detrital quartz grains. Individual silicified domains in ooid rim are in
'--
optical continuity with their quartz neighbors and represent "overgrowths' ~ Lower Cretaceous Gault Formation , Grisons, Eastern Switzerland.
Dimensions of ooid "" 0.43 x 0.64 mm.
Cf) (above right) Silicified centre of echinoderm ossicle showing microdolomite inclusions in identical crystallographic orientation. The
inclusions continue from the quartzine into the unreplaced calcite. Same thin section as (a). Long diameter of quartzine area "" .0.5 mm.
c
258 Diagenesis Geoscience Canada Reprint Series 4 c
c
statu nascendi by the growing fringing only partial replacement, and most Selective silicification of ooids, cal-
c
silica cement which thus is not a commonly they are unaffected by careous algae, bryozoans and echino- c
replacement.
Schmitt and Boyd (1981) use the
silicification.
The degree of selectivity of the sili-
derm fragments occurs in carbonate-
rich turbidites of the Lower Cretaceous c
terms "delayed" and "immediate
replacement" instead of the familiar
cification process apparently is a func-
tion of a number of variables including
Gault Formation of the East Alps
(Hesse, 1987). Calcitic or calcite-re-
c
terms "void-filling cement" and "re- pH, dissolved silicon activity, and the placed shells of molluscs are not c
placement" to describe different silici-
fication patterns of Permian pelecy-
extent of previous lithification of the
rocks (i.e., porosity and permeability
affected . The replacement quartz is
megaquartz, which forms a syntaxial c
pods and brachiopods in the Park City
Formation of Wyoming. With this termi-
reduction prior to silicification). Accord-
ing to Jacka (1974), both high-magne-
"overgrowth" on detrital quartz that oc-
curs as a nucleus of or in grain contact
c
nology the authors stress the point sian calcitic (fusulinids, bryozoans, with an ooid. Replacement is restricted c
that cementation of secondary pores
such as molds of fossil fragments and
echinoderm fragments) and aragonitic
skeletal elements (parts of molluscs
to the ooid cortex in contact with the
quartz grains; it does not affect the c
the replacement of such fragments by
another mineral are end-members of
shells) of the Getaway carbonate tur-
bidites of the Middle Permian Cherry
microspar calcite cement that en-
velopes both ooids and quartz grains
c
the same couple of chemical reactions, Canyon Formation of TexaslNew Mex- (Figure 3e). Detrital carbonate clasts, c
l.e., dissolution and precipitation. In
the case of cementation of dissolution
ico are replaced by quartzine and me-
gaquartz, but notthe micritic carbonate
both limestone and dolomite, are also
unaffected. These rocks had been ex- c
voids, these reactions are separated by
a finite time interval, whereas in the
matrix or intraclasts. Similar obser- tensively cemented by a calcitic micro- c
case of replacement, they are sepa-
vations were made on dolomitic lime-
stones in the Middle Devonian Colum-
spar prior to silicification.
In quartz-rich turbidites of the same c
rated by an infinitesimally brief interval.
Selective replacement. Where
bus and Delawareformations of Ohio by
Hatfield (1975). Many samples exhibit
formation which apparently were not
carbonate-cemented before silicifica-
c
there is evidence for replacement , the selective silicification of echinoderm tion, the replacement pattern is quite c
process is commonly highly selective;
certain components of the carbonate
fragments only, whereas in others
bryozoans,brachiopodsand coralswere
diffferent. Here, the ooid cortices are
completely replaced by micro- to cryp- c
host rock are replaced while others are
unaffected. Meyers (1977) found the fol-
silicified in addition. Inthe most intensely
silicified samples, the micritic carbonate
tocrystalline quartz. The syntaxial
megaquartz "overgrowths" of the calc-
c
lowing order in terms of decreasing sus- matrix also had been replaced. arenites (replacing the calcareous cor- c
ceptibility to replacement of various car-
bonate constituents by microquartz in c
the Mississippian Lake Valley Forma-
tion of New Mexico: carbonate mud,
c
bryozoans, thin-shelled brachiopods, c
crinoids, thick-shelled brachiopods,
syntaxial calcite cement rims on cri- c
noids. The last three components show c
c
fi~r.
c
orientatioll c-ni, c
I ~ quartzine c
c
/ lutecite c
a b c
chalcedony Figure 5 (8) Zoned silicified ooid cortex with (1) outermost near-opa-
que cryptocrystalline zone followed inward by (2) microcrystalline zone
e
and (3) macrocrystalline zone with concentrically arranged laminae of
carbonate inclusions. The inward increasing quartz crystal size repre-
c
sents a replacement sequence with decreasing nucleation rate. centre of c
zebraic chalc. ooid.not shown. Magnification 120x. (From Choquette, 1955).
(b) Zoned syntaxial overgrowth on well-rounded detrital quartz grain. c
Innerzone: euhedral quartz crystal with concentrically arranged laminae
of carbonate inclusions which show spherulitic extinction revealing an c
Figure 4 Orientation of fibre axes in fibrous silica minerals.
overall radial crystallographic orientation of the original carbonate crys-
tals. Outer inclusion-free zone. For interpretation seetext. Cortex zonation
c
(From Milliken, 1979). similar as in (a). Magnification 80 x. (From Choquette, 1955). c
c
c
c
c Origin of Inorganic and Replacement Cherts 259
r'--.-
r:
'-. tex of a quartz-nucleus ooid) were not microcrystalline central zone, and (3) an sediment. Meyers and James (1978)
r:
'-.-.,
observed. The small grain size of the innermost zone of macrocrystalline estimated that in this case early chert-
replacement quartz in the quartz-rich quartz with concentrically arranged ification took place under a maximum
turbidites suggests rapid (homoge- laminae of carbonate inclusions. This overburden of not more than 215 m (the

c
r
neous) nucleation. In the carbonate tur-
bidites in contrast, detrital quartz
zonation results from inward progres-
sion of the replacement and reflects de-
thickness of the Mississippian of the
region) and generally probably under
grains served as nuclei for slow hetero- creasing silicon activity or/and decreas- much less overburden, perhaps only a
geneous nucleation. This replacement ing permeability as the ooid rim gets few metres or tens of metres. Corre-
r fabric suggests relatively low silicon
concentrations in the pore fluids and/or
sealed off by silicification. The centre of
the ooid may consist of: (i) a moderately
sponding burial temperatures would
have been less than 30°C, based on an
restricted permeability in the calcaren- coarse-grained mosaic of (mega-) assumed mean annual surface temper-
r: ites so that the replacement phase quartz or (ii) a detrital nucleus, usually a ature of 20°C and a geothermal gra-

c could be precipitated as quartz rather


than as a less well-ordered silica
quartz grain with a syntaxial over-
growth. The latter reflects outward sil-
dient of 3.6°C per 100 m.
Another case for early, unconformity-

o phase. In the quartz-rich turbidites, on


the other hand, the fluids were probably
icification. Other descriptions of sil-
icified oolites are, e.g., by Swett (1965)
related chertification has been de-
scribed from the Lower Pennsylvanian
o highly supersaturated with respect to
quartz. They were conceivably also
and Chanda at at. (1976, 1977).
Timing of Silicification
Marble Falls Group of central Texas
(Namy, 1974). Chert occurs in and below
supersaturated with respect to opal-CT, Relatille to carbonate Cementation a thin (1 to 2 cm thick) crust of silicified
o which was likely the first silica phase to
be precipitated. This could explain why
and Diagenesis.
Chertification of carbonate host sedi-
oolite at the top of a 3-6 m thick oospar-
ite/biosparite horizon just beneath a
o detrital quartz grains in these rocks ments apparently occurs at different regional unconformity that extends for

o exerted no influence on the nucleation


of the silica precipitate. In the carbon-
times in their diagenetic history and
examples of early, intermediate and late
some distance from the north and east
flanks of the Llano Uplift. Silicification
o ate turbidites, homogeneous nuclea-
tion also occurred, but only in ooids
silicification have been described in the
literature.
decreases downward in the crust. At the
top of the crust, silicification is perva-
o with nuclei other than quartz. In that Meyers (1977) and Meyers and James sive. In the middle, ooid and pisolite

o case , it produced a few megaquartz


crystals in the cortex.
(1978)suggested early chertification for
the Mississippian Lake Valley Forma-
cortices are replaced by microquartz,
and pore spaces are filled with micro-
o, Silicified oolites have been a pre-
ferred object of petrographic studies of
tion, New Mexico. Relativetotheestab-
Iished carbonate cement stratigraphyof
quartz and/or chalcedony, but ooid and
pisolite nuclei are unaffected. Near the
L silicification, because they reveal an these rocks, pore-filling length-fast base of the crust, ooids are no longer
abundance of relict fabrics that offer chalcedony was precipitated before and silicified, but the pore-filling cement is
insight into the detailed mechanisms of after early carbonate cements. Part of partly calcitic and partly siliceous.
J the silicification process. For example,
the concentric fabrics of the ooid cortex
the chalcedony appeared before (1) a
first generation of non-ferroan, man-
Deeper in the Marble Falls oolite, car-
bonate cementation was not interrupted
r:
provide information concerning the ganese-poor, largely non-luminescing by silicification and progressed toward
direction of the advancing silicification calcite cement, whereas most post- complete elimination of porosity and
~)
front, which may be inward or outward. dates (2) the younger manganese-rich, recrystallization to a coarsely crystal-
It is clearly inward from rim to nucleus in brightly luminescing carbonate ce - line sparry calcite. The time of silicifica-
the case of incomplete silicification ment. All other carbonate cements are tion can be pin-pointed relative to car-
where innner lamellae of the ooid cor- younger than the chert. The first two bonate cementation. In the silicified '
tex have not been affected. It is outward carbonate cements are interpreted to crust, silica cement postdates a finely
from nucleus to cortex margin in the be due to phreatic meteoric diagenesis crystalline sparry calcite cement which
case ofthe "syntaxial overgrowth"-type related to two unconformities: (i) a pre- fringes the ooids. Since this calcite is a
of replacement (also called "under- Meramecian (pre-middle Visean) un- typical incipient submarine carbonate
growth") where detrital quartz forms conformity on top of the Lake Valley cement, the subsequent silicification
the ooid nucleus (Hesse, 1987). Formation and (ii) a post-Meramecian event was attributed to temporary emer-
Among the known oolite formations unconformity that terminates the over- gence of the oolite shoal above sea level
'-.- that have been completely silicified, the lying Rancheria Formation. Supporting when it was invaded by meteoric water
UpperCambrian State College Oolite of evidence for early chertification comes (Namy, 1974).Thetimelimitsof silicifica-
Pennsylvania is one that has been stud- from unconformity-associated chert tion can only be given in relative terms
ied since the last century and has been clasts that appear to have been chert- because incipient submarine carbonate
the subject of an early modern examina- ified before redeposition, and from dif- cements can exist in the marine environ-
tion (Choquette, 1955). Ooids of the ferential compaction. Chertified crt- ment for up to 50 Ma or longer without
State College Oolite show a tripartite noidal limestones, for example, show progressing to complete pore cementa-
zonation of the cortex (Figure 5a) con- minor compaction features, whereas tion. This is illustrated, for example, by a
sisting of the following characteristics: compaction is intense in their non- pre-Eocene oolite from a West Pacific
(1) an outermost cryptocrystalline, chertified equivalents. Stylolites are ab- seamount, which still contains open pore
mostly near-opaque rim, followed by (2) sent within chert nodules but com- spaces lined only with an incipient micro-
a somewhat coarser-grained, but still mon in the surrounding carbonate host spar cement (Hesse , 1973).
c
260 Diagenesis Geoscience Canada Reprint Series 4 c
c
Eocene to Pleistocene fluvial con- prior to or during silicification . The dis- took place "during ionic mobilization
c
glomerates of western Texas provide solution affected aragonite both in the that accompanied solution-precipita- c
textural, fabric, and isotopic evidence
for the origin of unconformity-related
cortex and in biogenic fragments form-
ing the nuclei of ooids . The best evi-
tion replacement of magnesium calcite
by silica". In other words, silicification c
silicification of carbonate pebbles by
ground water below the water table
dence for the simultaneous occurrence
of replacement and dissolution is pro-
and microdolomite formation would
have occurred simultaneously and prior
c
(McBride, 1988). The ground waters vided by grains with a quartz nucleus to the recrystallization of high-Mg cal- (
became silica-enriched after percolat-
ing through Neogene volcanic ashes,
mantled by a zoned syntaxial over-
growth: the inner zone of the over-
cite to low-Mg calcite. In the Gault For-
mation, on the other hand, Hesse(1987) c
and they selectively silicified the car-
bonate pebbles derived from uplifted
growth is riddled with radially oriented
carbonate inclusions, the outer zone is
observed that trains of microdolomite
crystals in quartzine continued with the
c
Cretaceous rocks. Microquartz and inclusion-free (Figure 5b). The quartz- same optical orientation and alignment c
chalcedony are the major silica phases;
lutecite and opal-CT occur as minor
overgrowth which mantled the detrital
nucleus initially found the aragonite
into the unsilicified portions of echino-
dermossicles(Figure3f).This ledhimto c
phases. In some pebbles, concentric
chert and carbonate bands that are
of the ooid cortex still in place and
replaced it. The outer inclusion-free
the conclusion that silicification fol-
lowed carbonate recrystallization. For
c
conformable to the pebble shape alter- zone formed when the adjacent arag- the Gault Formation, other independent c
nate rhythmically and may represent
Liesegang banding. Proper hydraulic
onite of the ooid cortex had been dis-
solved without a trace, not even of
lines of evidence support an interme-
diate burial stage as the time of c
and chemical conditions for chertifica-
tion may not have persisted for more
organic matter. Grains with eccentric
quartz nuclei also indicate partial dis-
silicification.
Review of the literature thus reveals
c
than a few million years underscoring solution of the cortex prior to comple- that virtually all possible sequences c
that the chertification process was
rapid (McBride, 1988).
tion of silicification: dissolution of inner
aragonite lamellae caused the nucleus
occur in the relative timing of silicifica-
tion and well-established· diagenetic
c
Other examples of early diagenetic to fall to the bottom ofthe partly silicified carbonate reactions: (1) silicification (;
chert formation havebeen documented
for the Ordovician Aleman Dolomite of
cortex. The geopetal fabric atthe centre
of"bipartite" ooids has the samesignifi-
before and alternating with the earliest
carbonate cements (e.g., Meyers, c
New Mexico (Geeslin and Chafetz,
1982), and for Silurian back- and inter-
cance: fine-grained, crypto- or micro-
crystalline quartz replaces micritic car-
1977); (2) silicification after incipient
pore-linings of calcitic microspar but
c
reef carbonates of Illinois and Indiana bonate that fell to the cavity bottom, but before complete pore cementation c
(Dapples, 1959). In the latter case, sili-
cification postdates early diagenetic
was not dissolved, and drusy mega-
quartz fills the upper part of the cavity.
(e.g., Namy, 1974); (3) silicification
before the aragonite to calcite conver- c
glauconite formation and predates
dolomitization.
Drusy fabrics of megaquartz in the
centre of ooids with inward increasing
sion and the high-Mg calcite stabiliza-
tion reaction (e.g., Jacka, 1974); (4) sili-
c
Jacka (1974) argued for silicification grain size and a lack of inclusions reflect cification during and after aragonite c
in the Getaway turbidites prior to the
aragonite to calcite transformation, and
complete nucleus dissolution prior to
silicification.
dissolution (e.g., Choquette, 1955); (5)
silicification after the aragonite conver- c
also prior to the high-magnesian calcite
stabilization reaction as discussed
Using evidence from carbonate inclu-
sions in authigenic quartz, Richter
sion, but before the high-Mg calcite
transformation (e.g., Richter,1972); and
c
below.The original structure offormerly (1972) found that silicification postdated (6) silicification after both the aragonite c
aragonitic shells was commonly pseu-
domorphed in silicified portions of the
the aragonite to calcite transformation,
but predated the high-Mg calcite stabil-
and high-Mg calcite transformations
(e.g., Hesse, 1987). c
fossils, but obliterated in calcitized
portions. This observation suggests
ization. Authigenic quartz in original
aragonite skeletons contained low-Mg
Silica Sources in Carbonates.
Most chert nodules in carbonates can
c
that the original aragonitic fabric was calcite inclusions as it also did in original be adequately explained by the redis- c
still in place during silicification, but had
been lost prior to calcitization. Silicifica-
low-Mg calcite skeletons. In original
high-Mg calcite skeletons, the carbon-
tribution during diagenesis of biogenic
silica contained in the host sediment.
c
tion preceded calcitization . In the Gault ate inclusions in authigenic quartz However, it has often been questioned c
turbidites by contrast, Hesse (1987)
found former aragonite shells replaced
showed elevated Mg contents.
Microdolomite in low-magnesium cal-
whether siliceous organisms are suffi-
ciently abundant ln shallow-water car- c
by fabric-destroying calcitic spar which
showed no signs of silicification. In pri-
cite is interpreted as an exsolution pro-
duct from former high-magnesium cal-
bonate sediments to provide the quan-
tities of silica required for the formation
e
mary calcite grains, original fabrics cite (Lohmann and Meyers,1977).lnthe of chert nodules (e.g., Dapples, 1959). c
were preserved, even after partial re-
placement by silica, suggesting silici-
Getaway turbidites, it was found only in
the silicified portions of former high-Mg
According to Knauth (1979), no example
has been reported in the literature for c
fication postdated aragonite conversion
to calcite.
shell fragments, but not in the unsili-
cified portions of the fossils (fusulinids,
modern shallow-water carbonate envi-
ronments with abundant siliceous or-
c
Choquette (1955) provided compel-
ling evidence that many of the quartz-
bryozoans, echinoderm plates) which
are now low-Mg calcite . Jacka (1974, p.
ganisms . For Paleozoic carbonates, on
the other hand, sponge spicules are a
c
replaced ooids in the State College 425) inferred from this observation that widely quoted source of silica, par-
(
Oolite underwent aragonite dissolution Mg-exsolution from the high-Mg calcite ticularly for the early chertification of c
(
c
c.
c Origin of Inorganic and Replacement Cherts 261

c,-
'-- lutitic limestones or dolomites (e.g., latest generation of hydrothermal jas- water early chert in limestone is con-
r:
I Meyers, 1977; Geeslin and Chafetz, peroid deposits associated with Lara- ceived by analogy with the Dorag mix-
<;
1982). As Knauth (1979) pointed out, mide ore deposition. ing-zone model for dolomit ization
[J nodular chert horizons may have re- For silicification during intermediate (Badiozamani, 1973).In the mixing zone
ceived the silica from pore waters that stages of burial diagenesis, pressure between meteoric and marine pore
C had previously percolated through and solution of quartz in the host sediment, waters in coastal areas, solutions may
C leached considerable thicknesses of
unlithified source sediment which now
together with the smectite to illite trans-
formation in associated shales have
become undersaturated, for example,
with respect to calcite. Undersaturation
C may be devoid of any silica . been invoked as silica sources in addi- occurs if the starting solutions havedif-
However, not all chert nodules in car- tion to biogenic silica (Hesse, 1987). ferent temperatures or partial CO2
bonates have a biogenic source. Banks Knauth's Geochemical Model and pressures, even if each of them alone is
(1970) discussed the example of the Isotopic Evidence for Early Chert originally supersaturated. Meteoric
Formation in Umestone. waters percolating through coastal car-
o cherty Mississippian Leadville Lime-
stone of Colorado which does not con- Silicification of carbonate sediments bonates will become saturated rapidly
o tain any sponge spicules or Radiolaria
or their pseudomorphs. An alternative
requires pore solutions that are super-
saturated with respect to the silica
with respect to calcite due to the dis-
solution of aragonite and Mg-calcite.
o source for the silica was seen in the
dissolution of quartz and other detrital
phase precipitated and undersaturated
with respect to the carbonate mineral(s)
Surface seawater in the tropics and
subtropics is also calcite-supersatu-
silicates in a hypersaline, marginal dissolved. Although this general geo- rated. The mixture of the two, however,
marine environment similar to the mod- chemical and thermodynamic require- may be undersaturated if the solutions
ern Coorong lagoon. Banks also found ment for chert formation by replace- mix in the appropriate ratio and the sys-
o eolian sands of the underlying (Upper ment is the same for deep-water pelagic tem is closed with respect to CO2 (Fig-

o Devonian) Chaffee Formation widely


replaced by carbonate; this could have
sediments and shallow-water carbon-
ates, the specific conditions under
ure 6). The same carbonate-saturated
meteoric waters may also become satu-
o provided the silica for the Leadville
nodular cherts by an upward advective
which it may be reached during early
diagenesis in shallow-water carbonates
rated with respect to opaline silica fol-
lowing dissolution of biogenic siliceous
process. Banks (1970) observed three may be quite differentfrom those during shells. However, upon mixing with
chert generations: (1) an early genera- the somewhat later and deeper burial marine connate water they will immedi-
tion formed in a hypersaline marine en- stages of silicification in pelagic sedi- ately become undersaturated with
vironment of high, but fluctuating, pH; ments. The sequence of silica phases respect to opal-A because of the low
r (2) a later generation precipitated after may also be different. silicon concentration in seawater. They
initial carbonate lithification; and (3) a Knauth's (1979) model for shallow- may not become undersaturated with
respect to opal-CT, however, and most
probably not with respect to quartz.
+1 ------quartz ---~ The mixing zone, therefore repre-
r sents a geochemical environment con-
~--opal-CT ---+-__ ducive to calcite dissolution and simul-
taneous silica precipitation as opal-CT
or quartz. This explains why in the mix-
o ing zone opal-CT or quartz can form

o under near-surface conditions and do


not require the deeper burial (of at least
o a few 100m)and longer periods of time
(1Q6 to 107 a) typical of deep-seacherts.
:J -I opal-A Opal-CT might bethefirstsilica phaseto
replace calcite, but at presentthere is no
compelling evidence that it does in fact
precede quartz in these shallow-water
carbonates. If the solutions in the mix-
ing zone are only supersaturated with
r
U o 5 10 25 50 15 100 respect to quartz, and not with respect
to opal-CT, then quartz would precipi-
% sea water tate directly, given that kinetics permit
nucleation .
If the system is open with respect to
Figure 6 Mixing model for silicification of shallow water carbonates through meteoric water
CO2 , calcite may not dissolve, because
influx during early stages of emergence. (Modified from Knauth, 1979). The saturation level is
the ratio of the ion activity product of the dissolved species to the equilibrium solubility of the
the solutions may not be calcite-under-
mineral. Positive log values = supersaturation, negative log values = undersaturation. Right saturated, but silica could still precipi-
side of diagram shows area where mixing ofmeteoric andconnate marine watercreates a pore tate as a pore-filling cement. In other
fluidsimultaneously undersaturated with respect to calcite andsupersaturated with respect to situations, dolomite may not becomesili-
opa/-CT and/or quartz. cified while calcite would, because the
c
262 Diagenesis Geoscience Canada Reprint Series 4 c
c
mixing-zone solutions may be super- carbonates of greatly differing ages (1979) have shown that the interpreta-
c
saturated with respect to dolomite, as from the Precambrian to the Cenozoic tion of isotopic compositions may be c
suggested in the original Dorag model.
The acidity ofthe pore solutions isone
(Knauth and Epstein, 1976). On 50/0180
plots, trend-lines for different age
quite complex. In the Mississippian
Lake Valley Formation discussed pre- c
additional factor that may be important
for the precipitation of silica in carbon-
groups of cherts are parallel with the
meteoric water-line (Figure 7). This sug-
viously, 01 8 0 values of early calcite
cements vary very little (+ 27.5 to
c
ate sediments. It is implicit in Knauth's gests that mixing of connate marine + 28.5%0 SMOW), whereas the silica C
model, but was already emphasized by waters to various extents with meteoric minerals of the associated early diage-
Lovering and Patten (1962). Their work waters is responsible for the isotopic netic chert fabrics (microquartz, chal- C
is one of the few experimental studies
bearing on the problem of carbonate
signatures of the cherts which precipi-
tated from these waters.
cedony, and megaquartz) span a con-
siderably wider range of values ( + 24.3
C
replacement by chert. In the meteoric- However, the detailed results of to + 29.8%0SMOW).The chert minerals C
marine mixing zone, the pH of the pore Meyers and James (1978) and Land must have precipitated from waters iso-
solutions is largely a function of the
C
availability of carbonic acid or the par- C
tial pressure of CO2 , Lovering and Pat-
ten (1961) tested the idea pursued in C
very early experiments (Church, 1862;
Cox et a/., 1916) that silica-supersatu-
C
rated solutions will replace carbonate C
minerals with silica at low temperature
and pressure in the presence of (but -20 C
not in the absence or at low partial pres-
sure of) CO2 , They found that solutions
C
supersaturated with respect to opal-A, C
when brought into contact with CO2 of
1 atm pressure at room temperature,
(
would decrease in pH from original C
values of 6.8 to 7.1 to values of 5.7 to 6.2. -60
They were capable not only of dissolv- C
ing calcite and dolomite, but also of
precipitating silica. On the other hand,
C
solutions in contact with air at a partial -80 C
pressure of CO2 of only 0.03 atm gener-
ally acquired a pH of 8.2 to 8.6. The C
higher pH apparently resulted from -1 00 C
buffering by carbonates. These solu-
tions did not precipitate silica, although C
some carbonate was dissolved. The dif-
ference in the partial CO2 pressures
-120 C
apparently was sufficient to cause silica
precipitation in one case, but not in the
C
other. It therefore seems that if acidic -140 C
solutions supersaturated with respect
to a given silica phase (e.g., opal-CT or C
quartz) come into contact with Ca or Ca-
Mg carbonates , they will dissolve car-
C
bonate and precipitate silica. Neutral or C
slightly basic solutions that are silica-
supersaturated, on the other hand, 16 20 24 28 32 36 40 c
may move for considerable distances
through carbonate rocks without pre- 618 0 (%0) e
cipitating silica. (
Knauth's model is consistent with the
Figure 7 Hydrogen and oxygen isotopic trends in Phanerozoic carbonate-hosted cherts.
various lines of evidence for early chert
Elongation of the trend fields parallel to the meteoric water line (set of diagonal lines) for
formation in shallow-water limestones
different geologic periods supports Knauth 's (1979) mixing model for early silicification in
(
enumerated in the previous sections. It shallow·marine carbonates. Temperatures of quartz crystallization are based on quartz-
deliberately does not take into account water isotope fractionation relationship 1000 In = 3.09 x 106 7-2 - 3.29, where a is the
C
kinetic considerations. The model finds
strong support from oxygen and hydro-
fractionation factor between quartz and water and temperature is in degrees Kelvin. (From
Knauth and Epstein, 1976). Line A: Isotopic composition of cherts in equilibrium with SMOW
C
gen isotopic studies of nodular cherts in at various temperatures. (.

c
c Origin of Inorganic and Replacement Cherts 263
cr
topically at least 5%0 lighter than those topic composition of the subaerially process. Clayton's (1986)detailed geo-
o from which the early carbonate cements
precipitated or at temperatures up to
exposed cherts did not show the ex-
pected 180 _or O-depletion indicative of
chemical analysis of a paramoudra
structure sheds light on the possible
c' 40°C higher than the carbonate ce- the involvement of meteoric water. sources and migration paths of some of
c ments. Petrographically, the silica min-
erals and carbonate cements occur in
Among the several explanations offered
by Land (1979)for this unexpected find-
the ions involved in the cementation and
replacement reactions.
( close association. Isotopically lighter ing is recrystallization of the micro- In the paramoudra structure, silica

c pore waters for silica precipitates than


for the carbonate cements are in line
quartz from an opal-CT precursor,
where the precursor's isotopic composi-
precipitationwasprecededbycarbonate
cementation inthe innerchalkcore. Both
with Knauth's model, if the former are tion was inherited. This would provide carbonate cementation and the subse-
affected by mixing with meteoric water an elegant solution , but is it feasible quent replacement by silica in the yet
o and the latter are equivalent to SMOW geologically without isotopic change? uncementedcarbonate aroundthechalk

o or only slightly depleted. Isotopic re-


equilibration at higher temperatures
Flint Formation in the Cretaceous
Chalk: A Geochemical Analysis.
core are related to reactions initiated in
the central burrow, as illustrated by the
o could also explain the data, but would
require an opal-CT precursor recrystal-
The "paramoudra structure" in the
Upper Cretaceous chalk of England is a
concentric geometry. The change from
carbonate precipitation to carbonatedis-
lizing to quartz. This would be possible tubular chert structure related to bio- solution and silica precipitation reflectsa

o for microquartz, but difficuIt to perceive


in the case of megaquartz, (and proba-
turbation (Bromley and Ekdale, 1986)
which provides a rare lucky break
change in pH. This resulted from bacte-
rial sulphate reduction and associated
o bly also of chalcedony).
Chert nodules in Miocene pelagic
revealing insight into the chemistry of
the carbonate/silica replacement pro-
iron-sulphide precipitation which was
limited by iron availability and isa proton-
o chalks exposed on the north Jamaican cess. It consists of a cylindrical flint consuming reaction (see e.g., Hesse,

o coast are different in their mineralogical


composition from those in downfaulted
nodule surrounding a chalk core which
in its centre contains the pyritized, glau-
1990a,for review).
Only a small portion of the cement
o age-equivalent rocks under water on conitized and commonly also phos- carbonate was provided by sulphate

o the north slope of the island: opal-C'T


characterizes the submarine occur-
phatized vertical burrow of Bathichnus
paramoudrae (Figure 8). The structure
reduction, because the cement is iso-
topically heavy.Sulphate reduction pro-
o rence, which probably did not experi-
ence any meteoric diagenesis, whereas
constrains the geochemical conditions
under which the replacement took
duces isotopically light carbonate (013C
= -20 to -25%0 POB),and less than 10%
microquartz occurs in the subaerially place in the chalk. This environment is of the cement could have been derived

o exposed material (Land, 1979). At first


glance, this seems to be a textbook
different from the one envisaged in
Knauth's (1979) model in that the
from this source. However, this small
fraction of the cement ions supplied by
o illustration of Knauth's model: direct
quartz-precipitation in a diagenetic
replacement seems to occur under fully
marine conditions and does not require
sulphate reduction seems to have been
sufficient to tip the balance in favor of
o environment affected by percolating
meteoric water, and opal-CT preserva-
mixing with fresh water. However, the
sediments may have been affected by
carbonate precipitation. The bulk of the
carbonate and all of the Ca2 + had to be
() tion in young (less than 10 Ma old) meteoric water influx at some later derived from dissolution of carbonate
o pelagic sediments. However, the iso- stage not related to the replacement host sediment (aragonite dissolution
and/or pressure solution of coccoliths
o during early chalk diagenesis). The

o decisive role of sulphate reduction for


carbonate precipitation was to raise the '
o pH through iron-sulphide precipitation
and to supply additional carbonate
() alkalinity. The 013C values increase
from centre to margin of the chalk core
(Figure 9) reflecting a decrease in the
c proportion of cement present which is
isotopically lighter than the host sedi-
[". ment. The time of carbonate cementa-
tion in the paramoudra structure is
B bracketed by porosities between 80
C and 650/0. (These were estimated from
the degree of AI dilution compared to
f-f1int-+-cnented-+-f11llt ---1 "undiluted" AI values in the slightly
chalk

".
(e) II (bl ~ (el a (dl r. .":'
..: .1
cemented chalk surrounding the para-
moudras ; samples Band G, respec-
tively, Figure 9).
r' .
Figure 8 Schematic three-dimensional view of paramoudra flint structure and sample Carbonate precipitation terminated
position. (8) Bathichnus sp. burrow; (b) pyrite; (c) calc ite cement; (d) disseminated pyrite when exhaustion of reducible iron stop-
and glauconite. (Modified after Clayton, 1986). ped iron-sulphide precipitation. In the
c
c Origin of Inorganic and Replacement Cherts 265

C'·
C model, the flint bands mark the position rocks which is quite unusual in the light fibrous quartz-overlays on euhedral
r: of the redox boundary which separates of the silicification mechanisms and the megaquartz consisting of intergrown
an oxic (above) from an anoxic environ- find ings of the DSDP for biogenic sili- chalcedony and quartzine as well as
CJ ment (below) at the time of silica pre- ceous deep-sea sediments discussed zebraic chalcedony; and (iv) so-called
"cubic quartz" crystals. These crystals
C cipitation. Silica precipitation thus
occurs very early during diagenesis, a
in the accompanying paper (Hesse,
1990b). The silicification history of the generally do not represent a pseudo-
C feature shared with Knauth's (1979) Cow Head is protracted, since it includes morphic replacement of cubic minerals,
model. Burial depth at the time of sili- later post-eompactional silica remobili- but are simple stubby crystals mostly
( cification may have been as little as zation and reprecipitation. without prism faces and often doubly
( 5-10 m. The rhythmic bedding of the terminated by one set of rhomb faces on
Chalk, exhibited by the regularlyspaced CHERT REPLACING EVAPORITES either end. Finally, (v) anhydrite inclu-
o flint bands In many coastal cliff sections,
may then reflect abrupt, stepwise rises
Petrographic Characteristics
and Fabrics of Chert-replaced
sions in megaquartz, quartzine and
microfamboyant quartz represent the
G of the redox-boundary related to basin- Evaporites. most convincing fabric evidence for
o wide sedimentation pulses and/or Given the geochemical environments of evaporite replacement by chert.

o breaks. Clayton 's (1986) work for the


first time provides a firm basis for an
chert formation discussed in earlier
sections, it is not surprising to find chert
Milliken (1979) listed the following
sequence of quartz fabrics in chert nod-

o evaluation of the geochemical environ-


ment of carbonate/chert replacements
commonly replacing evaporites. The
hypersaline and generally high-pH en-
ules replacing Mississippian evaporites
of southern Kentucky and northern Ten-
o in fully marine carbonates where the
replacement process is not affected by
vironment of evaporite deposition per-
mits silicon concentrations in solution to
nessee (in the order of their occurrence
from nodule edge to centre): (1) isolated
r meteoric diagenesis. The chalk is a build up to high levels. Milliken (1979) spherules of quartzine in randomly

or shelf equivalent of deep-sea pelagic


limestones which commonly also con-
summarized the petrographic features
of chert replacing evaporites. This chert
fibrous microcrystalline quartz; (2)
interlocking spherules of quartzine,
tain chert nodules probably formed is typically nodular. As pointed out in the lutecite, or microflamboyant quartz; (3)
spherules of quartzine, lutecite, or
o under similar conditions as the flint nod-
ules. It is not known though, whether
previous section, the most common sil-
ica fabric in chert-replaced evaporites is microflamboyant quartz grading into
o they also occur in bands.
Early diagenetic silicification in deep-
length-slow chalcedony or quartzine.
However, as a single criterion this fabric
"cubic megaquartz" ; (4) mosaics of
megaquartz spherules and undulose
o water limestones without meteoric
water influx has also been described by
is not sufficient evidence for the former
presence of evaporites if all other testa-
megaquartz; (5) simple quartz crystals
(normal euhedrally or "CUbically" ter-
L· Coniglio (1987) for the Cambro-Ordovi- ments have been lost. Other quartz fab- minated) and spherules of quartzine,
o cian Cow Head Group in western New-
foundland, Canada. Uncompacted sili-
rics found in chert nodules replacing
evaporites are (i) spherulitic quartzine,
microflamboyant quartz or megaquartz
which occur isolated in secondary
o cified burrows provide evidence for very lutecite, and microflamboyant quartz; cavity fillings of calcite or dolomite (Fig-

o early silicification in interbedded mud- (ii) strongly undulose megaquartz; (iii) ure 10d) indicating incomplete original

o
o
r
Figure 10 Common associations of silica
fabrics in chert nodules replacing evapo-
rites: (1) randomly fibrous microcrystalline
o quartz; (2) quartzine spherules; (3) anhy-
drite inclusions; and (4) calcite.
§ (l)
D (8) Thin rim of spherulitic quartzlne followed
inward by megaquartz of increasing grain- ~ (2)
size which often contains anhydrite in-
~ (3)
o clusions .
(b) Thick rim of spherulitic quartzine fol-
lowed inward by strongly undulose mega-
EJ (4)

quartz in the central part of nodule. Mega-


quartz may show crudely radial or fan-like
undulosity and may have a nucleus of spher-
ulitic quartzine or microflamboyant quartz
riddled with anhydrite inclusions.
'-'
(c) Very thin rim of spheruJitic quartzine fol-
v: lowed by megaquartz.
(d) Marginal spherulitic quartzine followed
inward by rim of palisade megaquartz and
large carbonate replaced centre of nodule
'-- .
with isolated inclusions of quartz crystals
indicating incomplete initial replacement of c
anhydrite by chert. (From Milliken, 1979).
........ '
c
266 Diagenesis Geoscience Canada Reprint Series 4 c
c
evaporite replacement by chert; (6) MAGADI·TYPE CHERTS the sodium ion activity. Dilution accom-
C-
overlays offibrous quartz (zebraic, chal- Cherts which result from the conversion plishes both. The conversion occurs in C
cedonic, lutecitic, or quartzinic) on of the chemically precipitated, silica- near-surface layers that are accessible
euhedral quartz terminations; and (7) rich mineral magadiite to silica form to rain and runoff waters . The interme- C
breccias of various of the aforemen- in alkaline lakes in semiarid cli- diate kenyaite has been observed in ·C
tioned quartz types in a secondary car- mates (Eugster, 1967, 1969; Hay, 1968; contact with magadiite in the field (Eu-
bonate cement filling of the cavity. The Maglione, 1979; Rooney et al., 1969). gster, 1969, fig. 4). Only microcrys- C
absence of such secondary carbonate Although related to a replacement pro- talline quartz, equant or fibrous, occurs
cementation leads to "rattling stones" cess, these cherts are quite different in in Lake Magadi cherts. The fibrous vari- C
("Klappersteine"), in which quartzcrys-
tals and quartzine spherules which
origin from most of the types hitherto
discussed and come close to directly
ety chalcedony may be length-fast or
length-slow and occur in spherulites. It
C
were formerly suspended in the anhy- precipitated inorganic cherts. is likely that initially opal-A may be in- C
drite fell to the bottom of the cavity (now Magadlite Precipitation. volved in the conversion, because for
geode) after anhydrite dissolution. The hydrous sodium silicate magadiite lowered pH values the solutions seem
C
None of the nodules studied by Milli- NaSi70, 3(OHh· 3H20 was precipitated to become ·h!ghly supersaturated with C
ken contain the entire sequence; one or from alkaline waters of Lake Magadi in respect to arrioephous silica. Eugster
more of the fabrics are usually missing the East African rift valley during the (1969) suggested tllat once some of the C
amorphous silica has recrystallized to
and the relative importance of individual
fabrics varies strongly between nodules
Late Pleistocene, at times when the lake
level was more than 10 m higher than microquartz, direct quartz precipitation
C
(Figure 10). In most nodules, the rim today. Eugster (1967, 1969) first de- may continue spontaneously, as long C
starts with fabrics (2)or (3). If the unce- scribed the conversion of magadiite to as the sodium produced is removed
mented central cavity is large, (4) may silica and analyzed the chemical condi- efficiently. However, if the solutions C
be missing. Fabrics (5)and (6) are mutu-
ally exclusive. However, the basic pat-
tions of magadiite precipitation and con-
version. Present-day Magadi brines
causing the conversion are sufficiently
dilute, direct microquartz precipitation
C
tern, which has been recognized for may contain more than 30 mM dissolved is possible. Eugster (1969) estimated C
more than a century, "is one of a rim of silicon (or 1900 ppm SiO~. These high that the minimum time necessary for
fibrous quartz (usually quartzine) fol- values are primarily obtained through the conversion was probably not more C
lowed inward by megaquartz.
Characteristics of the Replacement
evaporative concentration. Because of
high pH levels, the brines appear to still
than a few hundred years, perhaps
less, based on angular chert chips em-
C
Pore Fluids. be slightly undersaturated with respect bedded in gravel beds interlayered with C
From oxygen-isotope analyses, Milliken to amorphous silica. A very high l pH the cherts.
(1979) derived temperatures and com- results from the precipitation of trona Chert formations that have been in-
C
positions of the pore fluids whi2h (Na2Q03.e-NaHC03· 2H 20), which re terpreted as lacustrine Magadi-type C
replaced the evaporites with chert. For moves considerable amounts of bicar- cherts in the geological record include
the earliest microcrystalline quartz, bonate, thereby increasing the pH more examples from the Cambrian Officer C
Basin of South Australia (White and
connate marine water of ambient sea-
water temperature (25°-30°C) was con-
rapidly than the concentration of dis-
solved silicon (Jones et a/., 1967). In a Youngs, 1980),the Middle Devonian Old
C
sidered the most likely fluid which had stratified lake, magadiite precipitation Red Sandstone of northern Scotland C
caused silicification. Ouartzine and may periodically take place in water (Parnell, 1986), and Jurassic to Pleisto-
megaquartz, which follow In the diage- layers where lowering of the pH occurs ceneoccurrences in the western United C
netic sequence, formed at somewhat
higher temperatures (up to 40°C) from
without dilution. Thiscould happen near
the pycnocline where methane-oxida-
States (Surdam et a/., 1972; Sheppard
and Gude, 1986), including the well-
C
mixed marine-meteoric pore waters. tion would produce CO 2, Eugster (1969) known Eocene Green River Formation C
Zebraic chalcedony, which appeared viewed the fine lamination in magadiite (Eugster and Surdam, 1973).
after megaquartz, is isotopically slightly beds as varves. Magadiite also replaces C
heavier and was interpreted to have pre-
cipitated from meteoric water at some-
host sediment as, for example, at Alkali
Lake, Oregon (Rooney et a/., 1969).
INORGANICALLY PRECIPITATED
LAGOONAL AND LACUSTRINE
C
what lower temperatures than the pre- Here, veins at least 1 m deep are filled CHERTS C
vious quartz types. with magadiite precipitated by ground- Direct inorganic silica precipitation in
Other well-documented examples of water reactions. surface environments was first de- C
silicified evaporites have been pub-
lished by Folk and Pittman (1971) ,
Magadilte Conversion to
Quartz Chert.
scribed by Peterson and Von der Borch
(1965) from the Coorong Lagoon, the
C
Siedlecka (1972, 1976), Chowns and The conversion of magadiite to silica famous carbonate-precipitating locality (
Elkins (1974), Friedman and Shukla through dehydration and sodium lossmay from which primary dolomite formation
(1980), and Geeslin and Chafetz (1982). involve kenyaite (NaSi, ,02o.s(OH)4· was also first reported. The mechanism
C
Relict hopper moulds in the Rocklea
Dome cherts of the Pilbara Craton,
3H 20) as an intermediate phase, or it
may directly produce a silica phase (see
of direct inorganic silica precipitation
which was formerly held responsible for
C
Western Australia, probably preserve equations (2) to (4) in Eugster, 1969).(It the formation of bedded deep-sea C
the oldest evidence (3300-3500 Ma) for
halite precipitation on earth (Boulter
rarely leads to silhydrite 3Si0 2• H20;
Gude and Sheppard, 1972).The reaction
cherts, but proven wrong for these
deposits (Hesse, 1990b) occurs here
C
and Glover, 1986). is favoured by lowering of the pH or In the lacustrine environment. The C
C
C
c
( Origin of Inorganic and Replacement Cherts 267

C'
C discovery has already been referred to related to soil-forming and/or weather- Silcrete Fabrics.

c' in the context of silica-replaced carbon-


ates. In the playa lakes associated with
ing processes . Silcretes develop under
climatic and environmental conditions
Summerfield (1983) distinguished four
different fabric types in silcretes , simi-
( the Coorong Lagoon, silicon is dis- similarto other duricrusts (calcretes and lar to the five types of Smale (1973).
c· solved from detrital silicates (mainly
quartz) by alkaline lake waters (pH =
ferricretes) and laterites.
Summerfield (1983), in a study of sil-
These are: (1)grain-supported, (2)float-
ing, (3) matrix and (4) conglomeratic
c 9.5 to 10.2). It is precipitated when the cretes from southern Africa, distin- fabric. In the grain-supported fabric,

c. pH drops as a result of decaying plant


matter during evaporation and ensuing
guished "weathering-profile silcretes"
and "non-weathering-profile silcretes".
frame-work grains produce a self-sus-
taining fabric. The pore space is filled
c hypersalinity. The initial silica phase
impregnating the carbonates is opal-A.
The non-weathering-profile silcretes
occur in the Kalahari Basin as silicified
by optically continuous quartz over-
growths, or more rarely by opaline sil-
Disks of silica-impregnated sediment calcretes, playa sediments and other ica, chalcedony or microquartz. This
about 1 cm thick and 10 cm in diameter silicified evaporite-pan deposits. They variety corresponds to Smale's (1973)
( are formed from cracking of dried-up represent the type of environment that quartzitic type and is petrographically
o lake sediment.
Opaline cherts from Lake Bogoria of
is generally envisaged for silcrete for-
mation (e.g., Smale, 1973): semi-arid
very similar (identical according to
Smale) to sedimentary quartz arenites.
o the East African rift valley in Kenya climate, high evaporation rates, and Only its occurrence distinguishes this

o happen to be associated with an alka-


line lacustrine environment, but are in
highly alkaline pore-fluids that rise by
capillary action and precipitate silica
type of silcrete from the latter as sur-
face-formed. Ouartzitic silcrete is abun-
o fact hydrothermal-volcanogeniccherts ,
because they were precipitated from
upon mixing with descending fluids of
lower pH.
dant in the first occurrence of silcrete
from the Arabian Gulf area described
( hydrothermal hot springs (Renaut et al., The "weathering-profile silcretes" by Khalaf (1988). The floating fabric cor-

o 1986; Renaut and Owen, 1988). They


occur only at sites of hydrothermal ac-
are found in the Cape coastal zone asso-
ciated with deep weathering profiles
responds to Smale's terrazzo type.
Framework grains constitute more than
o tivity in the rift lake. Although they are
diatom-rich, alternative silica sources
up to 20 m thick. They occur under more
humid climatic conditions than the first
5% by volume, float in the cement, and
do not form a self-supporting fabric.
o besides hydrothermal are unlikely. type. The soils are poorly drained with The matrix fabric (which from a petrolo-
o These opaline cherts appear to have
formed from a gelatinous siliceous pre-
high organic activity, and pore-solutions
have fluctuating pH-values which tem-
gist's point of view should properly be
called cement fabric) contains less than
o cursor that began to Iithify before it was porarily fall below 4 (Summerfield, 5% framework grains and includes

c subjected to subaerial exposure. The


precursor was probably not magadiite,
1983). The evidence for low pH comes
from relatively high Ti02 levels (> 1%)
both Smale's Albertinia and opaline or
fine-grained, massive types. The con-
o otherwise the cherts would be expected
to have been transformed to quartz.
compared to the titanium-poor (Ti0 2
< 0.2%) non-weathering-profile sil-
glomeratic fabric consists of abundant
clasts ofthe floating or terrazzo type set
G Inorganic silica precipitation in the sub- cretes. The n02 occurs as iine-grained in a usually brick-red to brown siliceous
lacustrine environment resulted from a anatase within siliceous cements. cement. Some clasts are very irregular
() rapid drop in temperature and, possibly, Titanium is mobile as Ti(OH)4 at pH and angular in shape, indicating a local
o pH. The planktonic diatom Melosira,
which is abundant in these cherts, is
values below 5, but becomes insoluble
as Ti02 at pH levels above 2 upon
derivation without significant transport.
Others are remarkably rounded, either
o indicative of a considerably fresher lake dehydration. As these silicified rocks due to substantial transport or (and)

o (alkalinity of 5-6 rneq-L-l) at the time


of silica precipitation in the early to mid-
have lost their aluminum, pH must have
been below 4, at least temporarily or
chemical attack.
The quartzitic or grain-supported
o dle Holocene than today (900 meq- L'l).
At the same time, the lake was deeper
locally in micro-environments (Thiry
and Millot, 1987). (Alternatively, Al 20a
types with optically continuous quartz
overgrowths have in common that they
c than at present and the sites of chert for-
mation which are now exposed up to
was removed by organic complexation).
Although many silcretes are found at
occur topographically on elevated
grounds. This possibly reflects environ-
0' 1.7m above the lake level were 8-10 m the surface, not all of them have formed ments of relatively low supersaturation
C) under water.
An ancient analogue of Coorong-type
there. Woolnough (1927), Langford-
Smith and Drury (1965), and Hutton et
of the Silica-precipitating fluids, i.e.,
supersaturation with respect to quartz,
l chert occurs in the Triassic rift grabens al. (1972) considered silcretes to be sur- but not with respect to the less well-
of Eastern North America. Wheeler and face products. However, Frankel and ordered silica phases. Floating (or ter-
B Textoris (1978) described such cherts Kent (1937), Frankel (1952), Mountain razzo) types, on the other hand, are
l
,~
from the Newark Group in the Deep
River Basin of North Carolina and other
(1952), and Bruckner (1966) presented
evidence that silcretes may also form in
found on flats or below the surface
(Smale, 1973).
Triassic rift basins . the subsurface at depths of 20 to 30 m. Examples of Ancient Silcretes.
This point of view was also adopted by Ancient examples of silcretes and sil-
PEDOGENIC CHERTS: SILCRETES Exon et a/. (1970), and clearly docu- icified paleosols from the Eocene of the
Environments of Silcrete Formation. mented by Summerfield's (1983) work. Paris Basin and the Central Massif of
Another example of near-surface, in- Recent Australian silcrete studies are France are rich in titanium oxides and
organic silica precipitation is the for- by Watts (1978) and Langford-Smith appear to have formed under seasonal-
mation of silcretes, a process closely (1978). ly humid climatic conditions (Thiry and
c
268 Diagenesis Geoscience Canada Reprint Series 4 c
(

Millot, 1987). They occur in the lower HYDROTHERMAL-VOLCANOGENIC widespread and pervasive silicification;
c
Eocene as horizons up to 3 m thick with CHERTS (2) isolated ponds and depressions in c
a distinct zonation from granular (bot-
tom) through columnar to pseudobrec-
Silicification associated with hydrother-
mal activity is a major alteration mecha-
the median-rift valley of mid-ocean
ridges where the fluids discharge and c
ciated chert (top). Eluviation and iIIuvi-
ation features typical of soil formation
nism in volcanic sequences. The pro-
cess may occur at elevated tempera-
may accumulate siliceous sediments;
(3) high-temperature geothermal areas
c
are abundant. The mineralogy of the tures and fall on the borderline between on land associated with spreading linea- c
secondary (non-detrital) silica phases is
vertically zoned. Opal-A prevails at the
diagenesis and metasomatism/meta-
morphism. Davis' (1918) hypothesis that
ments, more commonly with volcanic
island arcs, and also with transform fault c
bottom, microcrystalline quartz in the
middle, and euhedral megaquartz in the
the silica in the Franciscan radiolarian
cherts in California was derived from
zones or continental intraplate volca-
nism (hot spots). They may accumulate
c
upper part ofthe profile (Figure 11). This silica-r ich sea-floor springs emanating large amounts of siliceous deposits. c
suggests downward-migrating solu-
tions of increasing silica supersatura-
from centres of submarine volcanism
gave rise to the view that chert in gen-
These environments of silicification
are typically sites of base-metal and c
tion. As emphasized by Thiry and Millot eral was of volcanic origin. This theory iron-enrichment. Attention invariably c
(1987), the presence of impurity ele-
ments has an important effect on the
prevailed for more than half a century,
until disproved by evidence from mod-
has centred on the valuable metals and
not on iron and silica, although the latter c
type and size of quartz crystallizing
from solution. Times of precipitation
ern sea-floor studies as outlined in
Hesse (1990b).
are much more abundantly transported
components in these systems. This
c
alternated with leaching periods during The problem of differentiating volca- accounts forthe common association of c
which clay minerals were dissolved and
detrital quartz grains corroded.
nogenic chert from other types of chert
in the geologic record remains never-
the ore bodies with iron-formation and
cherty siliceous strata (Hutchinson , c
Early to Middle Proterozoic silcretes
of the Churchill and Bear Provinces of
theless important. However, few stud-
ies of silica deposition and silicification
1982). Despite the large number of
occurrences, little is therefore known in
c
the Canadian Shield appear to be the in modern volcanic terrains or geo- detail about the silicification process.
oldest silcretes recognized in the geo-
logic record. They formed under arid
thermal areas seem to be available. The
only detailed studies are by Rimstidt
Apparently the ore-transporting fluids
which also affect silicification are c
climatic conditions, as suggested by
paleoclimatic indicators of aridity in
and Cole (1983)and Keith et al. (1978)in
active geothermal areas on land in
strongly chlorinated, highly reduced
and weakly acidic (Hutchinson, 1982).
c
associated formations (Ross and Chia- Nevada and Wyoming. Silicification Within Volcanic c
renzelli, 1985). They are low in Ti0 2 , but
titanium content alone without other
Environments of Volcanogenic Chert
Formation.
Edifices.
Within the volcanic edifices, silicifica- c
independent evidence would not be a
sufficient criterion for aridity in the Pre-
Silicification related to hydrothermal
activity occurs at different levels in vol-
tion occurs in alteration zones which
tend to be intensely pyritized and com-
c
cambrian, as these authors point out. canic edifices, both in submarine and monly sericitized. Sericitization indi- c
Titanium mobility would have been low
under both arid and hum id climatic
continental environments. Three set-
tings may be distinguished: (1) the
cates ac idic hydrothermal solutions
(Meyer and Hemley, 1967). Hydrother- c
conditions, because in the absence of a ascent-routes of the fluids within vol- mal silica precipitation within volcanic c
vegetation cover Precambrian soil
waters would not have become as acidic
canic complexes which experience sequences (type 1 above) occurs before
c
as under humid conditions later in the
Phanerozoic. Humid-climate P.recam-
STRUCTURES SILICA GRAIN SIZE
ILLUVIATED
c
brian soils, especially silcretes would,
SAND 10 1 01 001mm
c
therefore, also be low in Ti0 2 .
Other ancient examples include hal-
PSEUDO -BRECCIATED
c
ite silcretes in the Cambro-Ordovician
Whitehall Formation of eastern New
c
York State (Rubin and Friedman, 1981), c
c
COlUMNAR
and the Maestrichtian to Eocene aluni-
tic silcretes of western Portugal (Meyer
and Pena dos Reis, 1985). In the Plio-
cene Ogallala Formation of western
c:
Kansas weathering processes have led (
to the redistribution of biogenic (dia-
toms) and volcanogenic silica (benton-
GRANULAR c
ites) in the subsurface (Swineford and
Franks, 1959).
c
CLAYS c
Figure 11 Schematic vertical profile through Lower Eocene silcrete horizon, Paris Basin.
c
(From Thiry and Millot, 1987). (
~.

c
C
(
( Origin of Inorganic and Replacement Cherts 269
c
(
the solutions discharge on the sea graphic highs of exposed basement. In tions at depth must contain sufficient
( floor. The hot, silica-rich solutions rise exceptional cases, hydrothermal de- dissolved silicon to become supersatu-
through faults and poorly cemented vol- posits have been discovered in such rated with respect to opal-A during
( canic breccias and pillows. Upon cool- localities. For example in the Lau ascent when they cool below 100°C. In
( ing near the top of the sequence they Basin, a back-arc basin in the South- the reservoir, silicon concentration is
precipitate Si02 as long as no major west Pacific, hydrothermal opal and controlled by quartz solubility. A hydro-
( dilution by seawater takes place. barite occur on a sediment-free base- thermal solution precipitating opal-Aat
Silica Deposition by Submarine ment ridge 750 m above the basin floor 100°C must contain at least 370 ppm(or
( Exhalations. (Bertine and Keene, 1975). about 6 mM) dissolved silicon, which,in
The alteration zones typically mark the Ancient equivalents of type 2 quoted equilibrium with quartz, requires a res-
foot-wall alteration of ferruginous chert in Barrett (1979) include the siliceous ervoir temperature above 235°C (Fig-
( and other metal-rich deposits formed sinter, ironstone and Mn lenses in a ure 12). Foropal-A precipitation at50°C,
by exhalative volcanic activity on the Tertiary ophiolite suite in the British the reservoir temperature in the subsur-
sea floor (type 2 above). In the great Solomon Islands which occur above face must exceed 165°C to generate a
o majority of cases, the hydrothermal
solutions become diluted rapidly after
massive sulphide bodies and highly
altered silicified lavas (Taylor, 1974).
high enough silicon concentration from
quartz dissolution, excluding boiling as
o discharge by mixing with strongly silica-
undersaturated seawater.Therefore sil-
In Cyprus, Cretaceous ochres and
umbres with an average 20% Si0 2
in the 100°C situation. This quartz (or
silica) geothermometer (Fournier and
ica precipitation does not occur. Phan- (Robertson, 1976) overlie massive sul- Rowe, 1966) is widely applied in geo-
erozoic siliceous deposits in the pelagic phide orebodies and silicified, pyrite- thermal regions and its limitations were
sediments overlying the basaltic bearing stockworks of the Troodos discussed by Rimstidt and Barnes
oceanic crust are therefore almost ophiolite (Constantinou and Govett, (1980). Reservoirs with temperatures

o exclusively biogenic and not volcano-


genic in origin. Only where discharge
1972; Robertson and Hudson, 1973).
Carboniferous cherty ironstones at
lower than those calculated from the
quartz geothermometer are unlikely to
o rates are particularly high and/or dis- Tynagh, Ireland, have been interpreted produce siliceous sinter accumulations.

o charge takes place in topographic de-


pressions filled with stagnant brines, is
as exhalative deposits (Russell, 1975).
Other Paleozoic cherty iron-formations
The Beowawe geothermal system of
north-central Nevada has a tempera-
o silica precipitation likely to occur. This
is why so few examples of modern sub-
in the southern Urals are associated
with spilitic volcanics and silicified and
ture range of 200°-250°C near 3000 m
depth (Rimstidt and Cole, 1983). It
o marine hydrothermal silica deposits
have been reported from the recently
sericitized alteration zones pointing
toward a similar exhalative origin
occurs along the trace of a graben-
bounding fault and feeds boiling hot
discovered hydrothermal vents in the (Ivanov, 1971). Ordovician banded iron- springs with a temperature of 93°C
o median rift valley of the mid-ocean
ridge-system.
formations in the Bathurst mining dis-
trict, New Brunswick, fall into a similar
which is the boiling point of water at the
elevation of 1500 m.
o The first known example of this kind
was the Atlantis II Deep in the Red Sea
category although different geotec-
tonic setting (Troop, 1984). Finally,
The associated silica sinter deposit is
65 m thick and 1.6 km long. It is well
o (Bischoff, 1969). The nontronite (iron- many large massive sulphide deposits bedded and displays layering on the
o montmorillonite) and goethite-rich
hydrothermal sediment-layers in this
in the Archean greenstone belts of the
Canadian Shield are accompanied by
metre to millimetre scale (lamination).
Mineralogically it consists dominantly
o depression contain about 20 wt.% intense silicification and sericitization of opal-Awith traces of quartz. Opal-CT

o amorphous silica which was probably


chemically precipitated from solution.
which in all likelihood are of hydrother-
mal origin (Barrett, 1979).
is absent. Silica deposition occurs
through heterogeneous nucleation on
o The FAMOUS area on the Mid-Atlantic
Ridge is another site where silica- and
Silica Deposition in Geothermal
Areas on Land.
suspended solids. Homogeneous nu-
cleation is not possible in the area near
o
r:
iron-rich hydrothermal sediment was
precipitated in the immediate vicinity of
Siliceous sinter deposits in high-tem-
perature geothermal areas on land rep-
the vent where most of the precipitation
is observed because the level of super-
V the vent (Lalou et al., 1977). The silica resent the third type of volcanogenic saturation of the fluid is insufficient and
o apparently co-precipitated with iron-hy-
droxides and oxides and was followed
silica accumulations. They are low-tem-
perature surface or near-surface pro-
temperatures are too high. Agglom-
eration and attachment of suspended
C· by Mn-oxides. ducts of high-temperature processes in particles to the surface of the deposit is
As the oceanic crust migrates away the subsurface. Present-day systems aided by rapid precipitation of an opal-
6 from the ridge crest, hydrothermal are commonly associated with geyser ine silica cement once particles come
r· ,
'. circulation and discharge continue in activity. Recent or sub-recent deposits in contact with one another. High tur-
large cylindrical or ellipsoidal convec- that have been studied have undergone bulence of the water exiting the vent
tion cells of 5·10 km diameter, which only moderate to minor diagenesis. largely prevents deposition, and the
extend outward on the ridge flanks to 80 The sinter deposits may form ter- particles are swept off to be deposited
'- Ma old crust (Anderson et ei., 1979; races around hydrothermal vents and more distally.
Fehn, 1986). Whereas recharge occurs consist of Iight-coloured (white, tan or The Beowawe system provided im-
through wide sediment-covered areas, grey), commonly banded masses of fri- portant information on surface pro-
discharge appears to be focussed in able or dense, well-cemented amor- cesses of silica precipitation and de-
narrow zones along fault scarps ortopo- phous silica . The hydrothermal solu- position. In another study of a mod-
c
270 Diagenesis Geoscience Canada Reprint Series 4 c
(

ern system in the Upper Geyser Basin , crysts ; it is associated with celadonite, Churchill Provinces ofthe northwestern
c
Yellowstone National Park, Wyoming, montmorillonite and mordenite. The Canadian Shield (Ross and Chiaren- c
Keith et a/. (1978) documented the min-
eralogical and petrographic composi-
various silica phases show typical as-
sociations with particular zeolites:
zelli, 1985). However, the problem of
the origin of many of the Precambrian
c
tion of these deposits in the subsur- e-crlstobaflte with clinoptilolite; hydro- cherts, particularly the cherty iron for- c
face. It is based on two drill-holes up to
150 m deep . One is centred on the zone
thermal chalcedony or quartz with anal-
cime. Hydrothermal quartz forms con-
mations, remains unresolved. This
applies to the fine-grained banded iron c
of rising hot fluids and is very close to
hot spr ings, the other one is a little over
spicuous overgrowths on clastic quartz.
Cementation resulting from these al-
formations ofthe "Algoma type" as well
as to the coarser-grained " Superior-
c
a 100 m away. The hot spring water has teration processes, which also include type" deposits. c
a temperature of 93°C at the surface
and rises from a reservoir which is pro-
reactions other than those involving sil-
ica minerals, appears to have a self-
Models proposed for the dominantly
Proterozoic Banded Iron Formations c
bably at a temperature above 200°C.
Ground temperatures above 80°C are
sealing effect on the system . This is
shown by significant differences in fluid
(BIFs) range from organic (LaBerge,
1973) to inorganic (Cloud, 1973), and
c
encountered at depths of between 6 pressures at the base of the 50 m thick from continental-lacustrine (Magadi- c
and 15m. Silicification of the sediments
is by silica cementation, especially of
sedimentary section in the two drill
holes.
type, Eugster, 1969;Eugster and Chou,
1973), or continent-derived/fluviatile c
sinter. Devitrification of volcanic glass
contributes only minor amounts of silica
(Garrels, 1987) to restricted or open c
minerals. Hydrothermal activity in this
PRECAMBRIAN CHERTS
Cherts constitute a greater proportion
marine (Drever, 1974; Holland, 1973).
The latter models, which involve either c
area has probably continued for the last
12,000 years or more .
of the sedimentary record in the Pre-
cambrian than in the Phanerozoic be-
(i) stratified basins (or oceans), (ii) pre-
cipitation at the pycnocline or, (iii)
c
Sinter forms at the surface as layers
of amorphous opaline silica. These are
cause of the abundance of chert in Pre- oceanic upwelling, are particularly c
deposited from exiting hot spring water
cambrian (banded) iron formations (Pet-
tijohn, 1975, p. 594). Excellent Precam-
attractive as they invoke a reservoir of
reasonable magnitude for iron and sil- c
which has a maximum silicon content of
330 ppm and becomes rapidly super-
brian analogues of modern environ-
ments of chert formation have been
ica. As far as silica is concerned, the
stratified-basin requirement is not nec-
c
saturated upon cooling. Most deposits documented in literature, such as the essary, because the silica concen- c
consist of angular fragments of primary
sinter cemented by amorphous silica.
Proterozoic silcretes in the Bear and tration of Precambrian seawater may
c
At a depth of less than 8 m, o-crlsto-
balite (disordered opal-CT) appears at
c
the expense of opal-A. The overlap in c
the depth range of these two phases is
narrow. Chalcedony and occasionally c
quartz occur in veinlets at greater
depth. The silica minerals observed in [1000 c
the drill holes are interpreted as a pri-
Q,
c
mary sequence of precipitates which
reflect decreasing supersaturation of
>
--.t-... c
the solutions with increasing tempera-
ture, ratherthan an alteration sequence m c
which is plausible as little burial has :3
oU)
500 c
occurred.
Alteration of volcanic glass starts c
with hydration (perlitization), which in-
creases the water content by 2-5%.
c
(Non-perlitic obsidian has 0.3% H2 0 ). c
Unaltered rhyolitic obsidian still persists
in the center of a flow breccia at a tem- 100 200 300 c
perature of 170°C. This is apparently TEMPERA TURE, °c e
the result of reduced water accessibility
due to low permeability. Further altera-
tion leads to devitrification through zeo-
c
Figure 12 " Quartz-geothermometer " for hydrothermal systems using solubility of amor-
lite and smectite formation or complete
phous silica (opal-A) and quartz as a function oftemperature. (From RimstidtandCole, 1983). A
dissolution. Euhedral tridymite seems hydrothermalsolution precipitating opa/-A at 100°C contains 372ppm dissolvedsilicon which ,
(
to be a high-temperature devitrification in equilibrium with quartz, requires a reservoir temperature of 2380C.
product associated with lava extrusion; C
o-crtstoballte occurs mainly as an (
alteration product of obsidian filling the
holes of "sieved plagioclase" pheno- (
C
C
c
264 Diagenesis Geoscience Canada Reprint Series 4 c
c
chalk, the concentration of iron-bearing
c
minerals(mainly clay minerals)is notori- c
ously low. After the termination of sul-
phide precipitation, the build-up of HS- c
and S210wered the pH to the extent that
the system switched to carbonate dis- 1---+-+-+-+-+-+-+-+-+--::7'f--+--.."'.'--+-+-+--t---j
, / -', ... 1 c
solution and accompanying silica pre- Feb
r
Ca./_-t-r-t--t- t_\ . _ t--1I---+_ -i c
cipitation. Sulphate reduction extended
a certain distance from the burrow into
Mg 0.-8~-..B .... cC'"-S)",B'~
i ~~
1\
' ~I 1000
1 \ .FF
9 Mg c
the chalk because of increased organic
matter content and enhanced per-
1000
I-A '
0
.~-~:.: =p'=:
c
meability in the burrow. The latter facili- f- I~. ..
·~ri""ri~~:.J
;e"'~I--C
11
\
\
r :' i -
.1-.:'. !i~
c
tated the resupply of sulphate. The bur-
row and its immediate surroundings
I
1---+-+-+-+-+-+-+-+1
I 1.1\ I I
.
1:':; I
c
therefore became an anoxic environ- f-M,P-ng,:::g:"'O_6_6_0-0,,:".6,~, ~".....,Q:-:. ~~"'frn·;.::~~
·~."1-1--
:~"~.~n- c
I V-V"V"·v-·O:..... \" -N",+-:+ -+'
ment, whereas the host-sediment out- I , --+ I I I I I
side the paramoudra structure was K +' i'i'O,¥TI
-·+--+_+--+e.
, } ' N' -ee,' '.
W/
'0/:
0 .,
c
generally still oxic. Sulphide diffusing
outward from the sulphate-reduction
100 Ji
~~~~~~~33~\-':~
-: ti:
\0.=70:::.0:=
.,- I~
100 I--
c
zone of the paramoudra structure 1--+-+-+-+-+-1--1--+ I-~
1---+-+-+-+-+-+-+-+ 1-0-00"'
~o().-o :-I--+-~
'~+-1:- I - + - - - i c
toward the oxic surrounding therefore
would be re-oxidized bacterially lower-
,
0--0 c
ing the pH even more.
The transition from anoxic to oxic
c
conditions thus appears to coincide
I~ c
with the cemented chalk/flint boundary.
This is supported by the Fe and Mn dis- c
tributions. Fe is enriched in the cemen-
ted chalk over the slightly-cemented
c
carbonate host sediment because of o 0
c
Fe-sulphide precipitation in the chalk
core. It is strongly depleted at the chalk/
\,
c
flint boundary because of the termina-
tion of sulphide precipitation at that 1\ c
point. It shows a second maximum at
I
c
some distance from this boundary
(sample 3, Figure 9) revealing immobil- S'3C
ABC o EF GH 1 2 3 4 5 678 9 CA/4
S"O c
ization by oxidation of some reduced 1.80
I

/1 /t\ - ".60 c
iron that escaped sulphide precipita- -
tion. Mn 2 + , which is slightly more
I .
- c
mobile in a weakly oxidizing environ-
ment than Fe2+ • has a secondary max-
SI3C 1_1--1- 1 . c
1.60 %0 -1.0
imum at a slightly greater distance from ];/
~_I"
c
the boundary (sample 4) where it under-
went oxidation as well. S"O'l-I/
I - I - I..... ',+
-
- c.
The source of silica for the para- 1.40 %0 , .... - C
moudra structure in the chalk does not -1.50
pose a problem. Siliceous tests and
1.30
'+
-1.60 l
skeletons (sponge spicules, radiolaria, I I I I

diatoms) are abundant in the chalk. Dis- C

l!n::~::~Y~: "1mB
solution of the opaline silica increased
silicon concentration during early dia-
e
genesis beyond the solubility of opal- <..
CT, which, according to Clayton (1986),
was the first diagenetic silica phase to
-CEMENTED CHALK CORE I fliNT I UNCEMENTED- <..
HOST
precipitate. Today, the flint nodules con-
sist entirely of quartz and chalcedony.
C
The paramoudra structure has been C
used by Clayton (1986) as basis for a
general model for the formation of bed-
Figure 9 Trace element and carbon- and oxygen·isotope distribution across paramoudra
flint structure from central burrow (left) to sample Ca/4 in the host sediment. (Modified from
C
ded flint in chalk. According to the Clayton, 1986). (
C
C
( Origin of Inorganic and Replacement Cherts 271

c'
have been considerably higher (20 to evidence that the well-established se- the beginning of the century has only
e- 100 ppm according to Holland and
Malinin, 1979) than that of present-
quence of silica transformations in pe-
lagic siliceous sediments from opal-A to
been described from lacustrine, pedo-
genic and hydrothermal-volcanogenic
el day ocean water. Such concentrations opal-CT to microquartz may not be environments. Hydrothermal silicifica-
r: are plausible if there were no efficient adhered to in many nodular cherts in tion processes in and near modern
silica-consuming organisms to counter- limestones. vent systems on mid-ocean ridges have
c balance the silica input by rivers , sub-
marine volcanism, and the pore-water
The geochemical environment and
conditions of carbonate replacement by
been studied little so far because of
inaccessibility, but they offer a pros-
[J reflux in Precambrian oceans. This silica remain poorly known in detail. pective area of study for future ocean
c would also explain the occurrence of
Precambrian cherts in shallow to deep
Therefore, the differences between sil-
ica diagenesis in limestones on the one
drilling.
Much work, including experimental
marine environments, for which no evi- hand and diatomites and radiolarites on study, remains in order to elucidate the
dence of an evaporite association the other are incompletely understood. chemical conditions of chertification in
o exists. An alternative origin for these They are explained only in terms of carbonates. Answering the remaining

r cherts would be silicification by hydro-


thermal-volcanogenic replacement
Knauth 's (1979) general mixing model
for shallow-water carbonates which
unsolved questions on the origin of Pre-
cambrian cherty iron-formations will
o (e.g., Hughes, 1976; Simonson, 1985). awaits testing in a suitable ancient or potentially also shed light on the com-

o Simonson (1987) has presented evi-


dence for pervasive early diagenetic
modern example. An exception is Clay-
ton's (1986) study of flint formation in
position of seawater in Precambrian
times.
o chertification in these rocks, including
the silicification of carbonate ooids.
the English Chalk. The chalk is a shelf
equivalent to deep-sea pelagic lime- ACKNOWLEDGEMENTS
0, Walker (1984) suggested that early dia- stones, which commonly also contain Funding for the author's diagenesis

o genesis in the BIFs occurred under


suboxic conditions.
chert nodules probably formed under
similar conditions as the flint nodules.
research was provided by the Natural
Sciences and Engineering Research
The question of why nodules or concre- Council of Canada (Grant A7368). A
CONCLUSIONS tions grow exactlywhere they do and not slightly modified version of this paper
o Review of the literature on inorganic elsewhere is an unresolved dilemma was first published in Earth Science

o and replacement cherts shows that dia-


genetic pathways, phase transforma-
concerning nodular or concretionary
rocks. Clayton 's (1986) model attempts
Reviews(v. 26, p. 253-284). Permission
to reprint the article was granted by
o tions, reaction rates , timing and burial
depths at which silicification reactions
some answers to this question for the
flint nodule bands implying basin-wide
Elsevier. S. Calvert, E. McBride and T.
Barrett read earlier drafts of the manu-
o occur in these rocks may be quite dif- sedimentation pulses that might be script and suggested substantial im-

o ferent from those in biogenic siliceous


sediments in the open oceans dis-
related to sea-level changes or other
exogenic forces. In other cases, nodule
provements. Reviewers for Earth Sci-
ence Reviews were D. Houseknecht,
c cussed in the previous paper (Hesse, distribution is probably strictly stochas- G. de V. Klein and Anonymous, whose

o this volume, p. 227-251). In certain


cases, however, e.g., in silicified wood,
tic. The point of initial nucleation may
represent only a slight perturbation of
comments have been largely incorpo-
rated into the manuscript. The originals
on diagenetic phenomena may be similar
or identical to those in pelagic siliceous
the geochemical environment. Average
nodule spacing may be controlled by
for Figures 3c and 3d were provided by
B. Simonson. R. Yates helped with the
v sediments. diffusional distances. drafting and photography. Fortheirsup-

o The formation of nodular cherts in


limestones is instructive concerning
The variety of rock types and mater-
ials undergoing silica-replacement is
port and assistance the author wishes to
express his gratitude to these col-
o the timing of silicification reactions rel-
ative to well-established carbonate-dia-
impressive and the extent ranges from
minor to pervasive. Fossil wood, Phan-
leagues who gave freely of their time ,
particularly T. Barrett.
r. genetic reactions. Virtually all theoret- erozoic carbonates and carbonate-
REFERENCES
o ically possible sequences occur in
nature including very early chert forma-
bearing sandstones and evaporites
commonly undergo partial or minor sil-
o tion at very shallow burial depths. The
latter situation is very different from
icification. However, examples of com-
pletely silicified beds , members or for-
Silicification of Fossil Wood
Buurman, P., 1972, Mineralization of fossil
deep-sea siliceous sediments, in which mations are known . In Phanerozoic wood: Scripta Geologica , v. 12, p. 1-43.
the silica phase transformations take examples, the source ofthe silica forthe Drum, R.W., 1968, Silicification of Betula
millions or tens of millions of years and replacement is predominantly biogenic. wood tissue in vitro: Science, v. 161,
considerable burial depths to start. Lacustrine , pedogenic and hydro- p.175·176.
Field evidence has also been presented thermal-volcanogenic cherts are pre- Hesse, R., 1990b, Origin of chert: Diagene-
sis of biogenic siliceous sediments, in
for early chert formation in ancient dominantly inorganic in origin and have
Mcllreath, I.A. and Morrow, DW., eds.,
argillaceous continental margin sedi- the tendency for pervasive replacement
Diagenesis : Geological Association of
ments. This evidence remains contro- which, in volcanic edifices in particular, Canada, Geoscience Canada Reprint
versial, however, because it is difficultto may affect entire formations. Direct Series 4, p. 227-251,
'-
reconcile it with experimental results chemical silica precipitation from Leo, R.F. and Barghoorn , E.S., 1976,Silici-
suggesting slow reaction rates in argil- aqueous solution which was thought to fication of wood: Harvard University,
laceous sediments. There is conclusive be the main chert-forming process at Botanical Museum Leaflets , v. 25,47 p.
(
272 Diagenesis Geoscience Canada Reprint Series 4 C
(
(
Merrill, A.C. and Spencer, R.w., 1950,Sorp- Coniglio , M., 1987, Biogenic chert in the Hinman, N.W., 1987, Organic and inorganic
tion of sodium silicates and silica sols by Cow Head Group (Cambro-Ordovician), chemical controls on the rates of silica C
cellulose fibers: Industrial and Engi- western Newfoundland: Sedimentol- diagenesis: A comparison of a natural
neering Chemistry, v. 42, p. 744-747. ogy, v. 34, p. 813-823. system with experimental results, un- (
Murata, K.J., 1940, Volcanic ash as a source Cox, G.H., Dean, R.S. and Gottschalk, V.H., published Ph.D. thesis, University of
of silica for the silicification of wood: 1916, Studies on the origin of Missouri California at San Diego, 381 p.
(
American Journal of Science, v. 238, chert and zinc ores: Missouri University Jacka,A.D., 1974, Replacementoffossilsby (
p.586-596 . School of Mines and Metallurgy, Bul- length-slow chaldecony and associated
Sigleo, A.C., 1978,Organic geochemistry of letin, Technical Series, v. 3, no. 2, 34 p. dolomitization: Journal of Sedimentary (
silicified wood, Petrified Forest National Dapples, E.C.,1959, The behaviour of silica Petrology, v. 44, p. 421-427.
Park, Arizona: Geochimica et Cosmo- in diagenesis, in Ireland, H.A., ed., Silica Kastner, M., 1980,Length-slow chalcedony: (
chimica Acta, v. 42, p. 1397-1405. in Sediments: Society of Economic Pa- the end olthe newtestament: EOS,v. 61,
Stein, C.L., 1982, Silica recrystallization in leontologists and Mineralogists, Special p.399. (
petrified wood: Journal of Sedimentary Publication No. 7, p. 36-54. Keene, J.B., 1983,Chalcedonic quartz and
Petrology, v. 52, p. 1277-1282. Folk, R.L., 1975, Third-party reply to Hat- occurrence of quartzine (length-slow (
field : Discussion of Jacka A.D., 1974, chalcedony) in pelagic sediments: Sedi-
Chertificatlon of Carbonates and Fossils by length-slow chalcedony and mentology, v. 30, p. 449-454.
(
Carbonate-bearing Sandstones associated dolomitization: Journal of Knauth, L.P., 1979, A model for the origin (
Sedimentary Petrology, v. 45, p. 952. of chert in limestone: Geology, v. 7,
Badiozamani, K., 1973, The Dorag dolo-
mitization model - Application to the
Folk, R.L. and Pittman , J.S., 1971, Length-
slow chalcedony : a new testament for
p.274-277.
Knauth, L.P. and Epstein, S., 1976, Hydro-
C
Middle Ordovician of Wisconsin: Jour- vanished evaporites : Journal of Sedi- gen and oxygen isotope ratios in nodular (
nal of Sedimentary Petrology, v. 43 , mentary Petrology, v. 41, p. 1045-1058. and bedded cherts : Geoch imica et Cos-
p.965-984. Frondel, C., 1962, Dana's System of Miner- mochimica Acta, v. 40, p. 1095-1108. (
Banks, N.G., 1970, Nature and origin or alogy, v. 3: The Silica Minerals: Wiley, Land, L.S., 1979, Chert-chalk diagenesis:
early and late cherts in the Leadville New York, 334 p. The Miocene island slope of north C
Limestone , Colorado: Geological
Society of America, Bulletin, v.81,
Frondel, C., 1978, Characters of quartz
fibers: American Mineralogist, v. 63,
Jamaica:Journal of Sedimentary Petrol-
ogy, v. 49, p. 223-232.
C
p. 3033-3048 .
Bromley, A.G. and Ekdale, A.A., 1986, Flint
p. 17-27.
Geeslin , J.H. and Chafetz, H.S., 1982,
Lohmann , K.G. and Meyers, W.J., 1977,
Microdolomite inclusions in cloudy pris-
C
and fabric in the European chalk, in Ordovician Aleman ribbon cherts: An matic calcites : A proposed criterion for C
Sieveking, G. de G. and Hart , M.B ., eds., example of silicification prior to carbon- former high magnesium calcites: Jour-
The Scientific Study of Flint and Chert: ate lithification: Journal of Sedimentary nal of Sedimentary Petrology, v. 47, C
Cambridge University Press, p. 71-82. Petrology, v. 52, p. 1283-1293. p. 1078-1088.
Brown, G., Catt, J.A., Hollyer, S.E. and Hatfield, C.B., 1975,Aeplacementoffossils Lovering, T.G. and Patten, L.E., 1962,The C
Oilier, C.D., 1969, Partial silicification of
chalk fossils fromtheChiiterns: Geologi-
by length-slow chalcedony and associ-
ated dolomitization: Discussion: Jour-
effect of CO2 at low temperature and
pressure on solutions supersaturated
C
cal Magazine, v. 106, p. 583-586.
Chanda, S.K ., Bhattacharyya , A. and
nal of Sedimentary Petrology, v. 45,
p.951-952.
with silica in the presence of limestone
and dolomite: Geochimica et Cosmo-
C
Sarkar, S., 1976, Early diagenetic chert
nodules in Bhander Limestone, Maihar,
Henderson, R.A., 1984, Diagenetic growth
of euhedral megaquartz in the skeleton
chimica Acta, v. 26, p. 253-284.
McBride, E.F.,1988,Silicification of carbon-
C
Satna District, Madhya Pradesh, India: of a stromatoporoid: Journal of Sedi- ate pebbles in a fluvial conglomerate by C
Journal of Geology, v. 84, p. 213-224. mentary Petrology, v. 54 , p. 1138-1146. groundwater: Journal of Sedimentary
Chanda, S.K. , Bhattacharyya , A. and Hesse, R., 1973,Diagenesis of a seamount Petrology, v. 58, p. 862-867. C
Sarkar, S., 1977, Deformation of ooids oolite from the West Pacific, Leg 20, McBride, E.F. and Folk, A.L., 1977, The (
by compaction in the Precambrian DSDP, in Heezen, B.C., MacGregor, LD. Caballos Novaculite revisited: Part II:
Bhander Limestone , India: Implications
for lithification: Geological Society of
et a/.: Initial Aeports of the Deep Sea
Dr illing Project , v. 20 , p .363-387 :
Chert and shale members and syn-
thesis: Journal of Sedimentary Petrol-
C
America, Bulletin, v. 88, p. 1577-1585. United States Government Printing Off- ogy, v. 47, p. 1261-1286. (
Choquette, P.W., 1955, A petrographic ice, Washington, D.C. Meyers, W.J., 1977, Chertification in the
study of the "State College" siliceous Hesse, R., 1987, Selective and reversible Mississippian Lake Valley Formation , C
oolite: Journal of Geology, v. 63 , p. carbonate-silica replacements in Lower Sacramento Mountains, New Mexico:
337-347. Cretaceous carbonate-bearing tur- Sedimentology, v. 24, p. 75-105. C
Chowns, T.M. and Elkins, J.E., 1974, The bidites of the Eastern Alps: Sedimentol- Meyers, W.J. and James, A.T., 1978, Stable
origin of quartz geodes and caulifower ogy, v. 34, p. 1055·1077. isotopes of cherts and carbonate ce- C
cherts through the silicification of an- Hesse, A., 1990a, Early diagenetic pore ments in the Lake Valley Formation (Mis- (
hydrite nodules: Journal of Sedimentary water/sediment interactions: Modern sissippian), Sacramento Mts., New Mex-
Petrology, v. 44, p. 885-903.
Church, A.H., 1862, Observations on silica:
offshore basins, in Mcllreath, LA. and
Morrow, D.W., eds., Diagenesis: Geo-
ico: Sedimentology, v. 25, p. 105-124.
Michel-Levy, A.andMunier-Chalmas,C.P.E.,
C
Journal of the Chemical Society, v. 15, logical Association of Canada, Geo- 1892 , Memo ire sur diverse formes C
p.l07-110. science Canada Reprint Series 4, p. attectees par Ie reseau elementaire du
Clayton, C.J., 1986, The chemical environ- 277-316. Quartz: Bulletin de la Societe Francalse C
ment of flint formation in Upper Creta- Hesse, A., 1990b,Origin of chert: Diagene- de Mineralogie, v. 15, p. 159-190.
ceouschalks, in Sieveking, G. de G. and sis of biogenic siliceous sediments, in C
Hart, M.B., eds., The Scientific Study of
Flint and Chert: Cambridge University
Mcllreath, LA. and Morrow, D.W., eds.,
Diagenesis: Geological Association of
C
Press, p. 43-54. Canada, Geoscience Canada Reprint
Series 4, p. 227-251.
C
C
C
r
r
Origin of Inorganic and Replacement Cherts 273
r

r
Milliken , K.L., 1979, The silicified evaporite Milliken , K.L., 1979, The silicified evaporite Surdam, R.C., Eugster, H.P. and Mariner,
syndrome - two aspects of silicification syndrome - two aspects of silicification R.H ., 1972, Magadi-type chert in Juras-
history offormer evaporite nodules from history of former evaporite nodules from sic and Eocene to Pleistocene rocks,
southern Kentucky and northern Ten- southern Kentucky and northern Ten- Wyoming: Geological Society of Amer-
r nessee: Journal of Sedimentary Petrol - nessee: Journal of Sedimentary Petrol- ica, Bulletin , v. 83, p. 2261-2266.
ogy, v. 79, p, 245-256. ogy, v. 79. p. 245-256. White , A.H. and Youngs, B.C., 1980. Cam-
Namy, J.N., 1974, Early diagenetic chert in Siedlecka, A., 1972, Length-slow chalcedony br ian alkali playa-lacustrine sequence
the Marble Falls Group (Pennsylvanian) and relicts of sulphates - evidences of in the northeastern Officer bas in ,
of central Texas: Journal of Sedimentary evaporitic environments in the Upper Car- South Australia: Journal of Sediment-
Petrology, v. 44, p. 1262-1268. boniferous and Permian beds of Bear ary Petrology, v. 50, p. 1279-1286.
Richter, D.E., 1972, Authigenic quartz pre- Island, Svalbard: Journal of Sedimentary
serving skeletal material: Sedimentol- Petrology, v. 42, p. 812-816. Inorganically Precipitated Lagoonal and
o ogy, v. 19, p. 211-218.
Schmitt, J.C. and Boyd,D.W., 1981, Patternsof
Siedlecka, A., 1976, Silicified Precambrian
evaporite nodules from northern Nor-
Lacustrine Cherts

o silicification in Permian pelecypods and way: a preliminary report: Sedimentary Peterson, M.N.A. and Von der Borch, C.C.,

o brachipods from Wyoming: Journal of


Sedimentary Petrology, v. 51, p. 1297-1308.
Geology, v. 16, p. 161-175. 1965, Chert: modern inorganic deposi-
tion in a carbonate precipitating locality:

o Simonson , B.M. , 1987, Early silica cementa-


tion and subsequent diagenesis in
Magadi-type Cherts Science , v. 149, p. 1501-1503.
Renaut, R.W. and Owen, A.B., 1988, Opal-
o arenites from four Early Proterozoic
Iron Formations of North America: Jour-
Eugster, H.P.,1967, Hydrous sodium silicates
from Lake Magadi, Kenya: Precursors of
ine cherts associated with sublacus-
trine hydrothermal springs at Lake Bo-
o nal of Sed imentary Petrology, v. 57,
p.494·511,
bedded chert: Science, v. 157, p. 11n
Eugster. H.P.,1969,Inorganic bedded cherts
gor ia, Kenya Rift valley: Geology, v. 16,
p.699-702.
o Swett, K., 1965, Dolomitization, silicifica- from the Magadi area, Kenya: Contribu- Renaut, R.W., Tiercelin, J.J. and Owen,

o tion, and calcitization patterns in


Cambro-Ordovician oolites from North-
west Scotland : Journal of Sedimentary
tions to Mineralogy and Petrology, v. 22,
p. 1-31,
Eugster,H.P.andSurdam, A.C., 1973, Deposi-
R.B .• 1986, Mineral prec ipitation and
diagenesis in the sediments of the Lake
Bogoria basin , Kenya Rift Valley, in
Petrology, v. 35, p. 928-938. tional environment of the GreenRiver For- Frostick, L.E., Renaut, R.W., Reid,l. and

o Wilson, R.C.L., 1966, Silica diagenesis in


Upper Jurassic limestones of southern
mation: Geological Society of America,
Bulletin. v. 84. p. 1115-1120.
Tiercelin, J.J., eds. , Sedimentation in
the African Rifts: Geological Society
o England: Journal of Sedimentary Petrol-
ogy, v. 36, p. 1036-1049.
Gude, A.J. and Sheppard, R.A., 1972, Sil-
hydrite, 3Si0 2 • H20, a new mineral from
of London , Special Publication 25 ,
p.159-175.
o Wood, G.V. and Armstrong, A.K., 1975, Dia- Trinity County, California: American Wheeler, W.H. and Textoris, D.A., 1978,Tri-

o genesis and stratigraphy of the Lisburne


Group limestones of the Sadlerochit
Mineralogist, v. 57, p. 1053-1065.
Hay, R.L., 1968, Chert and its sodium sili-
assic limestone and chert of playa origin
in North Carolina: Journal of Sedimen-

o Mountains and adjacent areas , north-


eastern Alaska : United States Geologi-
cate precursors in sod ium-carbonate
lakes of East Africa: Contributions to
tary Petrology, v. 48, p. 765-776.

o cal Survey, Professional Paper 857,41 p. Mineralogy and Petrology, v.17,


p.255-274.
Pedogenic Cherts: Silcretes

o Chert Replaced Elfaporites Jones, B.F., Rettig, S.L. and Eugster, H.P.,
1967, Silica in alkaline brines: Science,
Bruckner, W.D., 1966, Origin of silcretes
of central Australia: Nature, v. 209,
o Boulter, C.A. and Glover, J.E., 1986, Chert
with relict hopper moulds from Rocklea
v. 158, p. 1310-1314.
Maglione, G.• 1980. An example of Recent
p.496-497.
Exon , N.F.• Langford-Smith, T. and
Dome , Pilbara Craton, Western Aus- continental evaporitic sedimentation; The McDougall , I., 1970, The age of geo-
tralia: An Archean halite-bearing evapo- Chadian Basin, in Busson, G., ed., Evapo- morphic correlations of deep weather-
rite : Geology, v. 14, p. 128-131. rite Deposits: Illustration and Interpreta- ing profiles, silcrete and salt in the
Chowns, T.M. and Elkins , J.E., 1974, The tion of Some Environmental Sequences: Roma-Amby region, Queensland: Jour-
origin of quartz geodes and cauliflower Edition Technip, Paris, p. 5-9. nal of the Geological Society of Aus-
cherts through the silicification of Parnell, J., 1986, Devonian Magad i-type tralia, v. 17, p. 21-30.
anhydrite nodules: Journal of Sedimen- cherts in the Orcadian Basin, Scotland: Frankel, J.J., 1952,Silcrete near Albertinia,
tary Petrology, v. 44, p. 885-903. Journal of Sedimentary Petrology, v. 56, Cape Province: South African Journal of
Folk, R.L. and Pittman , J .S., 1971, Length- p.495-500. Science. v. 48. p. 173-182.
slow chalcedony: a new testament for Peterson, M.N.A. and Von der Borch, C.C ., Frankel, J.J. and Kent, L.E., 1937, Grahams-
vanished evaporites: Journal of Sedi- 1965, Chert: modern inorganic deposi- town surface quartzites (silcretes): Geo-
mentary Petrology, v. 41, p. 1045-1058. tion in a carbonate precipitating locality: logical Society of South Africa, Trans-
Friedman , G.M. and Shukla , V., 1980, Sig- Science, v. 149, p. 1501-1503. actions, v. 40, p. 1-42.
nificance of authigenic quartz euhedra Rooney, T.P.. Jones, B.F.and Neal,J:r., 1969, Khalaf, F.I., 1988, Petrography and diagen-
-. after sulfates: Example from the Lock- Magadiite from Alkali Lake,Oregon:Amer- esis of silcrete from Kuwait , Arabian
port Formation (middle Silurian) of New ican Mineralogist, v. 54, p. 1034-1043. Gulf: Journal of Sedimentary Petrology,
York: Journal of Sedimentary Petrology, Sheppard, R.A. and Gude, A.J., 1986, Ma- v. 58, p. 1014-1022.
v. 50, p. 1299-1304. gadi-type chert - A distinctive diage- Hutton, J.T., Twidale, C.R., Milnes, A.A. and
Geeslin. J .H. and Chafetz. H.S ., 1982, netic variety from lacustrine deposits. in Rosser, H., 1972,Composition and gen-
Ordovician Aleman ribbon cherts: An Mumpton, FA, ed., Stud ies in Diagene- esis of silcretes and silcrete skins from
example of silicification prior to carbon- sis: United States Geological Survey, the Beda Valley. Southern Arcoona Pla-
ate lithification: Journal of Sedimentary Bulletin , Report B1578, p. 335-345 . teau, South Australia: Journal of the
Petrology, v. 52, p. 1283-1293. Geological Society of Australia, v. 19,
p.31-39.
c
274 Diagenesis Geoscience Canada Reprint Series 4 c
(

Langford-Smith, T., 1978, ed., Silcrete in Bishoff , J.L., 1969, Red Sea geothermal Rimstidt, J.D. and Cole, D.R., 1983, Geo-
c
Australia: Armidale, University of New brine deposits: their mineralogy, chem- thermal mineralization, I: The mecha- c
England, p. 304.
Langford-Smith, T. and Drury, G.H., 1965,
istry, and genesis , in Degens, E.T. and
Ross, D.A., eds., Hot Brines and Recent
nism of formation of the Beowawe, Ne-
vada, siliceous sinter deposit: American c
Distribution, character and attitude of
the duricrust in the northwest of New
Heavy Metal Deposits in the Red Sea:
Springer, New York, p. 368-40t
Journal of Science, v. 283, p. 861-875.
Robertson, A.H.F., 1976, Origins of ochres c
South Wales and the adjacent areas of
Queensland: American Journal of Sci-
Constantinou, G. and Govett, G.J.S., 1972,
Genesis of sulphide deposits, ochre and
and umbres: evidencefrom Skouriotissa,
Troodos Massif, Cyprus: Institute of c
ence , v. 263, p. 170-190.
Meyer, R. and Pena dos Reis, R.B., 1985,
umbre of Cyprus: Institute of Mining and
Metallurgy, Transactions, v. 81, p. B34-
MiningandMetallurgy, Transactions,v. 85,
p. B245-B25t
c
Paleosols and alunite silcretes in conti-
nental Cenozoic of western Portugal :
B46.
Davis, E.F., 1918, The radiolarian cherts of
Robertson, A.H.F. and Hudson, J.D., 1973,
Cyprus umbres: chemical precipitates
c
Journal of Sedimentary Petrology, v. 55, the Franciscan Group: University of Cal- onaTethyan oceanridge:EarthandPlane- c
p.76-85.
Mountain , E.D., 1952, The origin of silcrete:
iforn ia, Publication Bulletin , Depart-
ment of Geology, v. 11, p. 235-432.
tary Science Letters, v. 18,p. 93-10t
Russell, M.J., 1975, Lithogeochemical en- c
South African Journal of Science, v. 48,
p.201-204 .
Fehn, U., 1986, The evolution of low-tem-
perature convection cells near spread-
vironment of the Tynagh base-metal
deposit, Ireland, and its bearing on c
RUbin, D.M. and Friedman, G.M., 1981, Ori-
gin of chert grains and a halite-silcrete
ing centers: A mechanism for the forma-
tion of the Galapagos mounds and
ore deposition: Institute of Mining and
Metallurgy, Transactions,v. 84, p. B128- c
bed in the Cambrian and Ordov ician
Whitehall Formation of Eastern New
similar manganese deposits: Economic
Geology, v. 81, p. 1396-1407.
B133.
Taylor, G.R., 1974, Volcanogenic minerali-
c
York State: Journal of Sedimentary Pe- Fournier, R.O. and Rowe, J.J., 1966, Es- zation in the islands of the Florida c
trology, v. 5, p. 69-72.
Smale, D., 1973, Silcretes and associated
timation of underground temperature
from the silica content of water from hot
Group, B.S.I.P.: Institute of Mining and
Metallurgy, Transactions, v. 83, p. B120- c
silica diagenesis in southern Africa and
Australia: Journal of Sedimentary Pe-
springs and wet-stream wells : American
Journal of Science , v. 264, p. 685-697.
B130.
Troop, D.G., 1984, The petrology and geo- c
trology, v. 43, p. 1077-1089.
Summerfield, M.A., 1983, Petrography and
Hesse, R., 1~90b, Origin of chert: Diagene-
sis of biogenic siliceous sediments, in
chemistry of Ordovician banded iron
format ions and associated rocks at the c
diagenesis of silcrete from the Kalahari
Basin and Cape coastal zone, Southern
Mcllreath, LA. and Morrow, D.W., eds.,
Diagenesis: Geological Association of
Flat Landing Brook massive sulfide de-
posit, northern New Brunswick, M.Sc.
c
Africa : Journal of Sedimentary Petrol- Canada, Geoscience Canada Reprint thesis, University of Toronto, 178 p. c
ogy, v. 53, p. 895-909.
Swineford, A. and Franks, P.C., 1959, Opal
Series 4, p. 227-251.
Hutchinson, R.W., 1982, Syn-depositional Precambrian Cherts c
in the Ogallala Formation in Kansas, in
Ireland, H.A., ed., Silica in Sediments:
hydrothermal processes and Precam-
brian sulphide deposits, in Hutchinson, Cloud, p., 1973, Paleoecological signifi- c
Society of Economic Paleontologists
and Mineralogists, Special Publication
R.W., Spence, C.D. and Franklin, J.M.,
eds., Precambrian Sulphide Deposits:
cance of banded iron-formation: Eco-
nomic Geology, v. 68, p. 1135-1143. c
No. 7, p. 111-120.
Thiry, M. and Millot , G., 1987, Mineralogical
Geological Associat ion of Canada, Spe-
cial Paper 25, p. 761-791.
Drever, J.T., 1974, Geochemical model for
the origin of Precambrian banded iron
c
forms of silica and their sequence of Ivanov,S.N., 1971, Deposits of pyrite ores of formations: Geological Society of Amer- c
formation in silcretes: Journal of Sedi-
mentary Petrology, v. 57, p. 343-352.
Watts , S.H. , 1978, A petrographic study
eugeosynclinal regions, in Proceedings
ofthe IMA-JAGOD meetings '70, IAGOD
volume: Society of Mining Geologists of
ica, Bulletin, v. 85, p. 1099-1106.
Eugster, H.P., 1969, Inorganic bedded
cherts from the Magadi area, Kenya:
c
of silcrete from inland Australia: Jour- Japan,Tokyo,p.193497. Contributions to Mineralogy and Petrol- C
nal of Sedimentary Petrology, v. 48, Keith, T.E.C., White, D.E. and Beeson, ogy, v. 22, p. 1-31.
p.987-994. M.H., 1978,Hydrothermal alteration and Eugster, H.P. and Chou, I-M., 1973, The E
Woolnough, W.G., 1927, Presidential ad-
dress: Journal and Proceedings of the
self-sealing in Y-7 and Y-8 drill holes in
northern part of Upper Geyser Basin,
depositional environments of Precam-
brian banded iron formations: Economic
C
Royal Society of New South Wales, v. 61,
p.1-53.
Yellowstone National Park, Wyoming:
United States Geological Survey, Pro-
Geology, v. 68, p. 1144-1168.
Garrels, R.M., 1987, A model for the depo-
C
fessional Paper 1054-A, 26 p. sition of the microbanded Precambrian C
Hydrothermal-volcanogenic Cherts Lalou, C., Brichet, E., Ku,T.L.and Jahanno, iron formations: American Journal of
C., 1977, Radiochem ical, scanning elec- Science, v. 287, p. 81-106. C
Anderson, R.N., Hobart, M.A. and Lang-
seth, M.G., 1979, Geothermal convec-
tron microscope (SEM) and X-ray
dispersive energy (EDAX) studies of
Holland, H.D., 1973,The oceans: A possible
source of iron in iron formations : Eco- c
tion through oceanic crust and sedi-
ments of the Indian Ocean: Science,
a FAMOUS hydrothermal deposit :
Marine Geology, v. 24, p. 245·258.
nomic Geology, v. 68, p. 1169-1172.
Holland, H.D. and Malinin, S.D., 1979,The
e
v. 204, p. 828-832 .
Barrett, T.J., 1979, Origin of bedded cherts
Meyer, C. and Hemley, J.J., 1967, Wall rock
alteration, in Barnes, H.L. , ed., Geo-
solubility and occurrence of non-ore
minerals, in Barnes, H.L., ed., Geo-
c
overlying ophiolitic rocks in the Italian chemistry of Hydrothermal Ore Depos- chemistry of Hydrothermal Ore De- c
North Apennines, and implications of
the ophiolite-pelagic sediment se-
its: Holt, Rinehart and Winston ,
New York, p. 166-235.
posits, Second Edition : Wiley Inter-
science, New York, p. 461·508. c
quences for seafloor processes, un-
published D. Phil. thesis, Oxford Univer-
Rimstidt, J.D. and Barnes, H.I., 1980, The
kinetics of silica-water reactions: Geo- c
sity, v. 1, 288 p.
Bertine, K.K. and Keene, M.J., 1975, Sub-
chimica et Cosmochimica Acta, v. 41,
p. 1683-1699.
c
marine barite-opal rocks of hydrother-
mal origin: Science , v. 188, p. 150·152.
c
c
c
c Origin of Inorganic and Replacement Cherts 275

r
r Hughes, C.J., 1976,Volcanogenic cherts in
o the Late Precambrian Conception
Group, Avalon Peninsula, Newfound-
o land: Canadian Journal of Earth Sci-
ences, v. 13, p. 512-519.
c Laberge, G.L., 1973, Possible biological
origin of Precambrian iron formations :
o Economic Geology, v. 68, p. 1098-1109.

c Pettijohn, F.J., 1975, Sedimentary Rocks,


Third Edition: Harper & Row, New York,
c 628 p.
Ross, G.M. and Chiarenzelli , J.R., 1985,
o Paleoclimatic significance of wide-
spread Proterozoic silcretes in the Bear
o and Churchill Provinces of the north-

o western Canadian Shield: Journal of


Sedimentary Petrology, v.55, p.

o 196-204.
Simonson, B.M., 1985, Sedimentology of
o chert in the Early Proterozoic Wishart
Formation , Quebec-Newfoundland,
o Canada : Sedimentology, v. 32, p. 23-
40.
o Simonson, B.M., 1987, Early silica cemen-
tat ion and subsequent diagenesis in
o arenites from four Early Proterozoic
Iron Formations of North America: Jour-
nal of Sedimentary Petrology, v. 57,

o p.494-511.
Walker,J.C.C ., 1984,Suboxic diagenesis in
o banded iron formations : Nature, v. 309,
p.340-342.

o
o Accepted, as revised, 1989
o
o
o
o
o
o
o
o
;
c
276 Diagenesis Geosc ience Canada Reprint Series 4 c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
c
Backscattered-electron SEM photomicrograph of a pyritic aggregate from the Cretaceous Harmon Member in the Peace River
Formation of Alberta. Early framboidal pyrite, the bright globular areas, coalesced into a cauliform body which was , in turn, c
overgrown by an euhedrally terminated rim (indicated by arrow). This progression of morphologies indicates that early, rampant
nucleation ofpyrite under open-system conditions was followed by a reduction in the supply of sulphate that led to slower crystal c
growth and the development of a euhedrally terminatedrim . The bright zone along the margin is an edge effect. Barscale indicates
20jJm. Photograph courtesy of J. Bloch (University of Calgary).
c
c
c
c
e
c
c
c
C
l

c
c
c
c Early Diagenetic Pore Water/Sediment Interaction 277

C.'·
( released to, or the reactants consumed TERMINOLOGY
o from, the pore water through observed
concentration changes in vert ical or
The diagenetic evolution of pore water
starts with "connate water" which is the
o lateral profiles.
(2) Distinction between the principal
water trapped between the sediment
particles during deposition. Initially this
( connate water may considerably ex-
modes of solute transport, i.e,. between
o advection (convection) and diffusion,
and determination of their flux rates.
ceed the volume of the solids. Freshly
deposlted clayey-silty sediments may
c (3) Assessment of mineral-solution
equilibria. As it is a widely held view that
contain as much as 90% (by volume)
water, and sands up to 40% or 50%.
)
diagenetic processes in actively sub- However,with burial to depths of only a
Early Diagenetic
o Pore WaterI
siding sedimentary basins do not lead few metres the water content is very

o Sediment Interaction:
to thermodynamic equilibrium between
the potential reaction partners, pore-
rapidly reduced in volume.
There has been considerable confu-
o Modern Offshore
water chemistry can provide clues to
this question by providing the data ne-
sion in the literature concerning the
term "connate water". Due to reactions
( Basins cessary for calculation of the saturation with the solids, pore waters usually
state with respect to the minerals of undergo sign ificant compos it ional
interest. Such calculations have been changes in the subsurface. Buried in-
o Reinhard Hesse
Department of Ge%gical Sciences
carried out for common authigenic min-
erals in ancient basins on land (Merino,
terstitial waters commonly are strik-
ingly different in composition and total
o McGill University 1975; Nesbitt, 1980, 1985)and in a few amount of dissolved species from their

o 3450 University Street


Montreal, Quebec H3A 2A 7
cases also for modern offshore basins.
The general plan for this review is to
connate-water precursors in marine or
terrestrial environments. The term con-
follow the early diagenetic pore-water nate water, in the sense advocated by
INTRODUCTION evolution in modern offshore basins Case (1955), however, should be used
Rock-water interaction, which receives tracing the changes that occur with in- only for pore waters still displaying the

o so much attention by geothermal engi-


neers, igneous and metamorphic pe-
creasing burial from the sources to the
sinks of the dissolved species. The
compositional and isotopic signatures
inherited from their parental source in
trologists, is of tantamount interest to three principal processes causing the ocean or lake water bodies. Gener-
sedimentary petrologists studying dia- these changes are reactions, diffusion ally this applies only to the shallowest
o genesis. Water is the principal trans- and advection whose combination pro- levels of burial, often not more than a

o port medium in diagenesis acting as


the carrier of dissolved substances
duces nine different types of pore-
water profiles. These will be discussed
few centimetres or millimetres below
the sedimentlwater interface over
o from sites of dissolution to sites of pre-
cipitat ion in the sediment column and
in order of increasing complexity. Rela-
tively simple, more or less straight-line
which distance the pore water is still in
diffusional contact with the overlying
o facilitating chemical exchange be- pore-water profiles are encountered in water body. Only in exceptional situa-

o tween sedimentary basins and the hy-


drosphere. Where water is absent be-
low sedimentation-rate environments
of the pelagic realm and can be under-
tions, such as certain types of pelagic
sediments, may this zone of diffusional
o cause mineral cements or non-aqueous
fluids such as liquid or gaseous hydro-
stood in terms of diffusive and convec-
tive transport of solutes. These are dis-
or convectional exchange extend
downward a few hundred metres in the
) carbons fill the pores, diagenetic reac- cussed first together with some min- subsurface . The definition of "connate
o tions are inhibited or slowed down dras-
tically. For most diagenet ic reactions
eralization reactions that are character-
istic for the early diagenetic history of
water" by Kharaka et a/. (1985) as
"water that was deposited with sedi-
o the presence of water in the sediment these environments. The more complex
profiles observed in organic-matter
ments or other rocks in the basin and
which has been out of contact with the
o pores is thus a prerequisite. Pore-water
analyses are, therefore, of great signifi- rich, high sedimentation-rate basins of atmosphere since its deposition" is
cance in the study of diagenesis, par- the continental margins (with their reac- similar to White 's (1965) definition . This
ticularly early diagenesis for which tion-dominated trends) follow. In these definition appears too broad, because it
water is as volumetrically important as basins, extensive mineralization reac- does not take into account composition-
r the solid phases. Pore waters are much tions serve as sinks for the dissolved al changes that may take place immedi-
more sensitive to changes in diagenetic substances. They are treated in a sepa- ately after deposition and which may
environments than solids and therefore rate section. Ion exchange reactions become so profound as to obscure the
r: are the preferred diagnostic objects for and adsorption are additional sinks that origin and source of the water. To call
the study of early diagenesis. There are may help to understand the behaviour such pore waters "connate" would not
three aspects of diagenesis to which of some ionic species in these basins. be in line with the very meaning of the
pore-water studies contribute most: The definition of the boundary between word and intent ofthe earlyauthors (e.g.,
(1) The detection of diagenetic reac- the stages of early and intermediate Case, 1955) who introduced the term.
tions actively occurring in the sediment diagenesis is deferred to the end of the Changes in pore-water chemistry at
at the time of sampling (drilling) by article, because it is based on the delib- depth are often coupled with increasing
tracing the products of these reactions erations of this review. concentrations of dissolvedsolids. Maxi-
c
278 Diagenesis Geoscience Canada Reprint Series 4 c
c
imum salinities are encountered in the SOURCES OF PORE-WATER DATA source of information . There is not
c
deep parts of sedimentary basins, par- Information concerning the chemical much overlap with the results of the c
ticulary in the vicinity of salt domes or
deeply buried evaporites where values
evolution of pore waters during burial
diagenesis in modern offshore basins
DSDP, which concentrated on the
ocean basins and deeper portions ofthe c
of 200-300 g. L-1 of dissolved solids are
not exceptional (an up to eight-fold
comes from three principal sources:
(1) studies of piston and gravity cores;
continental margins and stayed away
from potential hydrocarbon provinces
c
increase compared to normal seawater (2) the interstitial water-sampling pro- on the upper margins and shelves on c
salinity). Salinities as high as 60%0 have
been reported, but these occur in ore
gram and related sediment studies of
the Deep Sea Drilling Project (DSDP)
which offshore oil drilling has focussed.
Penetration reached in exploration c
fluids of porphyry copper deposits and its successor program, the Ocean wells for oil and gas generally exceeds c
(Roedder, 1977) not related to burial
diagenesis .
Drilling Program (ODP); and,
(3) offshore oil and gas wells.
that of the drill holes of the DSDP and,
therefore , pore-water compositions c
Highly saline waters are called brines.
According to Carpenter (1978), brines
The first is restricted to the upper 10to
20 m of the sediment column in modern
from deeper, more advanced levels of
diagenesis may be obtained, which are c
have salinities in excess of 10%0, which
would limit application of the term to a
subaqueous environments, which is the
maximum depth of penetration by con-
the subject of a forthcoming article.
Extraction of the pore water from un-
c
relatively small sample of ali deep sub- ventional coring devices such as piston consolidated to moderately consoli- c
surface waters. Following Kharaka et al.
(1985a),salinities above seawater salin-
and gravity corers. Since the classical
study by Emery and Rittenberg (1952)
dated sediments by squeezing with
stainless steel squeezers (Manheim
c
ity of 3.5%0 are sufficient for a pore water on California Borderland basin sedi- and Sayles, 1974) may lead to systema- c
(or any other hypersaline body of water)
to qualify as a brine. In the petroleum
ments, this type of analysis has been
applied to surface sediments all over
tic errors due to temperature increases
between the ocean floor and the labora- c
industry it is common practice to call
pore waters encountered in oil-bear-
the world's oceans and of many lakes.
It covers the very earliest stages of
tory. Increases of 1 to 50% in chloride
and dissolved silica , for a temperature
c
ing sedimentary formations "formation diagenesis for which Berner (1980) difference of 20°C (Bischoff et al., 1970; c
waters", a term which strictly applies to
the "water present in the rocks immedi-
provides an excellent theoretical treat-
ment and review.
Fanning and Pilson, 1971) have been
observed. For potassium , enrichments c
ately before drilling", whereas the gen- In the past two decades, a second of up to 13% have been found, whereas
magnesium and calcium can show de-
c
eral term" interstitial water" is applica-
ble to all types of pore waters from all
important source of information has
been the Deep Sea Drilling Project. pletions of up to 2.5 and 5%, respec- c
depths and different kinds of sedimen-
tary basins: modern offshore basins
Although perhaps not as widely noticed
as some other of its spectacular re-
tively. These shifts can be avoided by
standardized extraction procedures un- c
on the continental margins and ocean sults, the interstitial water program has der regulated temperatures, including c
floors, modern lakes or river basins and
ancient basins on land, irrespective of
been one of the outstanding successes
of this project. It provided a consistent
centrifugation for less consolidated
samples. c
age or sampling procedure. Waters with
salinities lower than those of brines, i.e.,
data body of thousands of pore-water
analyses covering the depth range from
c
between 3.5 and 1%0, are simply called
"saline waters", those with salinities
a few metres to about 1500 m subsur-
face. As an outcome of this program
c
between 1.0 and 0.1%0 "brackish", and and the piston core studies mentioned C
those with still lower concentrations of before, we now have a fairly good un-
dissolved salts , "fresh waters". derstanding of the variations in pore-
G
Another important term is " meteoric water chemistry that occur in the upper C
water " originally defined as "water 1000 or 1500 m of the sediment column
that was recently involved in atmo- in different open-ocean as well as deep- C
spheric circulation" (White , 1957, p.
1661). This is "water derived from rain,
water continental margin environ-
ments. Between 1968 and 1983 more
C
snow, water courses , and other bodies than 1000bore holes were drilled by the C
of surface water that percolates in rocks
and displaces their interstitial water"
DSDPat 624drill sites and for more than
half of these pore-water data are avail- c
(Kharaka and Carothers, 1988). The
time of the last contact with the atmo-
able. Results have been summarized
during various phases of the project
e
sphere has been dropped intentionally (Manheim and Sayles, 1974; Sayles and c
from the definition by these authors,
because water with the characteristics
Manheim, 1975; Gieskes, 1975, 1981,
1983) and this article includes an up- c
of meteoric waters may be very old. A date of those earlier reviews.
0.1 I 10 100
Sed rmenrat ron Rate (g/cm 7/10 Ja) c
modifier such as " Miocene" or"Pleisto-
cene meteoric water" may be used,
however, to denote its age, i.e., the time
Innumerable holes drilled for oil and
gas or other resources in sedimentary
basins on the continental shelves and
c
Figure 1 Organic carbon accumulation
of its removal from contact with the slopes, from which formation waters rate as a function of sedimentation rate.
atmosphere if known. have been sampled, provide the third (From Heath et aI., 1977). c
c
c
c
c Early Diagenetic Pore Water/Sediment Interaction 279

c
c. DIAGENETIC REGIMES OF tration, therefore, determines the early tion rates. In stagnant or euxinic basins,
o PORE-FLUID EVOLUTION IN diagenetic reactivity of the sediment, bottom waters act as a trap for organic

o MODERN OFFSHORE BASINS


Diagenetic environments of subsurface
pore-water evolution in modern off-
that is, rates and types of reactions.
The correlation between sedimenta-
tion rate (expressed in g' cm-2 per 1000
matter protecting it from oxidation. Such
basins are rare , however, in modern
oceans . Excessive input of terrigenous
(
shore basins can be divided into two years (103 a» and organic carbon accu- materials has a diluting effect. thus also
( main regimes: mulation rate (expressed in the same producing a negative correlation be-

c I. Low to intermediate sedimentation-


rate basins (or environments) mostly as-
units) has been shown to be linear on
a logarithmic scale (Figure 1) for open
tween sedimentation rate and organic
carbon content (Gautier et al. , 1984;
o sociated with oxic and suboxic diagene-
sis and convection- and diffusion-con-
marine pelagic and hemipelagic envi-
ronments (Heath et el., 1977; MOiler
Johnson Ibach, 1982; Stein, 1986).
The effect of sedimentation rate on
c trolled pore-water profiles, and
II. High sedimentation-rate basins
and Suess, 1979). This is basically the
result of increased preservation of or-
the diagenetic evolut ion of pore waters
is two-fold. Apart from the effects
(; characterized by anoxic diagenesis and ganic matter in more rapidly deposited caused by coupling with organic matter
o reaction-controlled pore-water profiles.
Despite the great variation in the
sediments. The faster the sediment is
buried, the more rapidly its organic mat-
concentration, sedimentation rate also
controls pore-water evolution through
o chemical composition of pore-water
analyses from offshore basins all over
ter is removed from contact with oxidiz-
ing bottom and pore waters, in which
its effects on diffusion rates. Where
sedimentation rates exceed diffusion
the world, this broad classification in bacteria are most efficient in decom- rates, diffusive transport cannot keep
o terms of two main environments or re- posing organic matter. Rapid sedimen-
tation, therefore, is a prerequisite for
pace with burial. Chemical concentra-
tion changes produced by diagenetic
o gimes does justice to most of the data
and will help not to miss the wood for organic matter to survive the first steps reactions will be preserved much better

o trees. Situations not covered by this


simple two-end-memberscheme are in-
of deposition and burial and to become
available for subsequent diagenetic re-
during burial and for much longer
periods of time. An analogous relation-
cluded in a third category: actions . Variations in primary produc- ship exists between sedimentation rate

o III. Special environments.


The reason for the dominant effect
tion rate in the surface waters appear to
be of secondary importance only, as
and advection rate.
The linkage of sedimentation rate to

o of sed imentation rate on pore-water


chemistry, particularly during early dia-
demonstrated by those authors. Chan-
ges in productivity, to some extent, par-
the three pr incipal diagenetic pro-
cesses that control pore-water chemis-
o genesis in marine basins, is its close allel changes in sedimentation rate try, i.e., (1) chemical reactions in the

o positive correlation with organic matter


content of the sediments and its tend-
thus enforcing the positive correlation.
It is not clear whether this correlation
sediment/pore-water system triggered
by organic matter decomposition, (2)
o ency to counteract the role of diffusion .
Organic matter is the least stable and
also applies to terrestrial organic mat-
ter because of its greater resistance to
transport of solutes by diffusion, and (3)
transport by advection (convection), ex-
o most reactive sediment constituent. It is bacterial decomposition in the oxida- plains the overriding effect ofthis single

o metabolized rapidly by bacteria during


early diagenesis and the metabolites
tion zone (Waples , 1983). Positive cor-
relation between sedimentation rate
parameter on early diagenetic pore-
water evolution. Where sedimentation
o including the basic nutrients carbon,
nitrogen, phosphorus, sulphur, and hy-
and organic carbon content of the sedi-
ments is not universal, however, and
rates are low, the reactivity of the sedi-
ment during early diagenesis is low due
o drogen are released to the pore water.
These become involved in the first diage-
does not apply for stagnant or semi-
stagnant basins with oxygen-deficient
to reduced organic matter concentra-
tions. and diffusion (or advection) may
( netic mineralization reactions and trigger bottom waters. The same applies to efficiently dissipate existing concen-
o other reactions. Organic matter concen- areas with extremely high sedimenta- tration gradients. The result are simple.
often straight-line vertical concentra-
o Table 1 Major types of interstitial water profiles t ion profiles. Where sedimentation

o Low to Intermediate sedimentation rate basins


rates are high, the chemical reactivity
of the sediment is high due to gener-
(I 1. Convection-controlled profiles - no chemical gradients (Figure 6. DSDPsite 495) ally increased organic matter preserva-
2. Diffusion-controlled profiles with linear correlation between changes in Ca and tion. Consequently. early diagenetic re-
G Mg concentration (Figure 7)
3. Reaction-controlled profiles in suboxic environments (Figures 4, 6, site 495)
actions are intense. In these environ-
ments, the efficiency of diffusion (and
l II High sedimentation-rate basins
4. Reaction-controlled profiles in anoxic environments with no chloride gradients advection) in dissipating gradients es-
C (Figure 6, upper part of DSDP site 570) tablished by the reactions is low. Com-
plex pore-water profiles result.
5. Profiles with fresh water influx (Figure 14)
6. Gas-hydrate affected profiles with downward decreasing chlorinity and increas- Interaction of the three general pro-
ing 0'80 values (Figures 6, 17) cesses. i.e., reactions. diffusion, and
III Special environments advection , in the two or three main
7. (Thrust-)faulted sect ions with discontinuous chemical trends indicating lateral types of environments of pore-water ev-
pore-water flows (Figure 18) olution gives rise to the nine different
8. Evaporite-dissolution affected profiles (Figure 19)
types of vertical pore-water profiles
9. Hydrothermal activity and intrusion of igneous dykes and sills (Figure 20)
(Table 1 and Figure 2) mentioned in the
C
280 Diagenesis Geoscience Canada Reprint Series 4 C
C
2+Mg2+
CI- Ca 80:- NH3 PO:- Alk , £»
18
0 c
n""r" r r r""f1'
t~· ~rn!.,~: i'~'rf :J.Jo.~~. r, sr\.~lrV\·; C
:':no'" 'J .:( : ~;i It :' 5 1 4'.1:;, ~
;~ :~ ~I ~I ~I \V c
c

;~:n urlJV ® ~
~[J-
~.
nrlJrr @ ~c
:: If?rlTvvrr ® ~
:f71?I vPvf\ @ ~
::F rllJr@ ~
5~O Q' I I I ~4~~ I CD ~c
:r::h~rlrl@ ~
:F" """fVlrl ® ~ Figure 2 Chemical characteristics of major types of interstitial water profiles (see Table 1). L
(
c Early Diagenetic Pore Water/Sediment Interaction 281


c introduction. This list of nine is not not the rule although they may cause (5) the fermentation zone, and,
o meant to be exhaustive and is merely significant modification in certain (6) the thermocatalytic decarboxyla-

o intended to provide guidance in recog-


nizing general trends among the highly
variable pore-water compositions en-
basins or parts thereof .

EARLY DIAGENETIC
tion zone,
which represent a burial-depth zona-
tion. The first five zones require the
countered in the subsurface. It will ORGANIC-MATTER OXIDATION presence of bacteria. At the lower
( serve as a frame of reference in the Organic matter represents highly boundary of zone (5), bacterial activity
following discussion of the two or three reduced carbon compounds which are ceases and thermocatalytic reactions
C end-member environments of pore- among the strongest reductants in take over. This is a natural lower bound-
o water evolution . Before addressing
these environments , two of the general
freshly deposited sediments . The
organic matter dispersed in the sedi-
ary for the zone of early diagenesis.
(1) In the oxidation zone, freely dis-
processes, i.e., (1) early diagenetic or- ment provides an energy source for solved oxygen is available from sea-

o ganic matter oxidation as the key mech-


anism in early diagenetic reactions and
sediment-dwelling organisms, fore-
most bacteria, to maintain their metab-
water trapped in the sediment or sup-
plied by diffusion from the overlying
o (2) diffusion will be discussed in more
detail in the next two sections. The role
olism through oxidation reactions. Bac-
terially mediated oxidation of organic
bottom water. The pore water of the
oxidation zone may, therefore, be
o of the third mechanism, (3) advection, matter becomes the first and most effi- called "connate" in the strictest sense

o will be dealt with in connection with the


relevant types of pore-water profiles
cient mechanism to alter the chemical
composition of pore waters during early
of the word. Bacteria are not the only
oxygen-consuming organisms active in
o (i.e., types 1, 8 and 9).
Other geologic factors besides sedi-
diagenesis. The well-established or-
ganic matter oxidation reactions start
this zone, which is the habitat of a di-
verse group of endobenthonic micro-
o mentation rate such as the composition immediately after deposition. Accord- and macro-organisms. Aerobic bacte-
o of the starting fluids, i.e., the connate
waters (seawater versus fresh water) or
ing to the source of the oxidant (elec-
tron acceptor), six different zones or
ria are the most efficient users of oxy-
gen in this zone, however. The amount
o the tectonic stage of basin evolution
that would be equally important in a
stages have been distinguished in the
oxidative breakdown of organic matter
of dead animal or plant matter left un-
destroyed in the sediment after pas-
o global survey, may be considered sec- during burial (Claypool and Kaplan, sage through the oxidation zone is a
o ondary for the purpose of this review
article which is concerned solely with
1974; Curtis, 1978). These are (Figure3):
(1) the oxidation zone,
function of the residence time in this
zone. In oxidizing organic matter and
o modern marine basins. For these the
effects of diastrophism (uplift and defor-
(2) the nitrate reduction zone,
(3) the sulphate reduction zone,
breaking it down into smaller molecules
the bacteria gain energy for their me-
o mation) and meteoric water influx are (4) the carbonate reduction zone, tabolism. Because of their small size, in
o Stagnant (.uxinic)
the micron range, they possess a large
surface-area/mass ratio which favours
o V.ntilat.d Basin Basin the exchange of dissolved substances
~.!.!=.!~~--=-
o I .
: i
.
;
.
with the pore water through the cell
walls. Microbial degradation of organic
o } ..:
.
,I
'.
:
molecules leads to a loss of functional
groups, particularly hydrocarbonchains
o l
\
(
\
Anoxic
and carboxyl-groups and the smaller

o Oxic bottom wat.r \: l ;


bottom
water.
molecules are partly converted to car-
bon dioxide according to an overall re-
o I Oxidation Zan.
(2) Nitrat. r.ductionZon.
edimentl
~~;j Water
action which may be written as
CH20 + O2 CO2 + H20
o = Interface ->

where the bulk composition of organic


o (3) Sulfat. reduction Zone
matter has been simplified to CH20.

c The efficient use of oxygen by aero-


bic respirators may lead to temporary or
local oxygen depletion, particularly in
cOt. CH4
(4) Carbonate reduction @> ® @) and fermentation regions of rapid sedimentation where
6 replenishment from the overlying bot-
(5) and fermentation Zones tom water by diffusion may not keep
C pace with consumption. Obligatory
aerobic organisms will then cease to
(6) Thermocatalytic exist, but facultative aerobeswhich can
decarboxylation switch from an aerobic to an anaerobic
mode of respiration may still be present.
The oxidation zone is easily recog-
Figure 3 Stages of organic matter oxidation in anoxic sediments. (Modified from Claypool nized by its brownish-yellowish sedi-
and Kaplan, 1974). ment color, where it is present. In
c
282 Diagenesis Geoscience Canada Reprint Series 4 c
c
organic matter-rich sediments, it may where ammonia released from organic CONCENTRATION -+
c
be only a few centimetres or millimetres matter decomposition is oxidized c
thick - in contrast to the carbon-free
brown abyssal clay discussed below.
(Froelich et a/., 1979) . From th is
maximum, nitrate decreases down- c
In stagnant or euxinic basins the oxida-
tion zone is absent.
ward to zero at the base of the nitrate
reduction zone. The lower boundary of
c
(2) The nitrate reduction zone com- the nitrate reduction zone is charac- c
mences where the concentration of dis-
solved oxygen drops below about 0.5
terized by the change from positive to
negat ive electrochemical potentials c
mL 02 ·(L H20)-' (Devol, 1978), which and the appearance of anaerobic bac- c
correspondsto the oxygen levelat which
most benthonic macro-organisms dis-
teria. When the electrochemical poten-
tial is lowered sufficiently, oxides and ~ c
appear from the sediment (Rhoads and hydroxides of manganese, which at
~ c
Morse, 1971). Dysaerobic bacteria,
which live at dissolved oxygen levels
between to and 0.1 mL O2 . (L H20)-',
higher oxidation potentials have a very
low solubility, will be reduced and go ! c
are characteristic for this environment.
into solution as shown schematically in
Figure 4 (Froelich at a/.• 1979)thus serv- c
which may be called suboxic. The term
"suboxic diagenesis" thus refers to the
ing as an important source of oxidant in
c
nitrate reduction zone. Concentration Figure 4 (right) Schematic diagram for c
of nitrate tends to increase from the
ambient bottom water value of
the depth distribution of dissolved 02' NO-3
Mn 2 + and Fe2 + in suboxic environments
c
0.03-0.04 mM (mM = millimoles . L") (pore-water profile type 3). (From Berner,
to a maximum in the oxidation zone 1980, after Froelich et at, 1979).
c
Table 2 Stages of organic matter oxidation. (Modified from Froelich et al., 1979).
c
C : N : P = 106: 16 : 1 = Redfield ratio for primary organic matter.
The organic matter involved in reactions (1) to (4) does not necessarily have this ratio . c
~GO' of metabolic processes c
coupled with oxidation reactions
(in kcal- (mol)-' glucose) c
(1) Oxidation by freely dissolved O2 (aerobic respiration) c
-763 c
Manganese reduction c
(CH 20)'06(NH3l'6(H3P04 ) + 236 Mn02 + 472 H+ ..... -748 (birnessite) c
236 Mn 2+ + 106 CO 2 + 8 N2 + H3P04 + 366 H 20 -698 (pyrolusite)
c
(2) Nitrate reduction c
(CH 20)'06(NH 3),6(H 3P04 ) + 99.4 HN03 ..... c
106 CO 2 + 55.2 N2 + H3P04 + 177.2H20 -724
c
(CH 20),06(NH3l ,6(H3PO..) + 84.4 HN03 .....
106 CO 2 + 42.4 N2 + 16 NH 3 + H3PO.. + 148.4 H20 -658
c
c
Iron reduction
(CH 20),06(NH3),6(H3P04 ) + 212 Fe 203 (or 424 FeOOH) + 848 H+ ..... -337 (hemat ite)
c
424 Fe 2+ + 106 CO 2 + 16 NH3 + H3PO.. + 530 H 20 (or 742 H20) -318 (limonitic goethite) e
(3) Sulphate reduction
c
c
(CH 20)'06(NH3l'6(H3PO..) + 53 (504 ) 2 - .....
106 CO 2 + 16 NH 3 + 535 2 - + H3PO.. + 106 H20 -91 c
c
(4) Carbonate reduction
c
-84
c
c
c
c
c Early Diagenet ic Pore Water/Sediment Interaction 283

c
c addition to nitrate of the pore water. The dant (27 mM) in oceanic bottom waters significant CH4 production seems to
o exact Eh-Ievel at which manganese re- than nitrate. However, in organic-mat-
ter rich sediments the combined thick-
start only after the disappearance of
more than 80%, if not complete deple-
o duction occurs depends on the dif-
ferent oxides and hydroxides involved ness of the nitrate and sulphate reduc- tion of the dissolved sulphate (Sansone
r having different Gibbs free energies
(Table 2). Iron reduction will occur after
tion zones is often less than a few
metres and in certain regions may be as
and Martens, 1981). A possible reason
is that methane producing bacteria may
o manganese reduction at somewhat
greater depth, often overlapping with
small as 10or 20 cm (Reeburgh, 1983).
(4) In each of the three oxidation
not be able to tolerate the levels of H2S
or HS- existing in the sulphate reduc-
C- the sulphate reduction zone when the steps discussed so far one of the main tion zone, although this seems ques-
redox potential has been lowered fur- products of bacterial organic matter de- tionable in view of the fact that methane
O ther. Both manganese and iron reduc- composition has been carbonic acid bacteria have been found in the pre-
o tion are hydrogen-ion consuming re-
actions, as the equations in Table 2
and its dissociated species bicarbonate
HC030r carbonate CO~-. Below the sul-
sence of unreacted HS- below the sul-
phate reduction zone. Alternative ex-
o show, increasing the pH which may be phate reduction zone the carbonate it- planations are (i)that free hydrogenmay
o a prerequisite for the precipitation of
early diagenetic carbonates in concre-
self becomes one of the main oxidants
for further bacterial oxidation of organic
not be available for CO2 reduction in the
presence of sulphate reducing bacteria
o tions (see later section).
(3) Suboxic conditions of the nitrate
matter. In the carbonate reduction zone
bacter ial carbonate reduction leads -
or (ii) that the methane which may be
produced in the sulphate reduction
reduction zone are followed by the truly for the first time in the burial history of zone is immediately oxidized to CO2,
o anoxic conditions in the underlying
sulphate reduction zone. Although the
organic-matter rich sediments - to the
production of methane.
This latter process would also inhibit
the appearance of CH4 in the sulphate
o sulphate-reducing bacterium Desulfo- The process appears to require a re- reduction zone due to upward diffusion .

o vibrio desulfuricans is the dominant


bacterial species, as only few species
ducing intermediate (e.g., hydrogen)
also derived from bacterial organic
(5) The fifth oxidation mechanism is
bacterial fermentation where the oxy-
can tolerate the toxic effects of the hy- matter degradation (Berner, 1980). For gen contained in organic compounds is
drogen sulphide produced in this zone, example, the oxidation of ethanol will transferred to oxidize organic matter,
o it is not the only one. The sulphate re- yield acetic acid and hydrogen accord- simultaneously yielding CO2 and CH4 •
o ducers oxidize relatively small organic
molecules such as lactic acid and four-
ing to the reaction
CH3CH20H + H20-+CH 3COOH + 2H2·
From what has been said above it is not
clear whether this step is a separatestep
o carbon dicarboxylic acids. These are
produced by fermenting bacteria
The hydrogen may be used by true or whether in fact bacterial carbonate
reduction always requires fermentation
o whose symbiosis with the sulphate-re-
methanogenic bacteria such as Meth-
anobacterium thermoautotrophicum to processes as symbiotic reactions.
o ducing bacteria is required by the pro-
cess . A simplified equation for this
reduce CO2 produced in this and the (6) Bacterial activity decreases de-
cisively at temperatures above 75°C
o rather complex process is
previous zones (according to a reaction
of the general type CH20 + H20 -+CO2 and only few populations still exist at

o 2CH20 + SO~--+S2- + 2H+ + 2HC03.


As soluble ferrous iron usually be-
+ 4H which is enzyme catalyzed and
produces atomic H) by the redox
higher temperatures. Organic matter
oxidation, however, continues to pro-
o comes available through reduction of reaction ceed at temperatures above 75°C, but
under abiogenic conditions . Once the
o ferric oxyhydroxides and oxides in the
sulphate reduction zone and the lower
8H + CO2 -+ CH4 + 2H20 .
The process of methane formation
activation energy has been reached,

o part of the nitrate reduction zone of ter-


rigenous sediments, dissolved sul-
thus appears as a disproportionation of
the reactions will occur spontaneously.
These thermocatalytic reactions in-:
o phide concentrations remain relatively
low (less than 5 mM), because of the in-
organic matter into carbon dioxide and
methane (Goldhaber and Kaplan, 1974)
elude the decarboxylation of organic
acids according to the general formula
and it is not clear at present whether a R-COOH -+ RH + CO2 where the or-
stantaneous precipitation of meta- direct transformation of organic com-
stable iron-monosulphides which later ganic acid group COOH is converted
pounds into methane by bacteria is pos- to CO2 and R- is the organic radical.
transform to pyrite. In iron-poor marine sible. Although methanogenic bacteria This process occurs at more elevated
carbonate muds the process will take a exist over a wide temperature range temperatures (above 75°C) and deeper
different course of events. (0°-75°C, Zeikus and Wolfe, 1972), the burial levels and is probably very impor-
Sulphate reduct ion is diagnostic for optimum for individual species spans tant in generating aggressive acidic
the pore waters of marine sediments only a few degrees. For example, the pore waters at depths which may be
as compared to freshwater sediments, thermophylic M. thermoautotrophicum responsible for the dissolution of car-
which are often low in sulphate and has its optimal temperature range be- bonates and feldspars and the genera-
lack the sulphate reduction step in the tween 65°C and 70°C. tion of secondary porosity. These are
early diagenetic evolution of their pore Methane production and sulphate re- additional arguments for choosing the
waters. In marine sediments the sul- duction are not mutually exclusive pre- boundary between zones (5) and (6) as
phate reduction zone is considerably cesses (Claypool and Kvenvolden, the boundary between early (or shal-
thicker than the nitrate reduction zone 1983), but they seem to be fairly well low) and intermediate diagenesis as
because dissolved sulphate is about separated, because CH4 levels in the discussed more fully in the final section
three orders of magnitude more abun- sulphate reduction zone are low and of this article.
c
284 Diagenesis Geoscience Canada Reprint Series 4 c
c
c
c
Table 3 Diffusion in Sediments. (After Berner, 1980). c
Fick's First Law
c
ac.I Jj = flux of species i c
(1) J.
I
= _D·_
azI
OJ = diffusion coefficient [cm 2 • S-1 ] c
Fick's Second Law az-
aC j
= verticaI concentratton gra dllent
° ° c
c
c
Fick's Second Law in polar co-ordinates
c
a(r2 0 j aa~j}
c
3) aCj = _ aJ = j .....,1"....-~_ _ c
at ar r2 or c
Fick's First Law for charged species i
= mobility of i-th ion at infinite dilution c
Vi
c
~~ = gradient of electrical potential E c
Zj
B"
= charge of the i-th species
= Faraday constant
c
R = gas constant c
T = temperature in degrees Kelvin c
c
c
Sediment diffusion coefficient Os al
= az?; °
c
o
8
al
1 tortuosity
= actual path length of ion in solution
c
(6) o, = 02 8 = q,F, where q, is porosity c
Diffusion flux in sediments J s
R .
F is formation factor C
Js = -q,Os---az
ac F = o
e
-R,where
Re is electrical resistivity of
E
ac C
ac 1 aJ s 1 a(cP°s az} sediment

(7) at = --;az- = --; az


Ro is resistivity of pore water C
F = cP-n ,for n =2: D, = cP20 C
Mean diffusion path length
C
c
e
General diagenetic equation
v = velocity of advective flow
c
(
Rk = k-th reaction
c
(
c
(
c
c
c
c Early Diagenetic Pore Water/Sediment Interaction 285
c
r. The sequential order in which zones DIFFUSION AS A DIAGENETIC stant diffusion coefficient OJ which,
r (1) to (6) follow one another, most of TRANSPORT MECHANISM however, is not applicable for many dis-

o them apparently without significant


overlap, is related to the difference in
Diffusion operates to dissipate con-
centration differences. Thus the driving
solved species in natural sediments un-
dergoing compaction. For the common

r the Gibbs free energy associated with


each of the oxidation reactions listed
forces for diffusion are chemical poten-
tial gradients and gradients of the elec-
occurrence of concretion growth during
diagenesis, which is a diffusion-control-
o in Table 2 (based on glucose as or-
ganic substrate). Utilization of dis-
trical potential caused by charged spe-
cies. The flux J j of a dissolved chemical
led process, flux gradients are perpen-
dicular to a sphere or ellipsoid, for which
o solved oxygen as an oxidant is evi- species i due to molecular diffusion is Fick's law is more conveniently ex-
c dently the most energy efficient pro-
cess. For each later step in the se-
directly proportional to the concen- pressed in spherical co-ordinates
(equation (3), Table 3).
o quence the energy yield is less sug- tration gradient oCj • The factor of pro-
OZ
Reservoirs that are in diffusive com-

o gesting that specific bacterial popula-


tions associated with the various portionality is the diffusion coefficient
munication are connected by concen-
tration profiles of the dissolved species
o reactions in the subsurface follow each
other in the order of decreasing energy
OJ' If we restrict ourselves to vertical
concentration gradients, which are
which bridge the concentration dif-
ference and are straight lines, if the
o efficiency of their metabolic reactions. dominant during early diagenesis, then diffusion coefficients are constant, or

o Details of the biochemical reactions


involved in bacterial metabolism are
the flux J j is given by the one-climen-
sional form of Fick's first law of diffusion
curved ones, if the diffusion coeffi-
cients vary with time or depth of burial.
o still poorly understood. Probably all of
them include enzymatic reactions. It is
(equation (1), Table 3). Most dissolved
species are electrically charged ions .
Curved profiles, on the other hand, may
also result from transport by advection
o known, for example, that methanogens Therefore electrical potential gradients or reactions within the sediment. In the

o can only use acetic acid or acetate and


shorter hydrocarbon molecules for con-
have to be taken into account resulting
in a more complex version of Fick's law
general diagenetic equation (equation
(9), Table 3) the total flux of a dissolved
version into methane (Mechalas, 1974). (equation (4), Table 3). The unknown
Because acetic acid levels in the pore species J j or its gradient oCj is the sum
o waters of marine sediments are rela- electrical potential gradient oE can be
OZ
oz
o tively low, other strains of bacteria must
be present to produce the intermediate eliminated from (4) by using the electri-
of three terms, the diffusive flux, the ad-
vective flux and the flux resulting from
o substances which are then being used cal neutrality condition which requires ongoing reactions. To distinguish be-

o in the methane generating process.


Similarly, sulphate-reducing bacteria
that the sum of the electrical charges
associated with the fluxes of all species
tween the various contributions each
situation has to be analysed individually.
o use relatively short-chained organic
acids which must be provided by sym-
be balanced. In other words, E;ZjJj = 0
which leads to equations (4a) and (5)
A depth dependency of the diffusion
co-efficient is to be expected from its
o biotic bacteria breaking down larger or-
ganic molecules. Thus different inter-
in Table 3.
Variations in concentration with time
relation to porosity via tortuosity. Tortu-
osity 0 is a measure of the distortion of
o acting bacterial populations must be the diffusion pathway of solute species
o present at anyone time in the sulphate
reduction and methane producing
oCj which may result, e.g., from varia-
OZ
due to the presence of solid particles.
Tortuosity is a function of porosity and
o zones which are involved in a series of tion in the input rate of soluble sub- the formation factor F, which is the re-

o simultaneous and partially symbiotic


reactions. With the conventional spec-
stances during sedimentation, will cause sistivity ratio R.,IRo of a natural sedi-
ment (Re ) and its pore water (Ro) (see
o trum of pore-water analyses we only
see the end products of these chain
vertical gradients of fluxes oCj which
oz
Table 3). The bulk (or sediment) diffu-
sion coefficient Os, therefore, depends
reactions. are obtained from Fick's second law. In strongly on porosity and, for that mat-

o the form given (equation (2), Table 3)


it is based on the assumption of a con-
ter, on depth. For more compacted sedi-
ments considerably smaller coeffi-
c cients result. Apart from its effect on the
sediment diffusion coefficient Ds ' po-
Table 4 Diffusion coefficients and mean diffusion path length.
rosity cf> has to be included in all of the
Os Zm (in m)
equations (1) to (4) as a separate factor,
Na+ 7.4 154.2 because under diagenetic conditions
Ca2 + 4.4 117.8 diffusion occurs only in the pore water.
CI- 10.2 179.0 This leads to equations of the form
(50 4)2- 5.0 125.8 given in equation (7) (Table 3).
Where, Over what distances can diffusion af-
fect transport of dissolved species in
D, is the bulk sediment diffusion coefficient (1(}-6 cm 2·s·'). actively subsiding sedimentary se-
(Data from Li and Gregory (1974) for brown abyssal clay with a porosity
quences? It is possible to calculate the
of 71% at T = 20-25°C, quoted in Berner, 1980).
mean diffusion path length Zm (Gieskes,
Zmis the mean diffusion path length calculated for t (time) = 1 Ma.
1975), which is the distance over which
c
286 Diagenesis Geoscience Canada Reprint Series 4 c
c
diffusion will diss ipate concentration eupelagic or true pelagic sediments. cover (Figure 5), the third group in more
C
anomalies for a given period of time They represent the most slowly deposi- reactive pelagic sediments. The first r
"-
(equation (8), Table 3). For a period of
one million years diffusion path lengths
ted sediments on earth including the
brown abyssal clay, the prototype of a
group is convection-controlled, the sec-
ond diffusion-controlled and displays c
for young, unconsolidated sediments pelagic sediment, with sedimentation c
are characteristically between 100 and
200m (Table4), which exceed the thick-
rates of less than 5 rn- Ma-'. Biogenic
pelagic sediments are deposited some-
1\
25
o c
ness of most pelagic sediments accu-
mulated in a million years. It is, there-
what faster, at rates ranging from less
than 10 rn- Ma-' up to 100 m -Ma-' for
20

SITES I I1HOUI mDIUl

SllES11TH ;UDlUT
c
fore, entirely feasible that in pelagic most modern siliceous and calcareous
15 c
sediments the sediment-water inter-
face and the igneous rocks (layer 2) of
oozes (e.g., Scholle et et., 1983, p. 640).
Pore-water profiles for pelagic sedi- c
the oceanic crust are still in diffusive
communication, even after deposition of
ment sites of the DSDP display three
principally different trends: those with
10
c
several hundred metres of sediment. no pronounced gradients at all (type 1); c
This will always be the case, if the diffu-
sive communication length Z, which is
others with vertical gradients but linear
correlation between major ions', espe- c
the diffusion coefficient Os divided by cially calcium and magnesium (type 2); c
sedimentation rate CAl (Gieskes. 1975),
exceeds sediment thickness.
and a third group with gradients but no
linear correlation between the major Figure 5 Frequency distribution of drill
sites with and without concentration gra-
c
I. LOW TO INTERMEDIATE
ions (type 3). The first group of sites
occurs close to mid-ocean ridges
dients for major pore water cations in pe- c
SEDIMENTATION-RATE BASINS
(Pore-water Profile Types 1 to 3)
and has a limited sediment thickness,
generally less than 200 m, the second
lagic (and hemipelagic) sediments as a
function of sediment thickness on basaltic
crust (based on DSDP legs 1-85, data for
c
These have sedimentation rates of less group at greater distances from the legs 1-53 compiled by McDuff, 1981). n -
than about 50 m- Ma-1 characteristic for ridges and under a th icker sediment number of drill sites.
c
pH
C""
Sal
I%.'
a N. K Sr Co ...
1""""'.1
Alk Si0 2 6"01%.1 c
781620242832361418400 10IS0.0S0.2
r1i iii i I ~ r-""1n
101S203040!iO 02040
t'"T'TT"1r-T'l r"'"""'T"'"" ~
o,--,-,10 00.1
.,-, o 1020 0.7
rTTT"T'1 j ,
1.0
i i i 1'1
(SMOW)
1.201.0 c
1~ t c
200t
3001
400 ~
)J I \i
~~
~f '\ \( r
\.. I I
495
c
c
c
0.1 0.20.3
"T'T'T"M
0.1 ' 0.3 ' O:S ' 0:7 c
781620 24 28 32 36 1418400 10 0.05
ni i i i i i'r--n~n n
0 10 20 3040 !i080 70 408080100 101520 020.3 SO.5 0.7
t'T"1i i i i · i i i I i i i i i ~ -r-r-1n t"""T-r-1
01.0
~
3.0
C

~:l/!l!t;; W
E

c
400~ ,...., I"TI ~ iii ,,......,...., ,.-,
c
711620242132311418400 10 0.05
10 14 0 1020
010
02040 0 5 10 15 0 0.1 0.2
20304OtiO 020 408080- 5 101600.10.20.305150.10.70.8
0.4
o 1.0 0.3 c
or
,.,1 i , , I

r
il~""""r-

I~I
M rT"1i , I , , , iii i ~,..--.r--"'T" ",......., ~ ~

c
~1 \\
! I
J 100 ~ j Ii e
I~!(,) 1 497 c
I: ~t ]
Iil0
n
0.1
~
0 1020
i
o "un 0 Ii '0
c
c
Figure 6 (Above and opposite page) Pore-water chemistry and Isotopic composition of DSDP drill sites 495 (pore-water profile, mixed
C
type 1 & 2 & 3), 496 (type 6), 497 (type 6), 565 (type 6), 568 (type 6), and 570 (mixed type 4 & 6). Sites 495, 496, 497 (leg 67)(Harrlson et al.,
1982), Sites 565, 568, 570 (leg 84)(Hesse et aI., 1985; carbon-isotope ratios from Claypool et aI., 1985) on Middle America trench slope and
l
oceanic crust of the Cocos plate (site 495) off Guatemala. Sites 565 (continental slope off Nicoya Peninsula, Costa Rica) and 568: squares C
identify In situ water samples.
C
C
(
c Early Diagenetic Pore Water/Sediment Interaction 287

c
r Sal. cr K+ Sr 2 + Ca 2 + A1 3 +
c- pH Alk . SO/- H4Si04 6 '8 0

rmf$f l ~MI ~/OO SMOW)


(g/kgl (g/kgl (mMI (meq/kg) (mMI

o ,~ ty.....,..,,0:--~=-30
.-=-~. '~'
o
,
51015 0510'5200.40.60.81 .03.05.0".00.'0+3.0
I

1: \~~ :f~ "'


1\ 1
r
o ~ :. ~ 't ( 1\ > 4
200

( 300 81216 6510 0:20:4


I ,

o
o
o
o •
o _ _I

o 510
o
o 30

o
o
o
o
CH 4 ~D fl/ool CH ~ 13 C (" '00 1 tC0 ;, t 3 C to 001 tCO? ImMI

o 0 i
-200
, -180 -160
4
-80
i
-60 - 40
I i
,, -20
i
2

.' . 0
i
-20 . 40
, , , I.
0
i
•• •
, 20 40
I
60
i , 80
I
:00
i

o 100
• ••
••
• 585

o No dala


••
• •
••
o 200

• • ••
o 300

o , ,. 40, 40 tOO
o -200 -180 -160 I -80 - 60 -40 -20 0 -20 0 20 60 80
'. '-' i

.\
i_I i
0
•• ~ •• • •
o :§ 100
••••
•• ••
•• •
•• • 588
o .
~
Q
200 ••
•• • •
• •

\
~

o •• •
E
s
15
300 ..: • •
\
D
.Q
:> • •
'" •
e 400 • •

t OO

200
,- 200

i


r
••
••
-180 - 160
i i
-80

•••
,
,\ i ,
-60 - 40
i • •
-20
i
0
,
••



- 20
, ,-40, 0
i
20
i .'


, 60
••

40


I
80
i ,
tOO

570

300 .(
~. • ."\, •
• •

\ • •
400 •
c
288 Diagenesis Geoscience Canada Reprint Series 4
(
C
oxic to suboxic diagenesis. The third vection is no longer operative , diffusion to the different scales used for Sr2 + and
C
group is characterized by suboxic (to sets in to bridge the concentration dif- Si02 compared to most other ions.) C
anoxic) diagenesis and is react ion- ferences between seawater at the top Si02 , Sr2 + and Ca2 + are species in-
dominated, but formerly may have and hydrothermally altered fluids at the volved in active diagenetic reactions C
been convection-dominated.
Convective Pore-water Circulation
base of the sedimentary section, thus
smoothing out concentration gradients.
taking place in the sediment column
at the time of drilling. Strontium is re-
C
on the Flanks of Mid-ocean Ridges In discharge areas, porosity-reducing leased by carbonate recrystallization. C
(Type 1 Pore-water Profiles). processes, such as recrystallization Its maximum near 250 m sub-bottom
The first type of behaviour, i.e., profiles and cementation , may be accelerated depth occurs approximately at the level C
with no gradients for most ions, is illus-
trated by DSDP site 495 (Figure 6).
due to elevated temperatures sealing
off convection early, i.e., even under a
where the transition from calcareous
ooze to chalk is observed in the cores.
C
McDuff (1981) has argued that the relatively thin sediment cover. Thus dis- Silica concentration profiles are C
straight vertical profiles of seawater charge-related straight-line profiles known to be highly variable with depth
composition are probably caused by would not be expected. and dependent on lithology; site 495 C
convection of seawater through the
sediment column. This is in line with
An alternative explanation for the
straight-line profiles is by diffusion
is an excellent example. Increases
in dissolved silica in the upper few
C
geothermal studies (Anderson et et., from seawater reservoirs located both 100 m of biogenic pelagic sediments C
1977, 1979)which suggest that heat loss above and below the sediment section are related to the dissolution of opal-A
on the flanks of mid-ocean ridges is by (McDuff, 1984). This is based on the of the tests of siliceous organisms ,
C
convective rather than conductive trans- discovery of cold seawater circulating mostly diatoms and radiolaria, while C
port and that the heat-transporting flu- in the highly permeable uppermost ba- marked decreases in silica which occur
ids must percolate through the sedi- saltic oceanic crust under a thin cover at greater depths are related to the rep- C
ments (layer 1) of the oceanic crust.
Postulated convective flow cells have a
of young pelagic sediments which form
a relatively impermeable lid (Langseth
recipitation as opal-CT. In site 495, the
marked decrease in dissolved silica
C
diameter (or wavelength) of 5 to 10 km et a/.• 1984). near 325 m sub-bottom coincides with (
and several of them may occur side-by- Site 495 on the Cocos plate off the first porcellanite nodules observed (
side on the ridge flanks thus extending Guatemala is located about 20 km in this hole, conf irming the relationship
from the ridge crest outward to base-
ment ages of up to 80 Ma. The cell
oceanward from the Middle America
Trench and bottomed in basalt of Early
with opal-CT precipitation. The diagen-
esis of siliceous oozes and associated
C
structure requires that regions of dis- Miocene oceanic crust. At this site con- mechanisms of chert formation are dis- C
charge from the crust alternate with re- vection may have ceased not too long cussed in a separate article (Hesse,this
gions of recharge, but it is not clear how ago, but the previous convection-con- volume, p. 227-251.) C
the former manifest themselves in the
pore-water chemistry except at the
trolled profiles are still preserved due to
a lack or sluggishness of reactions in
Thus the two dissolved species of site
495 which display pronounced maxima
C
ridge crest where fluids are issued in layers 1 and 2. Its straight-line pore- in their concentration profiles, Sr2 + C
the "black and white smokers" of the water profiles with near seawater con- and Si02 , are clearly involved in ongo-
hydrothermal vent system (Edmond et centrations for most ions (Harrison et ing reactions. The convective flow sys-
C
a/., 1979,1982; VonDamm et a/., 1985a,
1987). Active hydrothermal systems
a/., 1982)are the more remarkable, be-
cause major lithological changes occur
tem appears to have ceased to operate
not too long ago at this site because it .
C
that have been drilled at various sites by in the sediment column penetrated by failed to obliterate the effects of these C
the DSDP are characterized by ongoing the drill - from Pleistocene to Upper reactions, and the reaction products
reactions in the sediments (Von Damm Miocene olive-grey hemipelagic mud liberated are redistributed by diffusion
E
et al., 1985b)or by intrusions of igneous (upper 170 m) through Middle Miocene (as in the case of Sr 2 +) or consumed by C
dykes and sills producing complicated brown abyssal clay (10 m) to Middle to the precipitation of solid phases (as in
pore-water profiles that are far from Lower Miocene white, pale brownish the case of Si02 ) . Site 495 thus, in fact, C
straight lines (pore-water profile type and greenish calcareous ooze and is a mixed site showing the effects of
8). Discharge associated with simple, chalk (120m)and pale brown to purplish former convection, of diffusion and of
C
convection-controlled vert ical profiles manganiferous chalk and limestone (30 ongoing reactions. Its sediment thick- C
may have been encountered in one
area at 20 0 S on the East Pacific Rise
m) overlying the basalt. As Figure 6
shows, none of the major ions seems to
ness exceeds 400 m, which is higher
than for most convection-controlled c
(Bendereta/., 1986),but only the upper-
most 2 m of the sediment were
be affected in its vertical trend by any of
the lithological boundaries (at 170 m,
sites (Figure 5), but this is notsurprising
in view of the mixed nature of this site.
e
sampled. For discharge areas, which
are probably much narrower and more
180 rn, 399 m and 428 m depth), al-
though these are relatively sharp.
Diffusion-controlled Pore-water
Trends (Type 2 Pore-water Profiles).
c
focussed than the broad recharge The only exceptions are silica and The brown abyssal clay is a good exam- l
areas, non-linear profiles would be ex-
pectedwith greater depth of penetration.
strontium and, in part, calcium, which
display appreciable variations although
ple for diffusion-controlled pore-water
profiles. It is virtually free of organic
C
Once the sediment cover on the these are also not related to any of the carbon. Any organic matter that may be (
oceanic crust exceeds a certain thick- major compositional boundaries be- deposited is removed by oxidation in
ness, it becomes a seal for convection tween the lithologic units. (These varia- the oxidation zone. A few tenths of a C
due to porosity reduction. When con- tions are exaggerated in Figure 6 due percent or less of highly refractory C
C
C
c
c Early Diagenetic Pore Water/Sediment Interaction 289
c
c organic matter may remain, according and led to different hypotheses. Sayles Ca and Mg are essentially diffusion-
c to analyses of many drill holes in the
Pacific (Initial Reports of the DSDP). In
and Manheim (1975) thought that the controlled. Considerable variations in

o the absence of reactive organic carbon,


diagenetic formation of high-magne-
sium calcite was responsible for the
the numerical value of the diffusion co-
efficients result from changes in poros-
c which is the main reducing agent in
marine sediments, iron and manga-
ACa-AMg correlation, a conclusion
which, if substantiated, would have
ity, temperature and tortuosity with
depth and these can be measured di-
o nese remain in their oxidized, higher va-
lence states in the sediment which
been in conflict with the common expe-
rience of carbonate petrologists that
rectly (porosity, drill hole temperature)
or indirectly (tortuosity) using electrical
o therefore retains its brown colour dur- high-Mg calcite transforms diagenet- resistivity determinations. By setting
ing burial. During later stages of burial ically to low-Mg calcite, but not vice the velocity of advective flow v and the
the sediment may gradually change to versa. Because the starting material in contribution from reactions R in equa-
c red when the brown iron hydroxides deep-sea sediments is low-magnesium tion (9) of Table 3 equal to zero, that is,

c are converted to hematite. Although


freely dissolved oxygen may disappear
calcite, a stable phase would have been
replaced by a less stable phase during
assuming that the two elements Caand
Mg behave conservatively and do not
o completely from these pore waters at
deeper burial levels, they do not nor-
progressive diagenesis, in violation of
Ostwald's rule. Donnelly and Merrill
experience lossesto, or additions from,
the sediment column, McDuff and
o mally become reducing enough to
change the Fe3 + to Fe2 + and thus
(1977) related the magnesium de-
crease with depth to silica diagenesis.
Gieskes (1976) were able to match cal-
culated profiles with the measured
leave the red colour unchanged. Lerman (1975, 1977) and Lerman and ones. Thus, only a diffusive flux seems
o Various other types of pelagic sedi-
ments besides the brown abyssal clay
Lietzke (1977) considered the effects of
diffusion but neglected to include vari-
to be important. Successful modelling
suggests that such an interpretation is
o display diffusion-controlled pore-water able diffusion coefficients which forced acceptable; it does not prove that it is
o profiles. These are characterized by lin-
ear correlation between the concentra-
them to invoke reactions in the sedi-
ment to explain the gradients. In their
the only possible one.
What arethe reactions in the basaltof
tion changes for calcium and magne- reevaluation of the problem, McDuff the oceanic crust that lead to the re-
sium as well as for oxygen isotope
o ratios. This phenomenon, particularly
and Gieskes (1976) and McDuff (1978,
1981) included depth-variable diffusion
lease of Ca and the consumption of Mg
underlying the linear correlation be-
o the inverse relationship between cal-
cium and magnesium (Figure 7) had at-
co-efficients, with the result that they
were able to argue successfully that
tween the changes (ACa-AMg)of these
two elements? These are generally
o tracted considerable interest in the past these profiles with coupled changes for hydrolysis reactions of the alumino-

Alkalinity

o o,..---
i meq l-I)
2 4
Sulphate (mM) Calc ium and magnesium (mY)

80
o I
,...,--r-~~.• ",~T"'>
I

o 200
o IT
o 400
ill
o 600 TIl"
o
o E

o -
s:
Q
QI
o
Stront rum (mM)

02 04 06
Potassium (mM)

o
I .-+-..:,.,I
l' •
~

eI• \---<,
200 ~
8
!•
C
r.
400 f-

600 L..-
f-
(·l

t.••
...J
------
e:::.
••

Figure 7 DSDP site 528 on the Walvis Ridge, South Atlantic, with linear correlation between downward Ca2 + increase and Mg2+ decrease
(pore-water profile, type 2). Dissolved Mg2 + drops rapidly to zero below the first basalt, at the same level Ca2 + increases rapidly. Dissolved
Sr2+ shows typical trend for pelagic carbonates with a maximum around 100 m, resulting from carbonate dissolution. Lithology: I: calcareous
ooze, II: nanna-fossil ooze and chalk, III: chalk with interbedded turbidites, IV: interbedded sedimentary rocks and basalt. (From Gieskes,
1983).
c
290 Diagenesis Geoscience Canada Reprint Series 4
(
C
silicates of the primary basaltic rocks. and Mg2+ that are linearly correlated is Miocene time. Hydrogen isotope ratios
C
They produce cations, hydroxyl ions their correlation with changes in oxygen of these pore waters also decrease C
and silicic acid as soluble species. isotope ratios (Figure 8). Often these downward at a rate of about eight times
Mg2+ produced in these reactions is display a distinct downward decrease of the 0180-decrease (Figure 9a) corre- C
taken up entirely by the basalt in sec-
ondary minerals such as brucite or sap-
0180 resulting in moderately negative
values at a few 100m subsurface depth.
sponding to the isotope fractionation
effect associated with evaporation of
C
onite. The hydroxyl ions produced are As pointed out by Lawrence et a/. (1975) seawater. The absolute values of the C
largely removed from solution by pre- and Gieskes and Lawrence (1981), the 0180 shift are small, however, amount-
cipitation with excess Mg2+ , i.e. , the only quantitatively important fractiona- ing to not more than 0.5%0 over 250 m
C
Mg2+ supplied by diffusion. In this way tion mechanism in pelagic sediments depth (Figure 9b).ln their detailed study C
basalt alteration provides a sink for that could bring about a preferential re- Bath and Shackleton compared the
Mg2+ and also a source for Ca2+. Ac- moval of heavy oxygen from the pore pore-water data with the 0180 values for C
benthonic foraminifera from the same
cording to McDuff (1981), Mg2+ uptake
may exceed Ca2+ release at low hydro-
water is the formation of phyllosilicates
in alteration reactions of basaltic miner- hole (Shackleton et a/., 1984)which dis-
C
lysis rates. Because the reactions af- als and glasses, either in the igneous playa downward decrease of 1.4%00180 C
fecting the basaltic rocks may also oc- part (layer 2) of the crust or in volcani- over the same depth interval. The nar-
cur in the lower parts of the sediment clastic sediments (layer 1). rower range forthe pore water is attribu- C
column, if these are rich in volcanic ma-
terial, dissolved Mg2+ may be reduced
It has been suggested, however, that
slight downward decreases in the oxy-
ted to diffusive dissipat ion. This raises
the difficulty that the diffusion coeffi-
C
to zero above the sediment/basalt gen isotope ratio observed in pore cient required to match the observed C
boundary. In this case, the continued waters of Miocene pelagic carbonates profile has a value of only 10-7 cm2. s-\
increase in Ca2+ downward, and the in the South Atlantic (hole 525B, leg 74 whereas diffusion coefficients com- C
hydroxyl production associated with it,
are compensated by a flux of Na + sup-
of the DSDP on the eastern flank of
Walvis Ridge) represent a fossil sea-
monly found for the types of sediments
in question are in the range of 10-5 to
c
plied from seawater by diffusion into the water trend reflecting the withdrawal of 10"6. With these higher coefficients the <:
oceanic crust, which is reflected in a
distinct depth gradient for Na + .
isotopically light water from the ocean
and storage in continental ice caps
gradient would have been smoothed out
at least 30% more. A large reservoir of c
The strongest argument in favour of
diffusion-controlled gradients for Ca2+
(Bath and Shackleton, 1984). An ice cap paleo-oceanwater with low oD and 01 8 0 c
started to form on Antarctica in mid- values might exist, however, in the
c
c
c
c
c
c
C
E
C
C
C
C
c
e
(
c
c
c
c
Figure 8 Negative correlation between dissolved Ca concentration and 6180 of DSDP pore-water profiles. (Modified after Gieskes, 1983;
data from Lawrence and Gieskes, 1981). c
c
c
(
( Early Diagenetic Pore Water/Sediment Interaction 291
(,

c (a) basalt of layer 2 of the ocean crust and


c might allow higher gradients in sedi-

o
(
o
+ +
+
+
+
ments of layer 1 to persist, as sug-
gested by Lawrence and Gieskes(1981),
iftransport in layer 2 is still by advection
and in layer 1 by diffusion . The 018 0
values show a linear correlation with Ca
(Figure 8, interstitial water data for Ca in
( site 5258 from Gieskes eta/., 1984)and,
c /
alternatively, could be related to altera-

+
~/
, tion reactions in the volcanic basement,
C- -4
whose products are distributed upward
by diffusion. However, this does not
O explain the hydrogen data, because
o no hydrogen-isotopic fractionation is
expected for this process. All known
o hydrogen-bearing low-temperature sili-

o cates are depleted in deuterium relative


to seawater or interstitial waters (Savin,
o 1980). oD values of interstitial waters
are, therefore, more reliable indicators
o for the isotopic composit ion of the origi-

o %0 POB +3.2 +3.0 +2.8 +2.6 +2.4 +2.2 +2.0


nal connate water than 0'80 values.
Withdrawal of fresh, isotopically light
%0 SMOW +0 .2 o -0 .2 -0.4 -0.6 -0.8 -1.0 water from the world ocean during gla-
o cial times is also the basis for the oxy-
gen isotope stratigraphy of the Plio-

o EE
Pleistocene (e.g., Shackleton and Cita,
1979). Evidence for an associated in-
o 40
EE
(b)
crease in seawater chloride has been

o Elk EE I
I
presented (McDuff, 1985).
Reaction-controlled Pore-water
o E
80 I
I Profiles in Suboxic (to Anoxic)

o ..
s:
Co
831
I
I
Pelagic to Hemipelagic Environments
(Type 3 Pore-water Profiles).

o Q)
0 120
831I
These have somewhat higher organic
matter contents than the previous
o ..E
0 I
I
,0= -7 2 ·1
group (type 2) but still low enough
values so that diagenesis remains oxic
o 0
.c 160
.iJ
I
I
I
10 em 5
to suboxic (Figure 4). In other words,

o :l
en I
I 83
the oxidant demand is such that the
free oxygen reservoir will be depleted
o 200 I
I
I
83 but not the nitrate reservoir. Many of the
DSDP drill sites grouped as type 2 or
o = ·6
I
2.1--.1
type 1 sites may in fact be mixed sites

o 240 D 10 em
I
I
5
EE
and belong to group 3, because the
upper few metres of the sediment col-
o I
I
I EE
EE umn, which are often left unsampled,
may show the effects of suboxic dia-
o 280 I

Figure 9 (a) Oxygen and hydrogen isotope data for DSDP hole 525B from Bath and
genesis. Deeperdown in the holes, how-
ever, these effects may have been
6 Shackleton (1984). The error bars are derived from the topmost 12 samples (small crosses), obliterated by diffusion. Piston-core
which all plot close to 0 on both co-ordinates. An error ellipse (1 standard deviation) has been
l drawn around the mean of these values and the diameters of this ellipse have been used for
studies with closely spaced samples in
the upper few metres of the sediment
( the errorbars of the remaining samples assuming that the variability among the top samples is
are the appropriate approach to this
a reliable estimate of the analytical uncertainty. The dashed line has a slope of 8, indicating
environment. MOilerand Mangini (1980)
that the isotopic trend reflects evaporation of seawater. (b) 3-point running average data
(open circles) for pore water 0' 80 values and (squares) for benthonic foraminifera from the estimate that sedimentation rates of
same hole. The less steep gradient for the pore-water data is attributed to diffusive dissipa - less than 40 m- Ma" are required for
tion. The two solid curves are calculated diffusion-controlled trends resulting from an suboxic diagenesis . For higher rates,
assumed isotopic composition of mid-Miocene (14 Ma) ocean water of -0.9%0 018 0 and two increased organic matter content will
different values for the average sediment diffusion coefficient. eventually exhaust the nitrate reservoir

l
c
292 Diagenesis Geoscience Canada Reprint Series 4 c
c
and establish anoxic conditions of the effect on Ca 2 + concentration gra- appears to be associated with a max-
c
sulphate reduction zone. dients. Recrystallization of deep-sea imum in the recrystallization rate. From c
"Mixed" site 495 apparently belongs
to this latter category. A close look at
pelagic carbonates in the subsurface
occurs because the small and delicate
this maximum, dissolved Sr2 + is trans-
ported by diffusion both upward toward c
Figure 6 reveals that some of the dis-
solved species, especially ammonia,
tests of foraminifera and coccoliths,
which are the only major carbonate con-
thesedimentlwater interface and down-
ward toward a sink deeper in the sedi-
c
phosphate and alkalinity show slight stituents of pelagic sediments, have a ment column or the basaltic oceanic c
enrichments whereas sulphate shows
a slight decrease near the top of the
large reactive surface area easily sub-
jected to pressure solution. Their Sr
crust. The ooze/chalk boundary may be
viewed as a diagenetic front which c
sediment column. This reveals that the
typical organic-matter decomposition-
content is three to five times higher than
that of the inorganic calcite reprecipi-
moves upward through the sediment
column as burial proceeds (Gieskes et
c
reactions discussed before do in fact tated from solution (Baker et al., 1982; a/. , 1986). Below the boundary, in the c
occur at present in this site, albeit appar-
ently rather sluggishly. This is what is
Elderfield et a/., 1982). Thus a distinct Sr
signal is observed, whereas the calcium
chalk, recrystallization is slowed down
considerably. According to Stout (1985) c
expected, because the hemipelagic (and magnesium) concentration is not the dissolved Sr2 + profiles with the c
muds in the upper 100 m of the column
still contain between 1 and 2% organic
much affected, particularly not in low
sedimentation-rate sites with low alka-
gradual downward increase toward the
maximum can be successfully model- c
carbon (Figure 10). They will have un-
dergone at least the first two stages, but
linity levels. In these sites about the
same amount of calcite that goes into
led assuming diffusive transport and a
constant production rate of Sr2 + for the
c
also part of the third stage of bacterial solution appears to be immediately re- reaction term in the general diagenetic c
organic matter oxidation, although not
much of this can be seen because most
precipitated, often as overgrowths on
single-crystal skeletal elements of the
equation (equation 9 in Table 3). As
shown by Baker et a/. (1982)this would c
of the existing gradients were probably
dissipated initially by convective flow
Coccolithophorida, especially discoas-
ters (Figure 12).In site 495, a small Ca2 +
still allow for variable recrystallization
rates, because the inorganically pre-
c
and later by diffusion. maximum is associated with the Sr2 + cipitated calcite consumes much less
In certain regions alternating zones
occur of oxic and suboxic diagenesis on
maximum (Figure 6), possibly indicat-
ing that in the absence of a diffusion
Sr2 + than is released by the dissolving
biogenic calcite. The lower sink toward c
the one hand and anoxic diagenesis on
the other, which show up in vertical pro-
supported Ca-flux from the basaltic
basement a signal stemming from the
which dissolved Sr2 + diffuses down-
ward, is provided by volcanogenic sedi-
c
files, e.g., as alternating brown and recrystallization reaction may still be ment deeper in the column or basaltic c
green layers and corresponding varia-
tions in pore-water chemistry. They are
preserved .
The maximum of dissolved Sr2 + near
basement which behave similar to mid-
ocean ridge basalt during low-tempera- c
caused by temporal fluctuations in or- the calcareous ooze/chalk boundary ture alteration. The rate of carbonate c
ganic mattersupply, which,for example,
may be associated with the influx of Corg(%1
c
rapidly deposited, organic-matter rich,
c
terrigenous muddy turbidites into an en- 0 1 2 3 4 2 3 4 5 o 1 2 3 o
-=:ttl
1 2 3 4 0 1 2 3

c
t
0 i
i i
I
~
I i i i
vironment of pelagic sedimentation
(Colley et a/., 1984). If the turbidites are .> I

~!
C
~I
~l
50
rich enough in organic matter, their

~ .>:
t
chemical signature may not be oblite-
rated by diffusion although an oxidation 100
E
front may move down (or up) from the
lj J I C
overlying (or underlying) pelagic sedi-
ment and turn the upper (lower) part
of the green or grey turbidite brown
(Wilson et a/. , 1985).
]

...
£
~
§ 200
150

~II
•.,. Cf-\
-----t-.
\J 1i •
I
• I C
C

?!
C
Recrystallization of Biogenic Pelagic
carbonates.
Biogenic pelagic carbonates provide
another example of diffusion- and reac-
j
.i>
ci! 250
fl
• I1
~
( I
c
e
tion-controlled pore-water profiles in 300 J i
.---1 • I
c
~ I
low to intermediate sedimentation-rate
..-1
areas, which unveil the role of solid sedi-
I c
> ~ l
350
ment constituents other than organic
matter in early diagenesis. It may be I
I c
surprising that the recrystallization of
c
400
496 497 494 499 495
pelagic carbonates which is reflected by
adistinctSr2 + anomalyata 100toafew
100 m subsurface depth (Figure 11 a)
Figure 10 Organic carbon distribution in DSDP drill sites on the middle (496, 497) and
lowerslope (494) ofthe Middle America Trench,in the trench (499) and on the adjacentoceanic
c
does not seem to have a significant crust of the Cocos plate (495) off Guatemala. (From Harrison et at, 1982). c
c
c
c
( Early Diagenetic Pore Water/Sediment Interaction 293
(
(
recrystallization in pelagic sediments heavier in strontium isotopes during the paleo-seawater curve (Figure 11b).
( depends also on sedimentation rate last 100 Ma toward the present, the Sr- The dissolved 87Sr/ 86Sr ratios are too
(Gieskes and Johnston, 1984), which maximum is a source of relatively light low to be due to upward diffusion, partl-
G controls the production of CO~- or Sr isotopes for the section above it and cularlyas insufficient carbonate is avail-
HC03' in the sediment, as discussed in of relatively heavy isotopes for the sec- able for recrystallization. Here, altera-
(' the section on "early diagenetic organic tion below it. tion of volcanic sediment particles with
o matter oxidation". The Sr2 + maximum
occurs thus at greatly variable subsur-
DSDP site 289 on the Ontong-Java
Plateau in the Southwest Pacific differs
low Sr-isotope ratios (of about 0.704)
must be invoked as the dominant source
( face depths. from other carbonate sites in thatthe Sr- of the anomaly (Gieskes et al., 1986).
c Direct evidence for the diffusive
transport of Sr2 + in pelagic carbonates
isotopic composition of the pore water
below the ooze/chalk boundary is very
Alteration of volcanogenic sediment as
a source of a light Sr-isotope signal is
( is provided by strontium isotope ratios. close to the paleo-seawater curve (Fig- often accompanied by magnesium

c Sr-isotope curves for the pore waters


of pelagic carbonates break down into
ure 11 b). Inthis site, maximum dissolved
Sr-concentrations are reached at about
losses from the pore water in excess to
those attributable to diffusive fluxes.
o two parts (Figure 11 b). In the upper part
above the Sr-maximum 87Sr/86Sr ratios
400 m sub-bottom and below this depth
no significant decrease is observed
OtherEarly Diagenetic Mineralization
Reactions in Pelagic Sediments.
o are generally lower than the contempo- (Figure 11 a) suggesting that the down- Zeolites provide additional, well-docu-

o raneous seawater curve of Burke at al.


(1982) and Palmer and Elderfield (1985).
ward diffusive flux in this thick chalk-
limestone section is very small or nil-
mented examples of early diagenetic
mineralization in slowly deposited pe-
o Below the maximum they tend to be
higher than or equal to paleo-seawater
in line with the isotopic data which
also suggest that in the chalk section of
lagic sediments, particularly volcano-
genic pelagic sediments (Kastner and
o ratios for coeval sediments. This re-
quires both upward and downward
this hole isotopic equilibrium exists
between the pore waters and their host
Stonecipher, 1978). The crystalliza-
tion of zeolites from volcanogenicmater-
() diffusion of dissolved Sr2 + from the site sediments . ial proceeds through the formation of
o of maximum recrystallization (i.e., the
dissolved Sr-maximum), where the iso-
In carbonate-poor sediments of sites
541 and 543 near the toe of the Lesser
palagonite, a yellow-brownish alteration
product of volcanic glass, which appears
topic composition is closest to that of Antilles island-arc slope, Sr-isotopic to be a common precursor of zeolites.

o contemporaneous seawater. Because


seawater has become increasingly
ratios of the pore waters in the upper
part of the holes fall much below the
The downward decrease of K + in the
pore waters of many pelagic drill

o (a) Sr 2+ (mM)
(b)
rn.o.
o 0.6 0.8 1.0 1.2
o 20 40
o 100
o .709
o 200

o 300
o
o E
400
.708
o ~

-
Cf)
:i: 500 CD

o
CI)
a. 0
<,
~
CP
0600 ,..Cf)
C 288
CI)

l 700
e 800
.707 • = 525
0 =528
C 0=543
o = 289
900 ... = 315
~ = 357
1000 • = 541
.706
Figure 11 (8) Typical dissolved Sr2 + concentration profiles in pelagic sediments, Pacific drill sites, DSDP. (Modified from Baker at aI., 1982).
(b) Sr-isotope ratios versus sediment age in pore waters from various DSDP drill sites and Sr-isotope curve of seawater (stippled) for the last 80
Ma . (From Gieskes et at, 1986).
"

c
(
294 Diagenesis Geoscience Canada Reprint Series 4 (
(
(
sites may be related to the formation of formation of smectite (Helm, 1985) additional source is marine organic
the main potassium-bearing zeolite, might be sufficient to account for the matter which is supplied at increased C
phill ipsite (K,Ca)AI 3Si sO'6 . 6H 20. dissolved aluminium decrease. rates in areas of high biogenic surface
Other common zeolites formed during These examples show that in a given productivity associated with regions C
early diagenesis in pelagic sediments drill site usually several mechanisms of upwelling of nutrient-rich deeper (
such as clinoptilolite and analcite leave contribute to the make-up of the pore- waters. Because zones of upwelling
a less characteristic imprint on pore- water chemistry. In low sedimentation- are concentrated around the margins (
water composition . As Kastner and rate environments such as the pelagic of the continents, continental slope and
Stonecipher (1978) have shown, phil- realm , convection- and diffusion-domi- outer shelf sediments may contain sig-
(
lipsite is most abundant in the youngest nated pore-water profiles prevail, but nif icant proportions of marine organ ic (
sediments at shallowest subsurface reactions may significantly modifyverti- matter which is highly reactive and has
levels and decreases in abundance cal trends as shown for Sr 2+, K + and a high potential for liquid hydrocarbon C
with age and burial depth, whereas clin- Si02. Thus every drill hole and every generation.
optilolite shows the opposite behaviour. element has to be investigated specif- In high sedimentation-rate basins, the C
The transformation of zeolites into
K-feldspar with progressive burial has
ically. In the following section, reaction-
dominated pore-water trends will be
role of diffusion in smoothing out con-
centration anomalies is suppressed,
C
been documented repeatedly and is analysed which are characteristic for because sedimentation rates exceed C
another sink for K + , as are adsorption high sedimentation-rate environments. diffusion rates. In addition, anomalies
and ion exchange with clays. Some of these can also be found, how- produced by ongoing reactions will be
C
Widespread neoformation of clay ever, in low-rate environments as exam- much more pronounced than in low-rate C
minerals does not seem to occur in ples of the foregoing discussion have basins because of the elevated con-
pelagic environments at shallow burial shown. centration of reactive organic matter. C
levels (Kastner, 1981). " Rev ersed Initial organic carbon contents of these (
weathering" (MacKenzie and Garrels, II. HIGH SEDIMENTATION·RATE sediments often exceed 2 or 3% (Figure
1966), which would have involved clay BASINS 10).
mineral reconstitution in the oceans
through the uptake of silica and cations
These are characteristic of the conti-
nental margins, where sedimentation
Pore-water Trends in Continental
Margin Environments: c
by amorphous aluminosilicates, has not
been found to occur on a large scale.
rates up to 500 rn- Ma-' and more, i.e.,
rates two orders of magnitude higher
Major Element and Isotope Chemistry
in Anoxic Sediments
c
Small amounts of very fine-grained than for the brown abyssal clay, are no (Type 4 Pore-water Profiles). c
smectite may form, however, in early
diagenetic environments (Chamley and
exception. High sedimentation rates at
the continental margins result from the
The sequence of organic matter oxida-
tion reactions discussed in a previous c
Millot, 1972; Johnson, 1976; Moberlyet
a/., 1968; Hein et a/., 1979a) and the
increased input of terrigenous material
which tends to be rich in terrestrial or-
section is best reflected in the vertical
trends of pore-water chemistry in ra-
c
«5'80 and Mg2+ decreases mentioned ganic matter. Rapid burial enhances pidly deposited sediments of the conti- c
earlier most likely involve newly formed
clay minerals besides zeolites .
preservation of this organic material. An nental margins. These sediments pass
c
DeLange and Rispens (1986) related c
sharp decreases in dissolved silicon
and iron below mud-turbidites of the c
Nares Abyssal Plain to the precipitation
of small quantities «0.1 wt.%) of an
c
amorphous Fe-Si mineral, possibly an c
iron-smectite precursor. Decreases of
dissolved aluminium at shallow subsur- c
face depths may also require the forma-
tion of small amounts of authigenic clay
c
minerals (Stoffyn-Egli, 1982) and this c
mechanism may also operate at deep-
er levels in the subsurface (e.g., high- c
sedimentation rate DSDP sites 565 and
568, Hesse et al., 1985; Figure 6). The
c
formation of AI-rich di-octahedral chlo- c
rites was suggested by Mackin and Aller
(1984) for shelf sediments of the East c
China Sea where other aluminium re- c
moval mechanisms such as complexa-
tion with dissolved organic matter or c
adsorption on amorphous silica sur-
faces are less likely to occur, whereas in
Figure 12 Calcite overgrowth with well-developed crystal faces on discoaster. Distal ends
of originalrays of discoaster markedby arrows. DSDP site 199, Caroline AbyssalPlain, 6090 m
c
the above DSDP sites these and the water depth, Early Pliocene carbonate turbidite, 59 m sub-bottom depth. c
c
c
c
r Early Diagenetic Pore Water/Sediment Interaction 295

c
c very rapidly through the oxidation and region as sulphate is absent in samples sively heavier, so does the methane
('
I....
nitrate reduction zones during burial taken below that depth. Carbonate produced from it at deeper levels.
and essentially experience anoxic dia- alkalinity rises to more than 120 milli- Through this feed-back mechanism (a
o genesis. The main chemical species re- equivalents (meq)- kg" between 23 and Rayleigh-distillation process) the O'3C-
leased to the pore water from the micro- 45 m sub-bottom in hole 496 - a record curves for both methane and dissolved
bial breakdown of organic matter and value only exceeded during recent drill- carbonate show parallel trends (about
o the concomitant reduction of oxidants
are the nutrients EC02 (including the
ing on the Peru continental margin
(ODP leg 112Scientific Party, personal
70 o-units apart) with depth. These are
often characterized by a slight de-
c species CO 2 , H 2C0 3, HC03" and communication). PO~- reaches a max- crease in O'3C at greater depths due to
CO~-), phosphate, ammonia and sul- imum of 0.4 mM and NHt of 21 mM in the release of relatively light carbon by
phide. The main oxidants consumed in the same hole. In comparison with the the continuing breakdown of organic
o the process are °2(aq), N03" and SO~­
and also CO~ - . CO2 production occurs
alkalinity maximum at 35 m sub-bottom matter in fermentation reactions . The

o at all stages from (1)to (6), consumption


depth, the other two maxima are dis-
placed downward to 56 and 175 m,
parallelism of the carbon-isotope
curves for methane and CO2 is convinc-
c from stage (4) downward. A distinction
between the CO2 released and the CO 2
respectively.
The fact that the carbonate alkalinity
ing evidence that carbonate reduction
is actually involved in biogenic methane
consumed at different stages is pos- maximum occurs within the carbonate generation. More recently (Claypool et
sible due to the strong isotopic frac- reduction zone (and not at its upper al., 1985)O'3Cvalues as high as + 36%0
tionation effects associated with some boundary) shows that carbonate (or to + 38%0 have been measured for CO2
c of the reactions, particularly methane
generation beginning in stage (4). In
bicarbonate) production continues in
this zone due to various fermentation
co-existing with methane as heavy as
- 41 %0 in deeper parts of DSDP holes
order to understand fully the chemical reactions, initially at a faster rate than 568 and 570 (Figure 6). Methane of bio-

o trends, reactions other than organic-


matter decomposition have also to be
consumption. Eventually, however, con-
sumption by methane generation (and
genic origin is usually lighter than
- 55%0, except where it is generated
considered. These include ion-ex- precipitation of carbonate concretions, from acetate, the fractionation factor of
change reactions, adsorption, and the as discussed later) become dominant. which is considerably lower (about
o precipitation of (early) diagenetic min- Direct insight into the interplay of 50%0). Jenden and Kaplan (1986) esti-
o erai phases. These, and reactions cou-
pled with phase changes (i.e., gas-
the various processes may be gained
from carbon-isotope analyses. During
mated that about 20% of the CH 4 in the
uppermost metres of the Guatemalan
hydrate formation). which introduce fur- the first three steps of organic-matter trench slope sediment could be ace-
ther fractionation effects and diver- decomposition (i.e., in the oxidation, tate-derived and that this fraction de-
sification of the chemical trends, will be nitrate reduction and sulphate reduc- creases to 0% at the bottom of the drill
discussed in the following sections. tion zones) negligible isotopic frac- holes at 400 m. o'3C-values heavier
Drill holes of the DSDP in the East tionation occurs. The CO2 (or HC03" , than - 45%0 are generally considered
o Pacific off Guatemala will again be used CO~ -) released has about the same characteristic for thermogenic gas

o as examples, because they are repre-


sentative for high-sedimentation rate
isotopic composition as the parent
organic material, i.e., a O'3C of about
(Schoell, 1983) with the exception of
acetate-derived CH4 • However, there is
o continental margin environments and
display some trends but also some spe-
- 25%0 (relative to the PDB standard) for
marine organic matter. The pore water
no evidence for upward migration of
thermocatalytic methane on the
n
~ cial features with unusual clarity. The becom ing enriched with CO2 from this Guatemalan trench slope .

o landward slope of the Middle America


trench off Guatemala was drilled during
source in the upper three zones will
gradually approach a O'3C value of
In, orlrnrnedlatelybetow, the sulphate
reduction zone, O'3C values for CO2 •
two legs of the DSDP (legs 67 and 84) in - 20%0 to - 25%0 (Figure 13, especially more negative than - 28%0 have been
r: two parallel transects close to each oth- site 174A). In the carbonate reduction observed locally, e.g., in DSDP hole 533
er thus providing a unique opportunity to and fermentation zones, however, the on the Blake Bahama Outer Ridge
r check the reproducibility of the results of disproportionation of organic matter (-31.4%0, Claypool and Threlkeld,
interstitial water analyses in nearby drill into CH 4 and CO 2 is accompanied by a 1983), which require a source more de-
o holes. A third transect of holes was drilled
in the same general area on the slope off
strong isotope fractionation effect. The
CH 4 generated has a C-isotopic com-
pleted in heavy carbon than average
organic matter. This could be due to the
Mexico (DSDP leg 66). position which is about 70% lighter than predominance of isotopically lighter
Drill sites 496. 497 and 568 which are the carbon of the parent material and terrestrial organic matter (Sackett and
located on the mid-slope in water may thus attain o'3C-values as negative Thompson , 1963) or the anaerobic oxi-
depths between 2000 and 2400 mare as - 90%0 or - 100%0. This is a kinetic dation of methane diffusing upward into
characterized by extreme maxima for effect (Rosenfeld and Silverman, 1959) the sulphate reduction zone. In ancient
carbonate alkalinity, ammonia and dis- by which the CO 2 with light carbon is rocks, a record of these processes may
solved phosphate in the upper parts preferentially reduced to CH 4 • The be preserved in carbonate concretions
between 50 and 200 m sub-bottom ' residual CO 2 consequently becomes which incorporate carbonate of given
(Figure 6). These maxima occur in the enriched in O'3C reaching positive isotopic composition from the pore
carbonate reduction and fermentation o-values (Figure 13)as high as + 15%0 to water (with a small liquid to solid frac-
zones, i.e., below the sulphate reduc- + 25%0 (e.g., Curtis et al., 1972). As the tionation) in their concentric growth
tion zone which is about 5 m thick in this dissolved carbonate becomes progres- shells (see below).
c
296 Diagenesis Geoscience Canada Reprint Series 4
c
c
c
Before following further the fate of the
products of organic matter decomposi-
0
-90 -80 -70 -60 - 50 -40 -
SCl3 (,,_ v. POB)
-20 -10
.--
0 +10 +20 c
tion in mineral izat ion processes, the
behav iour of some other major ele- 100
<,
-,
~ c
ments will be dealt with. Of the two ]200
-a. . . . .
-,
\
<l> c
main dissolved constituents of sea-
water, chloride and sodium , the former
:I:
t- 300
0..
\
ijJ
I
I
I
I
c
does not pa rticipate in reactions,
because of its large ionic radius which
UJ
0400 J d1 c
prevents it from incorporation into the
~
gsoo
t- t
t
I
I
I
c
crystal lattices of common authigenic or
hydrothermal mineral phases. As a non-
gsoo
lD r1J
I 10
,
I c
reactive species , chloride often does
not display vertical concentrat ion gra-
::::>
en I
c
dients, at least not at shallow bur ial SCl3 (%0 v. POB) (
depths. If, on the other hand, chloride
gradients are observed, one of the fol-
-80 -60 - 40 -20 0 +20
c
lowing processes may be inferred : (a) ~~ c
dilution by mixing with fresh water re-
leased from gas hydrates or by mixing
E
i 50 'a.'Q 0\
\
c
with meteoric waters; (b) salinity in-
creasedue to halite dissolution or loss of
t-
0..
UJ
lD
~
\ 0
\ c
water in hydration reactions, e.g., in
basalt of the oceanic crust; or (c) slight
0
~
gloo
\
80
01
e,
I
c
changes in seawater chlorin ity during
t-
0
I
'8
,
I <:
glacial-interglacial cycles.
The Effects of Gas Hydrates
lD
lD
::::>
8'
riP 4>
</>
I c
on Pore-water Chemistry:
en 150
rtJ I
c
Salt and Isotope Fractionation
(Type 6 Pore-water Profiles).
b c
An interesting freshwate r source of
a different nature is the occurrence of
-80 -so
SC I3 (%. v. POB)
- 40 - 20
.e--
0 +20 c
gas hydrates which will also leave a dis- G.... c
~
100
'~,
tinct isotopic imprint on the pore water.
A significant downward chlorinity de-
E
it- 200 ..
(!I} c
0» c
\
crease coupled with a 01 8 0 increase ~3oo 0
J

(up to 3.3%0) has been observed in gas-


hydrate bearing sections of DSDP drill
0
~4oo
0
[J
t /
/
/
0
c
holes (Harrison et al. , 1982; Jenden ~soo clIIJ cp C
and Gieskes, 1983; Gieskes et al. , 1985 ; 0
I
\
Hesse at al. , 1985) and interpreted as
release of fresh water from the thawing
gjsoo
::::>
en 700
SITE 174A
E
of hydrates, either at the base of hy- 008
I!l CH4
o !COz C
drate zones or in the sampling process
(Hesse and Harrison, 1981). Gas hy- SCI3 (%0 v. POB)
C
drates are ice-like substances which - 80 -60 -40 -20 0 + 20
C
form in organic-matter rich sediments
with strong bacterial methane produc-
100 <, (
Q ......
C
,
c
<,
<,
tion. The crystal structure of gas hy- ]200 6- ..... <,
drates (clathrates) is similar to that :I: '&b 0
of zeolites containing large cavities ti:
UJ
300
I
I
<;)
/
e
(cages) in which gas molecules, such
as CH4 , CO2 , H2S , N2 but also higher
0400
~
g500
12I
I
6
I
/
c
hydrocarbons up to the size of iso- t-
butane, may be accommodated. These gsoo
gas molecules are not chemically !II
::::>
en
c
bound in the structure, but are held in
the cages by van der Waals forces and c
hydrogen bonds, which make the struc -
ture more stable than that of normal
Figure 13 /l' 3C depth trends in CH. and CO2 in four DSDP drill sites (102: Blake-Bahama c
ice. The format ion of gas hydrates from
Outer Ridge; 147: Cariaco Trench; 174A: Astoria Fan; 180: Aleutian trench floor). (From
Claypool and Kaplan, 1974). c
c
c
r:
Early Diagenetic Pore Water/Sediment Interaction 297

water and methane involves a negative elevated pressures and relatively low latitudes where a prolific supply of ter-
o molar volume change. Prerequisites for
the formation and stability of methane
temperatures. These conditions exist in
terrigenous continental slope and rise
restrial organic matter to the oceans
may be added to abundant marine or-
8 hydrates are high gas concentrations, environments, particularly in the lower ganic matter below zones of upwelling.
In water depths between 500 and 5000
~
m, hydrostatic pressures are sufficient
o for gas hydrates to be stable up to
1O o-30 o e (Figure 14). Gas-hydrate
o 1000
zones can thus attain a thickness of up

o to 1 km (or more), depending on the


availability of methane-generating or-
ganic matter in outer, deeper continen-
tal margin environments. Because the
~ ground is frozen or partially frozen in
o hydrate zones, they appear as rela-
tively transparent zones on seismic
o profiles , often bound at the bottom by a
strong seismic reflector, the so-called
"bottom simulating reflector" (BSR)
o -'E
10 0 (Figure 15)which is named for its tend-
ency to occur at a constant distance
o ~ GAS + WATER below the ocean-bottom reflecting the
w pressure dependence of hydrate stabil-
o a:
::>
(f)
5 ity. The BSR is caused by the presence
r: (f) of free gas at the base of the hydrate
w 7 zone, where the hydrates thaw and reo
a:
o a.. lease quantities of gas well in excess of

o methane solubility in the pore water. An


amplitude reversal associated with the
o 10 1 Pure methane + J . 511 Na Cl
seismic signal from the BSR attests to
the presence of free gas, which is sea-
[ 2 Pure methane + pure water led in by the gas-tight cap of hydrate-

o 3 91' methane + 7' C02


4 98' methane + 2' C02
impregnated sediments above.
Like normal ice, gas hydrates do not
o 5 90.4' methane + 9.6' ethane
6 56.4' IIICthane + 43.6' ethane
7 Pure ethane
incorporate dissolved salts, but con-
centrate heavy isotopes of oxygen and
8 Pure propane hydrogen in their structure thus caus-
o 2~---'----'--~-~-~---'----'--~-""""
o 10 20 30 40
ing salt and isotope fractionation. As a
consequence, the remaining pore fluid
not involved in hydrate formation will be
TEMPERATURE (DC) enriched in dissolved salts and light iso-
Figure 14 Stability field of hydrates with various gas compositions. (From Hesse and topes. During burial and compaction
Harrison , 1981, after Tucholke et al. , 1977). Boxesindicate estimated poTconditions for DSDP when partial separation of the pore flu-
sites 497 (closely spaced diagonal lines) and 498A. ids and the solid sediment constituents
takes place, - the solids being buried,
sw ME the liquids moving up relative to the

:=J
BASEOf'
GAS H'fDIUlTE ( . S R)
• solids, - gas hydrates carry down
fresh water in solid, ice-like form to
greater burial depth. When the hy-
drates thaw at the base of the hydrate
r
-;
zone or in the sampling process, they
~
release this fresh water, which is also
isotopically heavy. Mixing with the re-
maining pore water, which due to com-
paction is much reduced in volume
compared to the uncompacted sedi-
ment near the sea floor where the hy-
drates first form, produces the ob-
Figure 15 Multichannel seismic reflection profile of gas hydrate zone with bottom simulat- served trends of down-hole chlorinity
ing reflector (BSR) on Blake-Bahama Outer Ridge. (From Shipley et al ., 1979). Vertical scale: decrease and 018 0 increase (Figure 6,
Two-way seismic travel time in seconds. sites 496, 497, 565, 568, 570).
c
298 Diagenesis Geoscience Canada Reprint Series 4 c
c
Positive <') 1 8 0 values are a reliable Ridge (Jenden and Gieskes, 1983) chlo- tinental margin environments does c
indicator for gas hydrates as fresh rinities fluctuate and minima probably not occur on a broad scale as a uniform c
water source, because fresh water from
a meteoric source would produce nega-
coincide with local concentrations of
gas-hydrates as massive layers or nod-
advection or diffusion front.
Attempts at sampling the pore fluids c
tive <') 1 8 0 values. However, positive
<') 1 8 0 values are not invariably associ-
ules in preferred horizons.
These considerations militate against
from hydrate zones in situ and retriev-
ing the expected high-salinity (high
c
ated with a chlorinity decrease related the possibility of upward migration by chlorinity) and isotopically light waters c
to hydrate decomposition, as shown by
the pore-water profile for site 565 drilled
diffusion or advection to the hydrate
zone of isotopically heavier waters that
that have been rejected from the crystal
lattices of hydrates have only been par- c
in 3 km water depth on the continental
slope off Costa Rica (Figure 6). Here, a
form at great depths in sedimentary
basins due to isotopic exchange reac-
tially successful. In situ water samples
taken during leg 84 of the DSDP at sites
c
more or less continuous downward tions between the pore fluids and solids 565 and 568 showed major element c
chlorinity decrease is accompanied by
a zone of negative 018 0 values at sub-
at more elevated temperatures (Clay-
ton et al., 1966; L. Land, personal com-
concentrations similar to the analyses
of pore waters squeezed onboard the c
bottom depths between 95 and 170 rn,
with a minimum o-value of - 1.26%0,
munication, 1985). If the isotopically
heavy pore waters recovered from hy-
drill ship except for the deepest sam-
ples in hole 568 which, however, were
c
(Hesse at al., 1985). Note that the ele- drate zones on the continental slope probably contaminated by seawater c
vated chlorinity values between 235
and 255 m are probably due to con-
were derived by advection or diffusion
of heavier flu ids from below, rather
(Hesse et al., 1985; see Figures 6, 16).
Oxygen and hydrogen isotopic ana- c
tamination by seawater, because Mg2+
and SO~- are also anomalously high. If
than by hydrate fractionation, why then
do we not see the same isotopic signal
lyses, on the other hand, showed the
expected depletions in the heavy iso-
c
the negative 01 8 0 values were the re- in hydrate-free environments of similar topes (Hesse, in press), but the number c
sult of meteoric water influx, one would
not expect the chlorinity to be lowered
tectonic settings? More importantly,
why then do the hydrogen isotopes
of samples was too limited for the re-
sults to be conclusive, demonstrating c
significantly, because pore waters in show the same trends as the oxygen the need for further sampling. A modi-
aquifers at 3.5 km subsurface depth
tend to have chlorinities considerably
isotopes in hydrate zones (e.g., in site
533 of the DSDP, Jenden and Gieskes,
fied sampling procedure with high-
pressure gas displacement of pore flu- c
higher than fresh water. Alternatively, if
the lowered chlorinity in those iso-
1983), whereas in deep formation
waters they do not, i.e., the deuterium
ids might shed light on this unsolved
problem in the future.
c
topically light zones is due to hydrate enrichment characteristically lags be- Gas-hydrate zones provide an oppor- c
decomposition as suggested by Hesse
et al. (1985), a different isotopic frac-
hind the enrichment in 5180? This again
is evidence that advection or diffusion
tunity to evaluate the amount of organic
carbon converted into methane during c
tionation mechanism producing iso-
topically light water has to be superim-
of deeper pore waters in modern con- early diagenesis, because most of the
c
posed on the hydrate fractionation c,- (g/kg) c
mechanism. This would be the altera-
tion of volcanic glass to zeolites and 0
0 10 20
c
smectites discussed before.
, c
Hesse and co-workers (1985) dis-
cussed the chlorinity versus depth
•+ 568 »e
~~'
I C
tre-nds for sites 496 and 568 and con-
cluded that, if the low-chloride waters
0
568 in situ
496
+

.~/'o
e /0
0
, I
E
in these sites were produced by down-
Advect ion-diffusion
I C
I,"

r+
ward diffusion of CI- toward (or upward E e I
advection of fresh water from) a pool of s: (no pore-water flow)
I C
low-chlorinity water below the hydrate 0.. 200
Ql
"0
i C
zone, a trend indicated by the dash-dot i
E
line in Figure 16 would be expected re- .9 Q' I C
flecting downward decreasing diffusion
coefficients. The trends actually ob-
'0
.0
.0
,0'+
' e I
I
c
served suggest that diffusion and ad-
vection in these high sedimentation-
:J
C/)

,0,
,P
I
i
; e
rate sites are insignificant and that the Ie) i
;+
c
gradual chloride profiles result from a
rather uniform distribution of hydrates
400 e /
/
+ c
with gradually increasing concentra-
tions downward. In other drill sites, e.g., ;'
/
/ -
c
site 570 on the Guatemalan trench ;'
;'
c
slope, sites 490 to 492 on the Mexican
trench slope (Gieskes et al., 1985) or Figure 16 Chlorinity versus depth profiles for DSDP sites 496 and 568. (From Hesse etal., c
site 533 on the Blake-Bahama Outer 1985).
c
c
c
c
c Early Diagenetic Pore Water/Sediment Interaction 299

c
c methane generated is probably still crease between the sea floor and 400 m the pore water by fresh water released
o trapped and little has escaped to the
ocean floor, in contrast to regions with-
sub-bottom is about 3%, or 1.5% Co r g
averaged overthe entire column (Figure
from hydrate decomposition at the base
of a 400 m thick gas hydrate zone (or
o
r:
out gas hydrate development and their
sealing effects. From the assumptions
10). Thus, most of this decrease can be
explained by bacterial organic matter
during sampl ing from within this zone)
offers an interesting possibility to evalu-
IistedinTable5afigureofabout 1.0wt.% decomposition and little is due to depo- ate the efficiency of the isotopic frac-
o of carbon is calculated that is lost to the
hydrate zone, or 25 to 30% of the or-
sitional factors . These calculations also
show that, in sediments with initial Co rg
tionation mechanism . Experimental de-
terminations have confirmed that the
o ganic carbon initially embedded in the concentrations above 3 or 4%, there is isotopic fractionation factor for a clath-
sediment. This is somewhat less than more than enough organic matter avail- rate-watersystem(a = 1.027, Davidson
( the loss of organic carbon seen in holes able for the formation of gas hydrates. et a/., 1983) is close to that of the ice-
o 496 and 497, where the downward de- The figure of at least 50% dilution of water system (a = 1.03, O'Neil, 1968).
With this fractionation factor 018 0
o TableS Amount of organic carbon converted to methane which is trapped in
values at the base of a hydrate zone,
o gas-hydrate zones.
where at least 50% of the pore water is
derived from hydrate melting, should be
o Assumptions
Thickness of gas-hydrate zone 400 m
about 1.4%0, compared to values of up
to 3.3%0 actually observed. Because
Average porosity over this thickness 500/0 advection or diffusion of isotopically
o Total water content of 400 m thick sediment column
Chlorinity reduction from top to bottom of hydrate zone
20 L H2 0 - cm·2
50%
heavy waters from greater depths in the
active margin environments considered
o (e.g., from 19% to 9.5% in sites 496 and 497)
Dilution of pore water by fresh water released
here is not very likely as discussed ear-

o from hydrates at base of hydrate zone 500J0


lier, a multiple fractionation mechanism
has been invoked (Hesseeta/., 1985),by
o at top of hydrate zone
Average dilution over 400 m thick sediment column
Average bulk density of 400 m thick sediment column
00J0
25%
1.5 g . cm-3
which the base of the hydrate zone
migrates vertically up and down with
time , e.g., as a result of heat-flow varia-

o Calculations
Total fresh water released from hydrates over 400 m 5L
tions. Heavy water released by melting
hydrates could again be used when the
o Number of moles H2 0 released
Number of moles CH4 corresponding to 277 moles H2 0 in
277 hydrate base moves downward to form
new, heavier hydrates.
o methane hydrate of compos ition CH4 • 6H2 0
Weight of carbon corresponding to 45 moles CH4
45
540 g
Besides hydrate decomposition, there

o Total weight of 400-m-thick-column' cm-2


Percent of organic carbon converted to methane still
60,000 9
are other dehydration reactions causing
fresh water release manifesting itself as
o contained in hydrate zone 0.9
salinity and chlorinity decrease at depth,

o km FROM SHORELI NE
o FERNANDINA-
JACKSONVILLE 0
TEST WELLS
50
I
100
I
150
I
200
I
250
I
300
I
350
I
400
I
450
I
o -20t.. _

o
o 4

o 3

o DePTH

-
10 20 0 10 20 30 9 tp 20 m ft

o 2[030_. MIOCEN[
O\.IGOCEIlt POST~ I
U"'u .... 1IODl.[ "0:[1<[
o 0

( UOPiil

=f"\
) lOWER 200
EOC[NE O\.IGOCENE "«[H[

e I:
Jsm[
L~NE
LOWEREOCENE 100
400

c
OLIGO( Ol..lGQC(H[ .
6 NLEOCENE _racENE
4 3 r~~i 100
r
lOffEA 200
EOCEN[

100

XJQ.J.. ,ooo

Figure 17 Fresh and brackish water in drill holes on the Florida continental shelf indicating subsurface discharge within carbonate
aquifers up to 120km from the coast (pore-water profile, type 5). (From Manheim and Sayles, 1974).
.......
r-
'--
c
300 Diagenesis Geoscience Canada Reprint Series 4 c
c
particularly in zones of abnormally high tive fracturing , development of "scaly section) , Banda (Breen et aI., 1986)and
c
fluid pressure . Because these are gen- clays", rehealing of the fractures by Japan-Nankai (Laubier et et., 1986; c
erally associated with more advanced
stages of diagenesis (middle diagene-
early diagenetic cements and a gener-
ally high degree of compaction. Associ-
Ohta and Laubier, 1987). ODP Leg 110
succeeded, for the first time in the his- c
sis) at greater burial depth, they will not
be discussed and we shall turn our
ated with these processes is intense
dewatering that should cause large-
tory of deep-sea drilling , to penetrate
the master thrust between the upper
c
attention to other processes operating scale fluid expulsion from these imbri- and lower tectonic plates in an active c
at shallow burial levels during early
diagenesis.
cated wedges (Carson et al., 1974; Car-
son, 1977; Bray and Karig, 1985). Theo-
margin. Site 671 at the toe of the Lesser
Antilles imbricated wedge off Barbados c
Profiles With Meteoric Water Influx
(Type 6 Pore-water Profiles).
retically, dewatering might be a diffuse,
trench-slope wide process or, alter-
penetrated the sediments accreted to
the upper (Caribbean) plate, the main
c
The influx of meteoric waters in subsur- natively, a process of concentrated flow decollement zone and the sediments of c
face aquifers at considerable depth and
distance from shore was demonstrated
along structurally controlled pathways.
In the pore-water profiles hitherto
the incoming lower (Atlantic) plate. A
distinct geochemical anomaly in the c
in some test drill holes for the Deep Sea studied, there is no indication what- pore fluids is associated with the de- c
Drilling Project on the continental shelf
off Florida (Manheim, 1967). In perme-
soever for a diffuse, uniform process.
Intergranular permeability in the fine-
collement which calls for active fluid
flow.The methane concentration, which c
able Eocene to Cretaceous limestones,
fresh water was encountered up to 120
grained sediments of imbricated tec-
tonic wedges is very low and does not
is close to zero in the upper plate sedi-
ments, rises sharply (up to 0.5 mM) in
c
km from shore (Figure 17). Fresh water permit dewatering. Water escape by the decollement zone and the closest c
buried during Pleistocene low sea-level
stands has been reported from the
diffusion or advection from these
wedge sediments is several orders of
fault zone immediately above it, where-
as chlorinity shows a sharp drop (Figure c
Black (Manheim and Chan, 1974; Man-
heim and Schug, 1978)and Baltic Seas
magnitude slower than the subduction
process.
18a).A permeable Eocene sand horizon
below the decollement also shows ele-
c
(Suess, 1976), when these inland seas On the other hand, direct or indirect vated methane levels, whereas faults in c
became lakes.
(Thrust-) faulted Sections With
evidence for fluid expulsion byfocussed
lateral flow along highly fractured fault
the imbricated wedge only a few tens of
metres above the decollement zone do c
Active Lateral Pore-water Flow
(Type 7 Pore-water Profiles).
and shear zones has been reported
from at least four active margins, i.e.,
not display the methane anomaly, but
still carry low-chloride water (site 674,
c
Sediments of subduction zone com- Barbados (Westbrook and Smith, 1983; Figure 18b). As the detailed chemical c
plexes beneath modern trench slopes
undergo active tectonic deformation
ODP Leg 110 Scientific Party, 1987),
Oregon (Kulm et al., 1986; see also
analyses of these pore-fluids are in pro-
gress, it is premature at the time of c
leading to thrust faulting, early penetra- Ritger at al., 1987 referred to in the next revision of this review (May 1989) to c
(a) 0
SoN «1"
(b) c
c
100
Site 674 c
200
o..
c
I
lQ{· ; ' s.,:I> - - - - j (=
JOO
] (
s:
f
c:
4 00 C
C
C
4Y.' ~ -
600
I c
700~-===~---,.----,-----~
,·00 l- e
soo !>40 580 0 200 400 600
40 C 44:; 480 !i20 560 0 100 10 20 c
c r.·c....ct" 1""\~ 1 Mr':"a'l,,' ,~M)
I C' (

Figure 18 (8) (left) Decollement zone between upper (Caribbean) plate and underthrusting lower (Atlantic) plate at the toe of the Lesser C
Antilles island-arc slope with methane and chloride anomalies (site 671). Note thatthe methane anomaly is assoc iated only with the decollement
zone and a fault immediately adjacent to it as well as with an Eocene sand horizon below the decollement, but not with faults higher in the l.
accretionary wedge (neither in hole 671 nor in hole 674).
(b) (right) Low-chloride waters, on the otherhand, are alsofoundin faultzones at greater distance from thedecollement(e .g., site 674, drilledup-
l
slope 17 km west of site 671). (From ODP Leg 110Scientific Party, 1987). C
C
C
r
r:
Early Diagenetic Pore Water/Sediment Interaction 301

r
c speculate on the origin of the methane- Gieskes et a/., 1980). In some of these files may also show downward in-
( bearing low-chlorinity waters, except the increase in chloride concentration creases in chlorinity as a result of water
that they have to come from a deeper- removal in hydration reactions (Figure
o
r:
seated source that is tapped by the
decollement zone probably several tens
is not accompanied by a corresponding
sodium increase, e.g., at site 374 in the
Balearic Basin of the Mediterranean
20). For example, site 477 in the
Guaymas Basin, Gulf of California, is
of kilometres away under more interior Sea (McDuff et a/., 1978) indicating located on a high heat-flow anomaly
parts of the wedge . dissolution of other complex chlorides associated with a local spreading axis,
Evaporite Dissolution at Depth (Figure 19). At this site, the rare mag- for which a geothermal gradient of
o (Type 8 Pore-water Profiles). nesium-rich mineral lueneburgite 88°C ·100m-1 was estimated for the
r Halite dissolution in the vicinity of salt-
domes and evaporite layers is the main,
(M93(P04)2B20(OH)4 . 6H20) was also
found (Muller and Fabricius, 1978).
sediment column leading to tempera-
tures of 200°C at the bottom of the
o although not the only source for high
salinity NaCI and (Ca, Na:z)CI2 brines.
Another mechanism that has been
invoked for the origin of high chlorinity
hole at 300 m sub-bottom depth. Dis-
tinct downward increases in Li +. K+ •
o These typically occur at great depths in brines at great depths in sedimentary and Rb + in the pore waters of this site
o sedimentary basins penetrated by
deeper wells (e.g., Hanor, 1987). How-
basins in which evaporites are absent
is membrane filtration by shales (e.g.,
are attributed to hydrothermal altera-
tion of the sediments, which become
o ever, relatively shallow increases in
chlorinity have been encountered at a
Graf, 1982). As the discussion on mem-
brane filtration has focussed on the
depleted in alkali metals as these are
released to the pore water (Gieskes et
number of drill sites of the DSDP in deeper parts of sedimentary basins, the el., 1982b). The observed Ca 2+ in-
o regions known to be underlain byevap-
orites, e.g., the Mediterranean Sea
somewhat controversial issue (e.g.,
Manheim and Horn, 1968; Dickey, 1969)
crease and Mg2 + decrease are similar
to diffusion-controlled sites, although
o (McDuff et aI., 1978;Sayles et aI., 1972), will not be taken up here . sedimentation rates are very high

o Red Sea (Manheim et al., 1974), Gulf of


Mexico (Manheim at al. , 1969), and
Hydrothermal Activity and Intrusion
of Igneous Dykes and Sills
(greater than 2000 rn- Ma-1 ) . These
changes probably result from the re-
o Atlantic continental margin provinces
offthe Guyanas (Waterman et a/., 1972),
(Type 9 Pore-water Profiles).
Hydrothermally influenced drill sites
lease of Ca2 + and uptake of Mg2 + by
the hydrothermally altered volcanics of
o Namibia (Sotelo and Gieskes, 1978) mentioned earlier in conjunction with the basaltic crust and the volcaniclastic
sediment particles. The Sr2+ maximum
o
r
and Morocco (Couture et et., 1978; convection-controlled pore-water pro-
at 140m sub-bottom depth may indicate
Alkal in ity removal of Sr2+ deeper in the hole by
Chlor ide (mM) basalt-sea water interaction at low rockl
o (meq lol)
water ratios, as observed elsewhere

o ° 2 4
I ° 1
,,
2000
I
4000
I
(Menzies and Seyfried, 1979), and this
may also be responsible for the down-
o
~.
1

\
ward decreasing 87Sr/86Sr ratios.

o
\
\
, The basaltic sill at 58 to 105.5 m sub-

.~.
bottom was apparently cool at the time
o of drilling. Its age of probably more than

n
'--"
~ ..
."'.'!!.,
20,000 years indicates that the thick-
ness of the sediment cover at the time of
the intrusion was probably less than
f- 25 m at this high sedimentation-rate
site. The sill has a distinct effect on the
dissolved Mg2+ and ammonia con -
E
Strontium (mM)
centrations, which are lowered, and the
MagneSium (mu) Cctcrurn (mM)
dissolved SUlphateconcentration which
1000 2000
0°;..--..----:.::;:.::.-....---=.::;:.::....... o 200 400 o 2 3
is raised in the pore waters of the sedi-
I I I I I I I
I
I
I I ment immediately above and below.
I I

r I
1
,
\
\
EARLY DIAGENETIC

I

200f-~ -~ MINERALIZATION REACTIONS IN
HIGH SEDIMENTATION-RATE

.
"----..~ <,
iJ.
BASINS

--._'" ~---'
Processes and chemical reactions of
pore-water evolution discussed so far
have centered on organ ic matter de-
composition reactions and the anions
Figure 19 Interstitial water profiles for DSDP site 374 in the Balearic Basin of the western and neutral species produced. In order
Mediterranean Sea indicating dissolution of evaporite minerals at 380 m sub-bottom depth to account more fully for the observed
(pore-waterprofile, type 8). (From Gieskes, 1983, after McDuffet aI., 1978). Lithology: I, marls; vertical trends, consumption of the dis-
II, nannofossil ooze; III, dolomitic marls; IV, gypsum, anhydrite; V, halite. solved metabolites by precipitation of
c
302 Diagenesis Geoscience Canada Reprint Series 4 c
c
(
authigenic minerals will be discussed tate as metastable iron monosulphides rated with respect to mackinawite but
next, which will also direct attention to such as mackinawite (FeSO•9 0 to FeSO•9 6 supersaturated with respect to pyrite
(
some of the dissolved cations. The first
mineralization reactions occurring in
with up to 10% Fe substituted for by
Ni2+ and C02+) , greigite (Fe3S 4 , a
and precipitate pyrite, whereas at
higher pH (above 6.5) they may be
c
freshly deposited sediments include cubic mineral probably with the struc- supersaturated with respect to both (
the formation of iron sulphides, rarely ture of an inverse spinel) and amor- minerals and favour precipitation of
manganese sulphide, and various car- phous FeS.These intermediate phases the more soluble phase mackinawite
(
bonates which form the main authi- are kinetically favoured at higher super- (Goldhaber and Kaplan, 1974). (
genic constituents of concretions. They saturation over the direct precipitation These relationships are corroborated
are a familiar feature of organic matter- of pyrite, which has a much lower solu- by the distribution of sulphur isotopesin C
rich sediments and have been studied bility product (2.4 x 10- 28 as com- pyrite-bearing carbonate concretions.
both in modern anoxic environments pared to 2.8 x 10- 18 for mackinawite ; A large isotopic fractionat ion effect is C
and their ancient equivalents, i.e., black
shales, although the number of studies
Berner, 1967; Goldhaber and Kaplan,
1974). Pyrite originating by transforma-
related to bacterial sulphate reduction.
The sulphide produced is about 50%
C
directed at the solid authigenic phases, tion from these precursor phases dis- lighter than seawater sulphate (Gold- C
particularly from modern offshore plays a characteristic framboidal haber and Kaplan, 1980) which at pre-
basins, is remarkably limited compared (raspberry-like) structure composed of sent has a 534S value of + 20%0 relative C
to the wealth of pore-water data avail-
able. In part , this reflects the difficulties
tiny euhedral crystals of uniform size.
This particular structure does not re-
to the COT (Canyon Diablo Troilite)
standard. Open-system conditions asin
C
of detecting some of the authigenic quire the involvement of spherical stagnant basins where sulphate reduc- C
solid phases. Pyrite and carbonates are micro-organisms, organic globules, a tion starts above the sediment/water
noticeable exceptions . Other examples gel stage or gaseous vacuoles as some- interface, should supply light sulphide C
of early diagenetic precipitates include times assumed in the older literature, with 534S values in the range of - 20%0 to C
the zeolites and certain clay minerals because it has been produced inorgan- - 30%0 to the sediment. Closed-system
such as smectites, which are character- ically in experiments by reacting iron conditions, as during rapid sulphate C
isticforvolcanogenic and slowlydeposi- monosulphides with elemental sulphur reduction in organic-matter rich sedi-
ted pelagic sediments discussed in a to pyrite (Berner, 1969; Farrand, 1970). ments on the other hand, should involve
C
previous section. Euhedral pyrite, which often over- a Raleigh distillation process leading to C
Early Diagenetic Sulphide grows the early framboidal pyrite , increasingly heavier sulphides as the
Precipitation. appears to form somewhat later and at light sulphur is preferentially withdrawn C
In the presence of soluble ferrous iron
the sulphide produced in the sulphate
lower saturation levels. The process
may also be pH-controlled, because at
in the early stages. The average isotopic
composition, however, would be equal
C
reduction zone will immediately precipi- low pH the solutions may be undersatu- to seawater sulphate. The sulphur-iso- C
Alkal i nit Y e Sulfate
Calcium and mcqnesrurn (mill)
C
(mMl

. ..
(meq l-I)
o 40 80 0 10 20 0
C
I~
-.,.. I
1--r"T"'T...,-iir'-T-rT..:r-r:...r-rT-n"l
C
. , .
'"
'.
, . .. J
. . . .. . ... oe .. "' . ..: ,. '.... - .. .... ...... . ~ .. ' r ": c I'
C
I~ l·-e
.............. C
, I

200 ?
(i~ C
AmmOnia
5 10 C
C
E
Stront ium (mill) Lithium (f£'IIl) Potassium (mill) Rub id ium (f£'IIl)
C
01 02 03 0704 0708 o 20 40 l
~ .... I
I
I 'I I
I I
e
100
. :;:::.. :r~:: .. . . .
~ c ...
..........
.... . ..." "
~...
1',. ..
....
-e-e
~ c
200 ?~ c
o

300 c
Figure 20 Hydrothermally influenced pore-water profiles of DSDP site 477, Guaymas Basin, Gulf of California (pore-water profile, type 9;
c
Gieskes, 1983, after Gieskes et aI., 1982b). Open circles: site 477A. c
c
c
c
Early Diagenetic Pore Water/Sediment Interaction 303

topic composition of early diagenetic growth under open-system conditions,


pyrite may then provide information not above the sediment/water interface
on the environment, in which anoxic, or- but close to it in the sediment (Figure
ganic-matter rich sediments were 22). Under these conditions isotopically
deposited. As Gautier (1985) found in light sulphur may be replenished from
Cretaceous shales from the Western seawater sulphate and the alkalinity
S''cCQCO.' ,
-I'~
'! . Interior Seaway, samples with high
organic matter concentrations (4-10%)
generated in the process of sulphate
reduction may still be lost to the ocean
c display a narrow range of very light iso-
topic sulphur compositions in pyrite
bottom by diffusion, which would ex-
plain the delay of carbonate precipita-
(034S = - 35%0 to - 25%0) indicating tion. Molecular diffusion and bioturba-
open-system sulphate reduction, in tional irrigation are also required to
large part probably in the water column explain the excess of solid sulphide
above the sediment under stagnant found in some organic-matter rich sedi-
o
r:
conditions. Samples with less than 3%
organic carbon, on the other hand,
ments over the sulphide concentration
that could be derived from the sulphate
show a wide range of 034S values (from initially present in the pore water pius
'0 - 35%0 to + 18%0) suggesting closed- the sulphur contained in the organic
system conditions or a rapid change matter (Goldhaber and Kaplan, 1980).
o '0 from initially open to closed system con- Monosulphidic precursors of the fram-

u
Pyrite '" ditions probably under oxidizing bottom boids are favoured by high supersatura-
o 20 waters. A similar grouping of sulphur
isotopic analyses into two main environ-
tion associated with the initial stages
of bacterial sulphate reduction, when
o ments was reported by Schwarcz and reactive organic matter concentration is
Burnie (1973). highest resulting in maximum reduction
l.."

~:f\.!. ~j
In Lower Jurassic carbonate concre- rates. In non-euxinic terrigenous sedi-
o tions from Yorkshire, England, Raiswell
(1982) found the lightest 034S values
ments, iron availability from highly reac-

o I Z:S .. 5 . 7' tKo,t


UA S'llillN""
I Z S" 5 17 1'1011"",
US .......
(-23%0 to -26%0, Figure 21) associ-
tive ferric hydroxides is generally not a
rate-limiting factor for sulphide pre-
ated with dispersed framboidal pyrite cipitation at this stage (Berner, 1984;
Figure 21 Centre-to-rim mineralogical occurring both in the host sediment Raiswell and Berner, 1985). Euhedral
and isotopic variations in Liassic (Lower and in the concretions. In this case, the pyrite, which in part nucleated on the
Jurassic) carbonate concretions from north-
o ern England. (From Coleman and Raiswell,
framboidal pyrite is interpreted as a
phase that formed prior to concretion
framboidal pyrite, becomes progres-
sively heavier from the center (034S =
n 1981).Centre of concretion: UA at sample 5;
'--' US at sample 6.
DIAGENETIC
CJ CONCENTRATION (mM!L)
DIAGENETIC
PRODUCTS
IN
13
8 C .... vsPDB

o 10 50 ZONES

O2
GAMMON SH

-.,,, :
-110 ,.0

FeS2·:~

In sol'
o ~
Z
:::>
>- :t
AEDUCEO

8 a:
< c.co 3
...
a:
iii a' C'·%2-
-3Z~
~ J

...r 'H. F.C0


<§> 3
...o
e, GENEAATION
.'3,. -1O~
4
~
,'3C .'S"'.
• @
.13c •. &~
- 20 -60

Figure 22 Relationship between early diagenetic mineralization reactions in carbonate concretions and depth trend of dissolved chemical
species and carbon isotopes in pore waters from which concretions precipitated. (From Gautier and Claypool, 1984). Note that the alkalinity
maximum often does not coincide with the base of the sulphate zone , but occurs deeper in the methane generating zone (cf. Fig. 6).
c
304 Diagenesis Geoscience Canada Reprint Series 4 c
c
- 24%0 to -14.5%0) toward the concre- which increasesthe pH such that super- "minus-cement porosity" is usedin the
c
tionmargins(c534S = -5.5%oto -2.5%0) saturation with respect to carbonates literature . High minus-cement poros- (
reflecting the establishment of closed-
system conditions. Because no new
and precipitation result. (The pH meas-
ured in DSDP water samples squeezed
ities in the range of 70 to 90% in the
inner shells of many concretions attest c
light sulphate is supplied from sea-
water by diffusion, preferred utilization
onboard the ship or in other deep
subsurface samples is generally differ-
to the common early diagenetic initia-
tion of concretion growth. It is impor-
c
of light sulphur early in the reduction ent from the in situ value due to lossesof tant that normally the growth of car- c
process makes the remaining sulphate
reservoir progressively heavier. Iso-
dissolved gases (C0 2 , H 2S) and
changes in temperature and pressure
bonate concretions is not displacive.
Particles of the host sediment are not c
topically heavy, large euhedral pyrite
crystals which line the rims of these
affecting the stability of hydrogen-bear-
ing aqueous species (Kharaka et al.,
pushed aside by the growing carbon-
ate crystals, in contrast to gypsum or
c
concretions show displacive and sec- 1980). With the computer program SOL- anhydrite nodules precipitated from c
torial growth forming hopper-shapes
and sometimes cone-in-cone structure
MNEQ II (Kharaka et al., 1985b) the
necessary corrections for in situ condi-
hypersaline brines. Grain-size of the
carbonates is usually micritic. An c
(Carstens, 1986).
The rare occurrence of authigenic
tions can be calculated).
Under these circumstances calcite,
exception are spherulitic carbonate
concretions and slowly growing cone-
c
manganese sulphide (alabandite) in dolomite, siderite, rhodochrosite and in-cone cements which cause some c
modern anoxic sediments of the Baltic
Sea (Baron and Debyser, 1957; Suess,
more complex iron-manganese car-
bonates may form in organic-matter
mechanical displacement of the host
sediment. In this case the carbonate
c
1979) has been ascribed to high dis- oxidation zones (2) to (5). Fe-carbon- content may not be used for porosity c
solved Mn2 + concentrations that are
typical for anoxic bottom water in local
ates cannot form in the sulphate reduc-
tion zone in the presence of dissolved
estimates. The samewarning appliesto
concretions showing signs of recrys- c
depressions of this restricted basin.
Thus alabandite precipitates rather
sulphide which competes for the dis-
solved iron. Likewise, experiments by
tallization. Cementation in the early
stages of concretion growth, on the
c
than the usual iron sulphides. Baker and Kastner (1981) suggest that other hand, is often not complete as c
Authigenic Carbonates:
Calcite and Siderite (Figure 22).
dolomite formation is inhibited in the
presence of substantial dissolved sul-
shown by septarian concretions. Their
cracks, which characteristically are c
A prerequisite for authigenic carbon-
ate precipitation in organic matter-
phate. Authigenic calcite, on the other
hand, is among the earliest diagenetic
widest in the centre and become nar-
rower toward the concretion margins,
c
rich sediments is a relatively high pH minerals and may start to precipitate in indicate post-cementation compaction. c
which is buffered by reactions other
than those of the carbonate system. If
the sulphate reduction zone together
with or shortly after the first mono-
They are shrinkage cracks showingthat
cementation initially left some pore c
pH is controlled by the carbonate sys-
tem, increased PC0 2 due to organic
sulphides.
The most conspicuous result of early
space unfilled. Near the termination of
concretion growth , cementation and
c
matter oxidation will raisethe bicarbon-diagenetic carbonate precipitation is compaction in the outer shells reach c
ate rather than carbonate activity and
lower pH. This appears to be the case in
the formation of concretions. However,
authigenic carbonates may also occur
about the same degree as in the sur-
rounding host sediments thus forming a c
oxic environments, in contrast to anoxic as dispersed crystals in the sediment, solid carapace around the concretion, c
environments. pH buffering by hydro-
gen sulphide and other weak acids in
form overgrowths on detrital cores, or
coalesce to produce laterally extensive
which allowed the centre to respond to
further dewatering by shrinkage. How- c
the sulphate reduction zone as well as
hydrogen ion uptake by the reduction
beds. In deep-water black-shale se-
quences of the Cambro-Ordovician
ever,the total volume of septaria in con-
cretions is generally small (less than
c
of manganese oxides and hydroxides Cap-des-Rosiers Formation in Quebec,
diagenetic envelopes have been ob-
3%, Gautier, 1985) and so is the pore
volume initially not filled by cement.
c
in the nitrate reduction zone (and iron
oxides and hydroxides in the sulphate served by the author on calcilutitic tur- Supporting evidence for the early c
reduction zone) will raise the pH suffi-
ciently to cause supersaturation with
bidites and around starved ripples of
clastic carbonate. These are similar to
diagenetic initiation of growth of com-
moncarbonate concretions comesfrom
c
respect to carbonates (Suess, 1979). the "basal micritic limestone" below numerous observations besides car- C
This involves reactions of the type Devonian carbonate turbidites from the bonate concentration, including the
Rhenish Schiefergebirge described by undisturbed nature of original bedding <..
Ma20a + 3H20 + 2e- -+ 2Me2+ + 60H-,
and 4MeOOH + H20 + CH2 0 .....
Eder (1970). Later diagenetic fabrics
also include replacements, particularly
features , the degree of preservation
of the original shape of fecal pellets
e
4Me2+ + CO2 + 80H-
where, Me2 + represents Mn2 + or Fe2 +
by dolomite crystals. and fossils , clay fabric analyses but c
ions. In the carbonate reduction and
In concretions or laterally extensive
diagenetic beds, the carbonates char-
most notably isotopic analyses.
Oertel and Curtis (1972) have shown c
fermentation zones, it is probably the _ acteristically are pore-filling cements
hydrogen consumption in the bacterial whose decreasing concentration from
that in the centre of some Carboni-
ferous carbonate concretions from En-
c
formation of methane in the presence centre (up to 85 or 90% by volume) to gland clay particle orientation is essen- (
of metal ions according to a reaction
Me2 + + 2HCO a- + 8H+ +8e- .....
rim (as little as 25%) reflect the porosity
at the time of precipitation. For poros-
tially random as it would be expect-
ed for a flocculated clay suspension c
CH 4 + MeCOa + 3H zO ities estimated in this way the term with 80 or 90% water content in

(
(
( Early Diagenetic Pore Water/Sediment Interaction 305
(
(
which carbonate precipitation oc- ferrous iron concentrations in the pre- "coal balls"). Downward diffusion of
( curred. Toward the concretion margins sence of dissolved sulphide (at con- marine pore-water and mixing with the
a distinct trend emerges of preferred centrations typically on the order of pore waters of underlying brackish or
C' orientation of the basal planes of clay 10- 3.5 moles-Lr t) are 10- 16 moles freshwater sediments may have some
particles parallel to bedding. Preferred L-1 (for pH = 7.5 and Eh = -0.245 effects upon concretion precipitation.
(
orientation is best developed in the host mV), far too low for iron-carbonates to Authigenic Dolomite
( sediment. This reflects the increasing form. Siderite formation requires dis- ("deep-sea dolomite").
effect of burial compaction with time as solved F&+ concentrations of at least Dolomite and high-magnesium calcite
( the concretion continues to grow. 10-7 moles· L -1 (Curtis, 1967). are other common authigenic carbon-
Chemical and isotopic compositions of Numerous examples have now been ates in anoxic sediments besides calcite
many carbonate concretions in black documented showing that concretions and siderite. The burial diagenetic ori-
c shale sequences reveal centre-to-rim may start to grow close to the sediment/ gin of dolomite in deep water, organic

o variations that can be explained in terms


of the organic-matter oxidation pro-
water interface. In the case of the Gam-
mon Shale, concretion growth was pre-
matter-rich terrigenous muds and bio-
genic siliceous oozes, i.e., of the so-
o cesses and related pore-water trends
discussed before (Curtis et a/., 1972;
sumably complete a few tens of metres
below the sea floor, perhaps as little as
called "deep-sea dolomites" is now an
accepted fact since a number of studies
o Irwin et a/., 1977). In the case of a concre-
tion starting to form in the sulphate re-
10m (Gautier, 1985). In other examples
there is evidence that siderite forma-
were performed on DSDP material (i.e.,
leg 63, Pisciotto and Mahoney, 1981; leg
( duction zone and continuing to grow in tion may have occurred at considerably 64, Kelts and McKenzie, 1982; leg 66,
o the carbonate reduction and fermenta-
tion zones, an early calcitic nucleus will
greater burial depth, e.g., 800 to 1200 m
sub-bottom on the East Coast continen-
Wada et a/., 1981; leg 76, Matsumoto,
1983). Identical occurrences of bedded
o be surrounded by a sideritic rim. Exam-
ples of this kind have been described
tal rise off the United States (DSDP leg
93, Botz and von Rad, 1987).
or nodular dolomite are exposed on
land, e.g., in the Ordovician Cloridorme
by Gautier and Claypool (1984) and Interpretation of 0-, C- and S-isotopic Formation in Quebec (Islam, 1981) or
o Gautier (1985) from the Upper Creta-
ceous Gammon Shale of the northern
results from the same concretion some-
times seems to lead to conflicting con-
the Miocene Monterey Formation of
California, for which an early diagenetic
o Great Plains of the United States. In clusions as in the case of a Lower Juras- origin was already recognized by Bram-

o these concretions a calcitic core with


a 013C value of about -22%0 and a car-
sic concretion described by Coleman
and Raiswell (1981). 018 0 values as low
lette (1946). Diatoms may be well pre-
served in the concretions as opal-A
bonate concentration of 85% iron-free as -9%0 to -10%0 require burial tem- when the surrounding siliceous sedi-
calcite is mantled by an isotopically peratures of 60°C or depths of 1to 2 km, ments have reached the opal-CT or
( heavier (013C increasing outward from which are incompatible with a shallow quartz stage. These dolomites display a
o -10%0 to -4%0) sideritic rim with
70-80% carbonate. Oxygen isotopes
burial origin suggested by carbon and
sulphur isotopes and other evidence.
wide range in 013C values from -30%0
to + 30%0 which has been interpreted
are similar to those of calcite precipitated Alternative isotopic fractionation mech- as evidence for their formation in the
from modern seawater at temperatures anisms, such as alteration of volcanic sulphate reduction, carbonate reduc-
above 15°C, i.e., 0180 values are glass to clay, would shift the oxygen tion and fermentation zones (Arthur at
between - 2%0 and - 3%0 and get pro- isotopic composition of the water, from a/., 1983, Gautier, 1985, Hennessy and
gressively lighter outward in the side- which the carbonate precipitated, in the Knauth , 1985).Baker and Burns (1985),
( rite rim (to about - 7%0). Because the cal- rightdirection, toward negativeovalues. for example invoke dolomite precipita-

o cite is associated with abundant fram-


boidal pyrite, there can be little doubt
However, it is difficult to accomplish the
magnitudeoftheshift required ( -6%oto
tion in the SUlphate reduction zone and
supply of magnesium by diffusion from
o that the iron-free calcite formed in the
sulphate reduction zone. More specif-
- 7%0) in the short depth interval avail-
able. If the shift is not caused by mete-
overlying seawater in the case of dolo-
mite-rich deep-sea sediments (contain-
o
r
ically, it probably formed in the lower
part of the sulphate reduction zone, be-
oric water influx in the subsurface, as
suggested for late diagenetic calcite fill-
ing more than 2 wt.% dolomite). Dolo-
mite formation in sulphate-bearing en-
cause the 013C of - 22%0 shows the ing septarian cracks in concretions of vironments is controversial, however
maximum effect of organic-matter oxi- the Jurassic Oxford Clay in England (see above), and is not required to ex-
dation and the carbonate crystals in (Hudson, 1978),then additional mecha- plain light carbon-isotopic composi-
contact with the pyrite framboids radi- nisms are required for which fractiona- tions. As the findings of Ritger at a/.
ate outward from the latter indicating tion by carbonate precipitation itself (1987)and earlier results of Russell et a/.
that these formed first. Uptake of iron in (Irwin et a/., 1977), but also gas-hydrate (1967)from the Oregon and Washington
the carbonate phase during siderite formation are possibilities. As noted by continental slope show, dolomite, high-
r: precipitation, on the other hand, shows Curtis and Coleman (1986), advection magnesium calcite and aragonite with
that the concretion continued to grow in of connate meteoric waters from fresh- extremely light carbon (013C ranging
the methane generation zones (4) and water deposits into overlying marine from - 32%0 to - 66%0) form as concre-
r-.
(5) where dissolved iron becomes avail- sediments in transgressive sedimen- tions, crusts and chimneys on the sea
able and the carbonate becomes iso- tary sequences as in the lower West- floor where they have been sampled by
topically distinctly heavier because of phalian coal measures of Yorkshire may piston cores and from submersibles.
the withdrawal of light carbon in meth- also explain 180 depletion in early dia- They are apparently related to active
ane. In the sulphate reduction zone, genetic calcite concretions (so-called sediment dewatering in the accretionary

r:
c
306 Diagenesis Geoscience Canada Reprint Series 4 c
c
prism above the subduction zone of the Complex Authigenic Carbonates. bottom at various DSDP drill sites dis- c
Oregon-Washington margin leading to The occurrence of complex authigenic cussed by Gieskes (1981). Because (
upward methane migration concen- carbonates rich in Mn and Fe, which these show a close correlation with
trated along localized, structurally con- show transitions to end-member rhodo- maxima in the dissolved silica profiles, c
trolled pathways. The bicarbonate de-
rived from oxidation of the methane to
chrosite and siderite, has only been
described from a few DSDP drill sites
Gieskes (1981) suggested Mn-release
from opal-A dissolution as a by-product c
CO2 raises alkalinity leading to carbon-
ate precipitation.
(e.g., Hein et aI., 1979b; Okada, 1980;
Wada et ei., 1981). The isotopic com-
of silica diagenesis.
Ion Exchange Reactions and
c
Dolomite concretions and beds of position of similar concretions in Creta- Adsorption. (
the Monterey Formation have received
special attention (Garrison et al., 1984),
ceous black shales of the Western Alps
(c5 13 Cvarying between -11%oand -6%0,
None of the processes discussed so far
for rapidly deposited, organic-matter
c
because of the interest in the Monterey c5 1 8() between -9.6%0 and -4.4%0; rich sediments explains the depths pro- c
as a major source for hydrocarbons in
California. A detailed isotopic study by
'fasse and Hesse, 1984) suggests that
they formed at somewhat greater burial
files for dissolved ammonia and phos-
phate. As the reader may recall from a c
Kushnir and Kastner (1984)showed that
nodular dolomite concretions span a
depths in the methane generation zone.
This requires mobilization of manga-
previous section, dissolved ammonia
often has a maximum below the alkalin-
c
wide range in c5 13 C values indicating nese at those depths, which is in line ity maximum (Figure 6), while the phos- c
growth over a considerable burial depth
interval and contrasting remarkably
with secondary maxima in Mn-depth pro-
files between a 100 and 200 m sub-
phate maximum occurs in an intermedi-
ate position. Build-up of both ammonia c
with bedded dolomite with a very nar-
row range in isotopic values. Compton
c
and Siever (1986) who analysed the pro-
1000 FeS2
OXIDAT~.ON '!!o.0 WATER
c
blem of an adequate magnesium source
concluded that diffusion from seawater
800
c
was adequate for these dolomites if pre- c
cipitation had occurred.
In drill sites of the DSDP with authi- c
genic carbonates, Ca and Mg depth
profiles are clearly reaction-controlled
c
as shown by sites 496,497, 565 and 568
400 c
to 570 (Figure 6). Ca decreases from
the seawater value are rapid and con- c
centrations remain low over most of
the depths penetrated with only slight
c
increases at the deepest levels. This
Eh
c
contrasts markedly with diffusion-con-
trolled sites and their pronounced mY 0 c
downward Ca-increases. Mg, after in-
creasing initially, is reduced consider-
c
ably more rapidly than in diffusion- c
controlled sites. The initial increase is
probably related to ion exchange reac- c
tions with clays, which, however, may
also contribute to the later decrease,
-400 c
in cases where this is not accounted for
WATER
UNSTABLE
,
",
c
by carbonate precipitation. In these
sites, carbonate consumption by pre- II " ,~It.,.
c
cipitation of solid carbonates is also
required in order to model successfully -800
ACID ALKALINE Jj~...... c
the EC02 and c5 13 C (of CO2 and of CH 4 ) o pH 2 4 8 8 10 12 c
depth profiles (Claypool et al., 1985).
e

Mg-depletion without attendant carbon-
ate alkalinity reduction in anoxic sedi-
GEOTHERMAL ~ RAINWATER. (
ments of the Santa Barbara Basin has FIELD EPIGENESIS
been attributed to uptake by clay miner- CONNATE l
als with high cation-exchange capacity WATER & mm1 IIESOGENESIS C
(Sholkovitz, 1973). The cation-exchange
EOGENESIS
IiWI
capacity is increased when iron-oxide C
coatings are removed from clay miner- Figure 23 pH/Eh fields of natural waters. (Adapted by II. Schmidt and the author from
als in reducing environments (Carroll, Fairbridge , 1967, based on data from Baas Becking et aI., 1960and Garrels, 1960). Stippled C
1958). area: realistic stability field of water.

c
(
c
( Early Diagenetic Pore Water/Sediment Interaction 307

c
(
and phosphate concentrations to their ammonia (as the pore-water profiles of many minerals under surface and sub-
( maxima in the methane generation suggest), but also different in that there surface conditions. Eh exerts a controll-
zones underlines the importance of con- are authigenic mineral phases incor- ing influence on the solubility of ions
tinuing fermentation processes (e.g., porating phosphate, namely apatite which occur in more than one valence
( deamination of proteins). (Cas(P04h(OH,F) or its cryptocrystalline state, e.g., Feand Mn. Theclassificationis
There are no known ammonia-bear- varieties collophane (carbonate-fluorapa- based on the classical work of Krumbein
( ing minerals in anoxic sediments except tite) and dahllite (carbonate-hydroxyl- and Garrels (1952) and showsthe field for
the highly unstable struvite (NH 4Mg apatite). Vivianite (Fe3(P0 4b . 8H 20) marine connate waters (or what is the
( (P0 4) . 6H 20), but its occurrence in is an iron-bearing phosphate. Apatite same: marine eo(dia)genesis) to cover a
modern marine sediments has yet to be precipitation is favoured overvivianite in pH range of 6 to 9.5 and Eh levels from
C' demonstrated. Decrease of ammonia the presence of fine-grained calcium + 600 to about 0 m\l. The diagenesis of
o from its maximum in the methane gen- carbonate as nuclei. In the absence of marine sediments (beyond the connate-

o eration zone can, in part, be explained


by downward diffusion (Lerman, 1977).
such nuclei, apatite formation is hin-
dered by Mg ions and vivianite may form
water or eogenetic stage) occurs under a
pH of 6 to 9 and Eh levels ranging from
o In gas hydrate-bearing sections, the
decrease is partially due to dilution
instead. However, due to the lack of
sufficient iron, supersaturation for viv-
mildly reducing to about - 300 m\l. This
classification has been useful in charac-
o from hydrate water. However, the rapid ianite is usually not reached (Berner, terizing the stability fields of detrital and

o drop generally seen in organic matter-


rich anoxic sediments requires addi-
1980). Earliest diagenetic precipitation
of collophane in shelf muds in regions of
authigenic minerals in sedimentary en-
vironments(interms of pH/Eh conditions).
o tional uptake by ion-exchange reactions
with clays, as the effects of diffusion in
upwelling off Peru is suggested by dis-
solved fluoride decreases in the pore
In practice it has not been too helpful,
particularly in the study of modern
o dissipating concentration maxima are waters to 35-45 x 10- 6 M (or about half unlithified sediments, as pointed out by

o minor for rapidly deposited sediments.


Ammonium ions are incorporated into
the seawater concentration) within the
uppermost 30-50 cm of the seamount
Berner (1981), mainly for two reasons.
First, the pH of most subaqueous sedi-
o interlayer positions of clay minerals with
high layer charges, particularly illites
(Froelich et a/., 1983). Solid phosphate ments,marine and non-marine,variesrel-
atively little, i.e., between 6 and 8, and, in
o and vermiculites as shown by Muller
minerals are often difficult to detect and
a significant portion of the phosphate fact, 90% of Berner's measurements in

o (1977, and references therein) for oxi-


dized pelagic sediments of the Central
fixation that is required to interpret the
downward decreases in the profiles of
modern marine sediments fell into the
narrow pH-range of 6.5 to 7.5. Secondly,
Pacific. Similar reactions are likely to dissolved phosphate probably occurs the Eh cannot be measured correctly be-

c occur in anoxic environments leading to


the fixation of dissolved ammonium in
by adsorption. cause many ionic species do not easily
react at a platinum or gold electrode to

o crystal lattices which will carry it to great


burial depth, down to the realm of meta-
GEOCHEMICAL CLASSIRCATION OF
EARLY DIAGENETIC ENVIRONMENTS
giveoff or accept electrons. Also,because
of kinetic inhibition, unstable speciesper-
o morphism (ltihara and Honma, 1979). Natural waters have been classified from sist into forbidden Eh-domains. The

o Phosphate diagenesis in rapidly de-


posited hemipelagic sediments of the
a geochemical point of view in terms of
their pH/Eh-fields (Figure 23). pH is the
measured electrode potential, therefore,
does not generally agree with the values
o continental margins is similar to that of master variable controlling the solubility calculated from thermodynamic data. Pt
and Au eletrodes, so to speak, do not
o Table 6 Geochemical classification of early diagenetic environments. "see" ions that are not electro-active.

o (Modified after Berner, 1981). Berner (1981), therefore, proposed a


new, more practical geochemical classi-:
o Environment Molar concentration
[02 ] [H 25]
Diagnostic authigenic minerals
and sediment characteristics
fication of sedimentary environments in
terms of the concentration levels of dis-
o Oxic ~ 1Q-6 < 1Q-6 Hematite, goethite, Mn02 minerals,
solved oxygen and total sulphide (H2S

o (no reactive organ ic matter)


plus HS-, Table 6). This scheme has the
advantage of wider applicability as the
Anoxic < 1Q-6 two parameters used involve species
Sulphidic ~ 1Q-6 Pyrite, marcasite, rhodochrosite, which are mutually exclusive at measur-
( alabandite; organic matter. able concentration levels. That is, if sul-
Stagnant Light 034S, no bioturbation. phide and dissolved oxygen are brought
E7 Oxic bottom waters Trend toward heavier 0345; together at concentrations greater than
bioturbated. 1Q-6M,andatapHof6t08,theywitl reactin

c Nonsulphidic
Post-oxic < 1Q-6
< 1Q-6
< 1Q-6 Glauconite and other Fe2+ - Fe3+
a matter of minutes or hours, to form sul-
phate and water. Furthermore, the pre-

c (=Suboxic) minerals; no sulphides .


(Siderite, vivianite, rhodochrosite).
sence of one or the other, even in trace
amounts,has vital (or lethal)effectson the
Minor organic matter. population of organisms living in the sedi-
Methanic < 10-6 < 1Q-6 Siderite, vivianite, rhodochrosite. ment and consequently on the bacterially
Organic matter. mediated mineralization reactionsdiscus-
(
sed before. Obligatory anaerobicbacteria
\....

c.
c
308 Diagenesis Geoscience Canada Reprint Series 4 c
c
cannot tolerate the presence of dis- paragenesis. Suboxic environments at about 75°C where biogenic decom-
c
solved oxygen, even in trace amounts may, by definition, contain only small position reactions oforganic matter give c
- they die, and sulphide minerals will
be oxidized. Vice versa, obligatory aero-
quantities of reduced authigenic Fe-
Mn-minerals. Berner's classification is
way to thermocatalytic reactions, is
fundamental enough to be used as the c
bic bacteria cannot tolerate H2S even
in trace amounts and, in its presence,
independent of pH and salinity and
should, therefore, apply to all sedi-
lower boundary of the "early diagene-
tic regime". Further burial and attend-
c
oxide minerals will be converted to sul- ments, although it may be difficult to ant temperature increase lead to ther- c
phides. Dissolved oxygen and sulphide
are, therefore, ideal candidates for
be applied to certain low-iron and low-
anganese sediments.
mal maturation of kerogen and to the
release of carbonic acid and organic c
parameters to be used in a geochemical
classification of sedimentary, specif- DEFINITION OF "EARLY"
acids. Thesetrigger carbonate and feld-
spar dissolution, generate secondary
c
ically early diagenetic environments. In DIAGENESIS porosity in sandstones, liberate potas- c
the proposed classification scheme of
Berner (1981) each category has its in-
It seems that the term "early diagene-
sis" as generally used in the literature is
sium andaluminumandinitiatethe smec-
tite to illite transformation inclayey sedi- c
dicator minerals (Table6) which will, at rather loosely defined and, in the sense ments, which does not seem to start to c
least in part, be preserved if the sedi-
ment passes from one environment to
applied by the majority of authors, re-
fers mostly to diagenetic processesthat
any significant extent at temperatures
less than about 75°C . A whole new set c
another during burial. The diagnostic
value of most ofthese indicator minerals
can be studied in piston cores. Even
Berner (1980)in his masterly treatment
of important diagenetic reactions be-
gins at this temperature which appears c
is evident from the discussion in the of the subject leaves the definition to be a threshold in terms of activation c
section on "early diagenetic mineraliza-
tion reactions" and needs no further
open-ended by stating that "early dia-
genesis ... refers to changes occurring
energies for thermocatalytic organic
matter decomposition. The presence c
comment. The dividing line between
the two main environments "oxic" and
during burial to a few hundred metres
where elevated temperatures are not
of this natural boundary shows up
clearly on diagrams displaying the tem-
c
"anoxic" is the presence (i.e., at concen- encountered...... perature variation of gas composition
trations greater than 1Q-6M) or absence
(i.e., presence at concentrations less
In the writer's opinion the natural inci-
sion, which occurs in burial diagenesis
and yield in fine-grained, organic-mat-
ter rich sediments (Figure 24). It is c
than 1Q-6M) of dissolved oxygen. The
anoxic environment is subdivided fur- Sapropelic Humic c
ther into "sulphidic" and "nonsul- 20 Source Source c
phidic" by the same principle, i.e., pre-
sence or absence of reduced sulphur
(68)
Diagenesis
c
compounds. In sulphidic environments
alabandite is thermodynamically stable 50
c
relative to rhodochrosite only at very (122) c
high H2S concentrations. Rhodochro-
site, which is the more common Mn min- c
erai in this zone, however, is also char- ,-.
~
c
acteristic for anoxic-nonsulphidic en-
vironments and, therefore, not diag- °'o- ' 100 c
nostic. °U
...
(212)
c
Further distinction of the nonsulphid-
ic anoxic environments into "post-oxic" -:s
eu
Catagenesis
c
and "methanic" is based on the pre-
sence or absence of pyrite. The post-
Q.
au c
oxic (= "suboxic" sensu Froelich et af.,
1979,used here) environment does not
f-<
c
contain enough organic matter for sul-
150
(302) c
phate reduction to take place. Because
of the lack of H2S (and O~ Fe2+ can c
build up to saturation with glauconite.
The methanic environment, however,
e
may follow a sulphidic anoxic stage and, 200 (
may therefore, contain pyrite, but this is
not a necessary condition as fresh-
(392)
Metamorphism • • c
water methanic environments may be
free of pyrite. Distinction between the
C
Relative Yield of Gas from
two nonsulphidic anoxic environments, Organic Matter in Fine-Grained Sediments (
therefore, depends critically on the
interpretation of types and concentra- Figure 24 Yield andcomposition of natural gas from different types of organic matter. (From
C
tions of authigenic minerals found in Hunt, 1979).
C
C
C
(
c Early Diagenetic Pore Water/Sediment Interaction 309

c
c· therefore suggested that this tempera- There are, nevertheless, numerous profiles . The situation may be quite dif-
(, ture be used to differentiate early and open questions, which emerge from this ferent, however, for sandlmud alterna-
intermediate diagenetic regimes. Or- review and need further studies . One tions with their porosity and permea-
c ganic geochemists, of course, use this of these is the mass-balance problem . bility contrasts (as shown by DSDPsites

c temperature as the boundary for dia-


genesis versus catagenesis, the latter
Can the early diagenetic mineralization
products such as carbonate concre-
499 and 500 , Harrison et al. , 1982).
Here, the problem is a technical one,
c term being equivalent to intermediate tions or pyrite nodules be accounted for that is, of obtaining uncontaminated

c plus advanced diagenesis in the petrolo-


gist's vocabulary. Early diagenetic burial
by relatively short-distance diffusional
transport within a limited sediment
water samples from the sand layers.
These questions are of considerable
c· depths range from about a 100 m for
high heat-flow areas (such as the Salton
volume, that is, essentially by closed -
system conditions, or are open-system
interest for the petroleum industry.
None of the studies described in this
c Sea geothermal area) to 2 or 3 (or more)
km for moderate to low geothermal gra-
conditions required as suggested by
Compton and Siever (1986)forthe early
article is of purely academic interest.
As has become obvious, organic matter
( dient areas. Characteristic physical con- diagenetic dolomite in the Monterey plays the key role in early diagenetic
c ditions of the "early diagenetic regime"
defined in this way are listed in Table 7.
Formation? The model of Wigley et al.
(1978) for partially open-system diage-
pore-water/sediment interact ion. The
early diagenetic changes that affect
o Another important caesura in terms netic processes and its application by the dispersed organic matter in the sedi-

o of burial temperatures which is tenta-


tively proposed as the boundary be-
Claypool and Threlkeld (1983) are en-
couraging steps to tackle this problem.
ment have important consequences for
what happens later during burial , when
o tween the intermediate and advanced
stages of diagenesis occurs at about
A second problem, which is indirectly
related to the first, concerns the role of
the sediment enters the "oil window".
Organic matter that has lost most of
( 140°C where the transition from ran- advection as a major transport process its oil-generating capacity before reach-
dom mixed-layer smectite-illite to or- for solutes. This problem has major geo- ing the "oil window" because of intense
( dered mixed-layer clay minerals takes dynamic implications for trench-slope early diagenetic modifications includ-
o place. As the transition from diagenesis
to anchimetamorphism may be placed
areas and fore-arc basins of island-arcl
trench systems where active dewatering
ing biogenic methane production, ob-
viously isof less interestfrom an econom-
o around 200°C, the realm of diagenesis of the sediment prism is known to occur, ic point of view than that which passes

o is subdivided into three about equal


temperature intervals, but it is beyond
but the flow patterns are not known in
detail. The first step in successfully tack-
through the early diagenetic stage with
less severe alteration.
the scope of this paper to give a more ling this problem was done by ODP leg In the years ahead, deeper penetra-
elaborate justification for the proposed 110, and similar attempts should be tion by ODP drillholes is required in
boundaries (and to outline their vari- undertaken elsewhere. orderto acquire the same level of knowl-
o ability). Another big unknown concerns the
effects of lithologic alternations on pore-
edge for the intermediate stage of dia-
genesis that now exists for early dia-
o SUMMARY AND OUTLOOK
This review of pore-water studies from
water Chemistry, for example, of inter-
stratified mud and sand layers, or inter-
genesis. This will be amajoreffortwhich
awaits the application of higher tech-
( modern offfshore basins shows the re- layered hemipelagic sediments and tur- nology to scientific ocean drilling .
o markable progress that has been
achieved over the last 15 years, largely
bidites, or any other short-distance
alternations between lithologically dif- ACKNOWLEDGEMENTS
c reflecting the impact of the Deep Sea ferent sediments. The works of Colley This work and the author's research on

o Drilling Project. As a result, it appears


that, for these basins, the principal
et al. (1984), Wilson et al. (1985) and
Delange (1986) show great promise in
gas hydrates, pore waters andcarbonate
concretions was funded by the Natural
o trends in the chemical evolution of pore
waters with progressive burial down to
this respect. In low-sedimentation rate
areas, lithologic differences between
Sciences and Engineering Research
Council of Canada . J.M. Gieskes, B.
o about 1.5km subsurface depth are more
or less established today. The observed
interstratified sediments in a vertical
column may have no effects on pore-
Hitchon, L. Land, E. McBride, A. Mucci
and another reviewer of the Journal
trends provide important insights into water chemistry whatsoever, as DSDP provided helpful critical comments at
( the sources and sinks for the dissolved site 495 shows, because diffusion (or various stages on earlier versions of the
species and into ongoing diagenetic re- convection) may dissipate any chemical manuscript. A. Kosowski typed the man-
actions in the subsurface. gradients or changes in the pore-water uscript and R. Yatesdid the photographic
and drafting work. This helpand support
E7 Table 7 Early diagenesis. is gratefully acknowledged.
l
Temperature range: o to 75°C
C (Upper limit of 75°C is limit for
biogenic methane generation)
C. Burial depths : 0.1 to 2-3 km
Porosity of clayey sediments: 90% (sea floor) to 30%
Vitrinite reflectance under oil: Ro less than 0.5%
Clay minerals: detrital parageneses, no newly
formed illite

c.
c
310 Diagenesis Geoscience Canada Reprint Series 4 c
c
REFERENCES Curtis, C.D., 1978, Possible links between Goldhaber, M.B. and Kaplan, LA. , 1974, The
c
sandstone diagenesis and depth-related
geochemical reactions occurr ing in en-
sulphur cycle, in Goldberg, E.D., ed.,
The Sea, v. 5, Marine Chemistry: John
c
General closing mudstones: Geological Society Wiley and Sons, New York, p. 569-655. c
Thesecover the sections including Intro-
(london), Journal, v. 135, p. 107-117.
Delange, G.J., 1986, Early diagenetic re-
Harrison, W.E., Hesse, R. and Gieskes,
J.M., 1982, Relationship between sedi- c
duction , Terminology, Sources of Pore-
Water Data , Diagenetic Regimes of
actions in interbedded pelagic and
turbid itic sediments in the Nares Abys-
mentary facies and interstitial water
chemistry in slope, trench and Cocos c
Pore-Fluid Evolution in Modern Offshore
Basins, Geochemical Classification of
sal Plain (western North Atlantic) :
Consequences for the compos ition of
plate sites from the Mid-America
Trench transect, active marg in off
c
Early Diagenetic Environments, Defini-
tion of Early Diagenesis, Summary and
sediment and interstitial water: Geo-
chimica et Cosmochimica Acta, v. 50,
Guatemala, Leg 67, DSDP, in VonHuene,
R., Aubouin, J., et al., Initial Reports
c
Outlook). p. 2543-2561. of the Deep Sea Drilling Project , v. 67, c
Baas Becking, L.G.M ., Kaplan , LA. and
Devol, A.H., 1978, Bacterial oxygen uptake
kinetics as related to biological processes
p. 603-614: United States Government
Printing Office , Washington, D.C. c
Moore, D., 1960, Limits of the natural
environments in terms of pH and oxida-
in oxygen-deficient zones of the oceans:
Deep Sea Research, v. 25, p. 137-146.
Heath, G.A., Moore, T.C. and Dauphin, J.P.,
1977, Organic carbon in deep sea sedi- c
tion-reduction potentials: Journal of
Geology, v. 68, p. 243-284.
Emery, K.O. and Rittenberg, S.C., 1952,
Early diagenesis of California bas in
ments, in Andersen, N.A. and Malahoff,
A., eds., The Fate of Fossil Fuel CO2 in
c
Berner, A.A., 1980, Early Diagenesis. A the-
oretical approach: Princeton University
sediments in relation to orig in of oil:
American Association of Petroleum
the Oceans: Plenum Press, New York,
p.605-625.
c
Press, Princeton Series in Geochemis- Geologists, Bulletin, v. 36, p. 735-806. Hunt, J.M., 1979,Petroleum Geochemistry c
try, 241 p.
Berner, R.A., 1981, A new geochemical clas-
Fairbridge, R.W., 1967, Phases of diagene-
sis and authigenesis, in Larsen , G. and
and Geology: Freeman, San Francisco,
617 p. c
sification of sedimentary environments:
Journal of Sedimentary Petrology, v. 51,
Chilingar, G.V., eds., Diagenesis in Sedi-
ments : Elsevier, Amsterdam, Develop-
Johnson Ibach , L.E., 1982, Relationship
between sedimentation rate and total c
p.359-365.
Bischoff, J.L. , Greer, A.E. and luistro, A.O.,
ments in Sedimentology, v. 8, p. 21-89.
Fanning, K.A. and Pilson , M.E.a., 1971, In-
organic carbon content in ancient ma-
rine sediments: American Association
c
1970, Composition of interst itial waters
of marine sediments; temperature of
terstitial silica and pH in marine sedi-
ments: some effects of sampling pro-
of Petroleum Geologists, Bulletin, v. 66,
p.170-188.
c
squeezing effect : Science, v. 167, cedures : Science , v. 173, p. 1225-1231. Kharaka, Y.K. and Carothers , W.W., 1988, c
p. 1245-1246.
Carpenter, A.B., 1978,Origin and chemical
Froelich, P.N., Klinkhammer, G.P., Bender,
M.L., luedtke, N.A., Heath, G.A., Cullen,
Geochemistry of oil field waters from
North Slope, Alaska, in Grye, G., ed., c
evolution of brines in sedimentary basins,
in Johnson, K.S. and Russell, J.A., eds .,
D., Dauphin, P., Hammond, D., Hartman,
B. and Maynard, V.,1979,Early oxidation
Geology and Exploration of the National
Petroleum Reserve in Alaska, 1974 to c
Geology of Industrial Minerals, 13th
Annual Forum: Oklahoma Geological
of organic matter in pelagic sediments of
the eastern equatorial Atlantic: suboxic
1982: United States Geological Survey,
Professional Paper 1399, p. 551-561. c
Survey, Circular 79, p. 60-77:
Case, L.C., 1955, Origin and current usage
diagenesis: Geochimica et Cosmochim-
ica Acta, v. 43, p. 1075·1090.
Kharaka, Y.K., Hull, A.W. and W.W. Car-
others, 1985a, Water-rock interactions
c
of the term , " connate water ": American
Association of Petroleum Geologists,
Garrels, R.M., 1960, Mineral Equilibria at
low Temperature and Pressure: Harper
in sedimentary basins, in Gautier, D.L.,
Kharaka, Y.K. and Surdam, R.C., eds.,
c
Bulletin, v. 39, p. 1879-1882. and Row, New York, 254 p. Relationship of Organic Matter and c
Claypool, G.E. and Kaplan, LA. , 1974, The
origin and distribution of methane in
Gautier, D.L., Clayton, J.L. , Leventhal, J.S.
and Reddin , N.J., 1984, Origin and
Mineral Diagenesis: Society of Eco-
nomic Paleontologists and Mineralo- c
marine sediments , in Kaplan, LA. , ed .,
Natural Gases in Marine Sediments:
source rock potential of the Sharon
Springs Member of the Pierre Shale,
gists, Short Course, v. 17, p. 79-176.
Krumbein , W.O. and Garrels , A.M., 1952, c
Marine Science, v. 3, p. 99-140.
Claypool, G.E. and Kvenvolden , K.A., 1983,
Colorado and Kansas, in Woodward, J.,
Meissner, F.F. and Clayton, J.L., eds.,
Origin and classification of chemical
sediments in terms of pH and oxidation-
c
Methane and other hydrocarbon gases Source rocks of the Rocky Mountains: reduction potentials: Journal of Geol- c
in marine sediment: Annual Reviews of
the Earth and Planetary Sciences, v. 11,
Rocky Mountain Associat ion of Geolo-
gists, p. 369-385 .
ogy, v. 60, p. 1-33.
Li, Y. and Gregory, S., 1974, Diffusion of ions c
p.299-327.
Claypool, G.E. and Threlkeld, C.N., 1983,
Gieskes , J.M., 1975, Chemistry of intersti-
tial waters of marine sediments : Annual
in seawater and in deep sea sediments:
Geochimica et Cosmochimica Acta, c
Anoxic diagenesis and methane genera-
tion in sediments of the Blake Outer
Reviews of the Earth and Planetary Sci-
ences , v. 3, p. 433-453 .
v. 38, p. 703-714.
Manheim, F.T. and Horn, M.K. , 1968, Com- c
Ridge, DSDP Site 533, leg 76, in Sher-
idan, R.E., Gradstein, F.M., et al., Initial
Gieskes , J.M., 1981, Deep sea drilling inter-
stitial-water studies: Implications for
position of deeper subsurface waters
along the Atlantic continental margin:
e
Reportsofthe Deep Sea Drilling Project, chemical alteration of the oceanic crust , Southeastern Geology, v. 9, p. 215-236. (
v. 76, p. 391-402: United States Govern- layers I and II, in Warme, J.E., Douglas, Manheim, F.T. and Sayles, F.L., 1974, Com-
ment Printing Office , Washington, D.C. A.G. and Winterer, E.L., eds., The Deep position and origin of interstitial waters l
Colley, S., Thomson, J., Wilson, T.R.S. and Sea Drilling Project: A decade of pro- of marine sediments, based on deep sea
Higgs, N.C., 1984, Post-depositional gress: Society of Economic Paleontolo- drill cores, in Goldberg, E.D., ed., The C
migration of elements during diagene- gists and Mineralogists, Special Publi- Sea, v. 5, Marine Chemistry: John Wiley
sis in brown clay and turbidite sequen- cation , v. 32, p. 149-167. and Sons, New York, p. 527-568.
(
ces in the North East Atlantic: Geochim-
ica et Cosmochimica Acta, v.48,
Gieskes,J.M., 1983, The chemistry of inter-
stitial waters of deep-sea sediments: In-
Mechalas, B.J., 1974, Pathways and en-
vironmental requirements for biogenic
C
p. 1223-1235. terpretation of Deep Sea Drilling Data, in
Riley, J.P.and Chester , R., eds., Chemi-
gas production in the ocean, in Kaplan,
LA., ed., Natural Gases in Marine Sedi-
C
cal Oceanography, v. 8, p. 221-269. ments: Marine Science, v. 3, p. 11-26. C
C
,c. Early Diagenetic Pore Water/Sediment Interaction 3 11

(
C' Merino , E., 1975, Diagenesis in Tertiary Wilson, T.R.S ., Thomson , J., Colley, S., DeLange, G.J. and Rispens, F.B., 1986,
( sandstones from Kettleman North Dome, Hydes, D.J., Higgs, N.C. and Sorensen, Indication of a diagenetically induced
California. II. Interstitial solutions: dis- J., 1985, Early organic diagenesis: The precipitate of an Fe-Si mineral in sedi-
tribut ion of aqueous species at 100°C significance of progressive subsurface ment from the Nares Abyssal Plain,
and chemical relation to the diagenetic oxidation fronts in pelagic sediments: western North Atlantic : Marine Geology,
mine raology: Geochimica et Cosmo- Geochimica et Cosmochimica Acta, v. 73, p. 85·97.
chimica Acta, v. 39, p. 1629-1645. v. 49, p. 811-822. Donnelly, T.W. and Merrill , L., 1977, The
C MOiler, P.J .and Suess, E., 1979,Productiv ity, Zeikus, J.G. and Wolfe, R.S., 1972, Meth- scavenging of magnesium and other
rr sedimentation rate, and sedimentary or-
ganic matter in the oceans - I. Organic
anobacterium thermoautotrophicum sp.
n., an anaerobic, autotrophic, extreme
chemical species by biogenic opal in
deep-sea sediments: Chemical Geol-
carbon preservation: Deep-Sea Re- thermophile: Journal of Bacteriology, ogy, v. 19, p. 167-186.
search, v. 26A, p. 1347-1362. v. 109, p. 707-713. Edmond, J.M., Measures , C., McDuff, R.E.,
Nesbitt, H.W., 1980,Characterization of min- Chan, L.H., Collier, R., Grant, B., Gor-
eral-formation water interactions in Car- Low to Intermediate Sedimentation-rate don, L.1. and Corliss , J.B., 1979, Ridge
o boniferous sandstones and shales of the Basins crest hydrothermal activity and the bal-

o Illinois Sedimentary Basin: American


Journal of Science, v. 280, p, 607-630. Anderson, R.N., Hobart, M.A. and Langseth,
ances ofthe major and minor elements in
the oceans : The Galapagos data: Earth

o Nesbitt, H.W., 1985,A chemical equilibrium


model for the Illinois Bas in format ion
M.G., 1979, Geothermal convection
through oceanic crust and sediments of
and Planetary Science Letters, v. 46,
p. 1·18.
waters : American Journal of Science, the Indian Ocean: Sc ience , v.204, Elderfield, H., Gieskes, J.M., Baker, P.A.,
v. 285, p. 436-458. p.828-832. Oldfield , R.K., Hawkesworth, C.J. and
Reeburgh, W.S., 1983, Rates of biogeo- Anderson, R.N., Langseth, M.G. and Sclater, Miller, R., 1982, 87Sr/86Sr and 180 /160
chemical processes in anoxic sediments : J.G., 1977, The mechanics of heat trans- ratios, interstitial water chemistry and
o Annual Reviews of the Earth and Plane- fer through the floor of the Indian Ocean: diagenes is in deep-sea carbonate sedi-

o tary Sciences, v. 11, p. 269-298.


Rhoads, D.C. and Morse, J,W., 1971, Evolu-
Journal of Geophysical Research, v. 82,
p.3391-3409.
ments of the Ontong Java Plateau: Geo-
chimica et Cosmochimica Acta, v. 46,

a tionary and ecologic significance of oxy-


gen-deficient marine basins: Lethaia,
Baker, P.A., Gieskes, J.M. and Elderfield, H.,
1982, Diagenesis of carbonate in deep-
p. 2259-2268 .
Fehn, U., 1986, The evolution of low-tem-
v. 4, p. 413-428. sea sediments - Evidence from Sr/Ca perature convection cells near spread-
Roedder, E., 1977, Fluid inclusions as tools in ratios and interstitial dissolved Sr2 + data: ing centers: A mechanism for the forma-
c mineral exploration: Economic Geology,
v. 72, p. 503-525.
Journal of Sedimentary Petrology, v. 52,
p.71-82.
tion of the Galapagos Mounds and
similar manganese deposits: Economic
Sansone, F.J.and Martens, C.S., 1981, Meth- Bath,A. andShackleton,N.,1984,Oxygenand Geology, v. 81, p, 1396-1407.

c ane production from acetate and associ-


ated methane fluxes from anoxic coastal
hydrogen isotope studies in squeezed
pore waters, Deep Sea Drilling Project,
Gieskes, J.M., Elderfield, H. and Palmer,
M.R., 1986, Strontium and its isotopic

o sediments: Science, v. 211, p. 707-709.


Sayles , F.L.and Manheim, F.T., 1975,lntersti-
Leg 74, hole 525B: Evidence for mid-Mio-
cene ocean isotopic change, in Moore,
composition in interstitial waters of
marine carbonate sediments : Earth and
tial solutions and diagenesis in deeply T.C., Jr., Rabinowitz, P.O., et a/., Initial Planetary Science Letters, v. 77,p. 229-
buried marine sediments: Results from Reports of the Deep Sea Drilling Project, 235.
o the Deep Sea Drilling Project: Geo-
chim ica et Cosmochimica Acta, v. 39,
v. 74, p. 697-699: United States Govern-
ment Printing Office, Washington, D.C.
Gieskes, J.M. and Johnston , K., 1984,Inter-
stitial water studies, Leg 81, in Roberts,
o p. 103-127. Bender, M.L., Hudson, A., Graham, D.W., D.G., Schnitker, D., et a/., Initial Reports

o Stein, R., 1986, Organic carbon and sedi-


mentation rate - further evidence for
Barnes, R.O., Leinen , M., and Kahn, D.,
1986, Diagenesis and convection re-
of the Deep Sea Drilling Project, v. 81,
p. 829-836: United States Government
r anoxic deep-water conditions in the flected in pore water chemistry on the Printing Office, Washington, D.C.
Cenomanian/Turonian Atlantic Ocean : western flank of the East Pacific Rise, Gieskes,J.M .,Johnston , K., Boehm, M. and
Marine Geology, v. 72, p. 199-209. 20 degrees south: Earth and Planetary Nohara, M., 1984, Interstitial water stud-
Waples, D.W., 1983, A reappraisal of anoxia Science Letters, v. 76, p. 71-83. ies, Deep Sea Drilling Project, Leg 75, in
and organic richness, with emphasis on Burke, W.H., Denison, R.E., Hetherington, Hay, W.W., Sibuet, J.-C., et a/., Initial
r Cretaceous of North Atlantic: American E.A., Koepnick, R.B., Nelson, H.F. and Reports ofthe Deep Sea Drilling Project,
Association of Petroleum Geologists, Otto, J.B. , 1982, Variation of seawater v. 75, p. 959-963: United States Govern-
( Bulletin , v. 67, p. 963-978. 87Sr/86Sr throughout Phanerozoic time: ment Printing Office, Washington, D.C.
White , D.E., 1957, Magmatic, connate, and Geology, v. 10, p. 516-519. Gieskes, J.M . and Lawrence, J.R., 1981,
metamorphic waters: Geological Society Chamley, H. and Millot, G., 1972, Neo- Alteration of volcanic matter in deep sea
of America , Bulletin, v. 68, p. 1659-1682. formation de montmorillonite a partir de sediments : evidence from the chemical
r White , D.E.. 1965,Saline waters of sedimen- diatomees et de cendres dans Ie sedi- compos ition of interstitial waters from
C7 tary rocks, in Young, A. and Galley, J.A., ments marins de Santorin (Mediter- deep sea drilling cores: Geochimica et
eds., Fluids inSubsurface Environments: ranee orientale): Comptes Rendus, Aca- CosmochimicaActa, v. 45, p. 1687-1703.
(
American Association of Petroleum Geo- demie des Sciences, Ser. 0, t. 272, Hein , J.R., Yeh, H.W. and Alexander, E.,
I.... logists, Memoir 4, p. 342-366. p. 1132-1134. 1979a, Origin of iron-rich montmoril-
Wigley, T.M., Plummer, L.N. and Pearson, Colley, S., Thomson, J., Wilson, T.R.S. and lonite from manganese nodule belt of
F.J., Jr., 1978, Mass transfer and carbon Higgs, N.C., 1984, Post-depositional the north equatorial Pacific : Clays and
isotope evolution in natural water sys- migration of elements during diagenesis Clay Minerals, v. 27, p. 185-194.
tems : Geochimica et Cosmochimica in brown clay and turbidite sequences in
Acta , v. 42, p. 1117-1139. the North East Atlantic: Geochimica et
Cosmochimica Acta, v. 48, p. 1223-1235.
'-..,
(

312 Diagenesis Geoscience Canada Reprint Series 4 C


C
Helm, A., 1985, Mineralogy and diagenesis Mackin, J.E. and Aller, R.C., 1984, Dis- Scholle, PA , Arthur, MA and Ekdale, AA ,
C
of slope sediments offshore Guatemala solved AI in sediments of the East 1983, Pelagic environment, in Scholle, C
and Costa Aica, Deep Sea Drilling Project China Sea: implications for auth igenic P.A., Bebout, D.G. and Moore, C.H.,
leg 84, in Von Huene, R., Aubouin, J., mineral formation : Geochimica et eds., Carbonate Deposit ional Environ- C
et a/., Intitial Aeports of the Deep Sea Cosmochimica Acta , v. 48, p. 281-297. ments: American Association of Petro-
Drilling Project , v.85, p.571-594 : McDuff, R.E. , 1978, Conservative be- leum Geologists , Memoir33, p. 619-691. C
United States Government Printing Off-
ice, Washington, D.C.
haviour of calcium and magnesium in
interstitial waters of marine sed i-
Shackleton , N.J., Hall, M.A. and Boersma,
A., 1984, Oxygen and carbon isotope
C
Johnson, T.C., 1976, Biogenic opal preser-
vation in pelagic sediments of a small
ments: Identification and interpretation,
unpublished Ph.D. thesis, Sc ripps
data from Leg 74 foraminifera, in
Moore, T.C., Jr., Rabinowitz, P.O., eta/.,
C
area in eastern tropical Pacific: Geologi- Institution of Oceanography, University Initial Aeports of the Deep Sea Drilling C
cal Society of America, Bulletin, v. 87, of California, San Diego, 183 p. Project, v. 74, p. 599-612: United States
p. 1273-1282. McDuff, A.E., 1981, Major cation gradients Government Pr inting Office, Wash - C
Kastner, M., 1981, Authigenic silicates in in DSDP interstitial waters : the role of ington, D.C.
deep-sea sediments: formation and dia- diffusive exchange between sea water Stoffyn-Egli, P., 1982, Dissolved aluminium C
genesis, in Emiliani, C., ed.,The Sea, v. 7,
The Oceanic Lithosphere: John Wiley
and upper oceanic crust: Geoch imica et
CosmochimicaActa, v. 45, p. 1705-1713.
in interstitial waters of recent sediments
from the North Atlantic Ocean : Geo-
C
and Sons, New York, p. 915-980.
Kastner, M. and Stonecipher, SA, 1978,
McDuff, A.E., 1984, The chemistry of inter-
stitial waters from the upper ocean
chimica et Cosmochimica Acta, v. 46,
p. 1345-1352.
C
Zeolites in pelagic sediments of the Atlan- crust , site 395, Deep Sea Drilling Project Stout, P.M., 1985, Chemical diagenesis of C
tic, Pacific and Indian Oceans, in Sand, Leg 78-B, in Hyndman , R.D., Salisbury, pelagic biogenic sediments from the
L.B. and Mumpton, FA, eds., Natural M.H. et et., Initial Reports of the Deep equatorial Pacific, unpublished Ph.D. C
Zeolites: Occurrence, properties, use: Sea Drilling Project, v. 78B, p. 795-799: thesis, Scripps Institution of Ocean-
Pergamon Press, New York, p. 199-220. United States Government Printing Off- ography, University of California, San C
Langseth, M.G., Hyndman, A.D., Becker, K.,
Hickman, S. and Salisbury, M.H., 1984,
ice, Washington, D.C.
McDuff, R.E., 1985, The chemistry of inter-
Diego, 220 p.
Von Damm, K.L. and Bischoff, J.L., 1987,
C
The hydrogeologic regime of isolated stitial waters, Deep Sea Drilling Project Chemistry of hydrothermal solutions
sediment ponds in mid-ocean ridges , Leg 86, in Heath, R.G., Burckle , L.H. et from the southern Juan de Fuca Aidge:
in Hyndman, R.D ., Salisbury, M.H .
et el., Initial Aeports of the Deep Sea
a/., Initial Aeports of the Deep Sea Drill- Journal of Geophysical Research, v. 92, c
DrillingProject, v. 78B, p. 825-837: United
ing Project, v. 86, p. 675-687: United
States Government Printing Office,
p. 11334-11346.
Von Damm, K.L., Edmond, J.M., Grant, B., c
States Government Printing Office ,
Washington, D.C.
Washington, D.C.
McDuff, A.E. and Gieskes , J.M. , 1976, Cal-
Measures , C.L , Walden, B. and Weiss,
A.F., 1985a, Chemistry of submarine c
Lawrence,J.R. and Gieskes, J.M., 1981,Con-
straints on water transport and altera-
cium and magnesium profiles in DSDP
interstitial waters: diffusion or reaction? :
hydrothermal solutions at 21°N , East
Pacific Rise: Geochimica et Cosmo-
c
tion in the oceanic crust from the iso-
topic composition of pore water: Jour-
Earth and Planetary Science Letters ,
v. 33, p. 1-10.
chimica Acta, v. 49, p. 2197-2220.
Von Damm, K.L., Edmond, J.M., Measures,
c
nal of Geophysical Research, v. 86 ,
p. 7924-7934.
Moberly, A., Jr., Kimura, H.S. and McCoy,
FW. , Jr., 1968, Authigenic marine phyl-
C.L and Grant, B., 1985b, Chemistry of
submarine hydrothermal solutions at
c
Lawrence, J .R ., Gieskes, J.M. and losilicates near Hawaii: Geological Guaymas Basin, Gulf of California: Geo- c
Broecker, W.S., 1975, Oxygen isotope
and cation composition of DSDP pore
Society of America, BUlletin , v. 79 ,
p. 1449-1460.
chimica et Cosmochimica Acta, v. 49,
p. 2221-2237. c
waters and the alteration of Layer II
basalts: Earth and Planetary Science
Muller, P.J . and Mangini, A., 1980, Organic
carbon decomposition rates in sedi-
Wilson , T.A.S., Thomson, J., Colley, S.,
Hydes, D.J., Higgs, N.C. and Sorensen, c
Letters, v. 27, p. 1-10.
Lerman , A., 1975, Maintenance of steady
ments of the Pacific manganese nodule
belt dated by 230Th and 231Pa: Earth
J., 1985, Early organic diagenesis : The
significance of progressive subsurface
c
state in oceanic sediments: American and Planetary Science Letters, v. 51, oxidation fronts in pelagic sediments: c
Journal of Science, v. 275, p. 609-635.
Lerman, A., 1977, Migrational processes
p.94-114.
Palmer, M.A. and Elderfield, H., 1985, Sr
Geochimica et Cosmochimica Acta,
v. 49, p. 811-822. c
and chemical reactions in interstitial
waters, in Goldberg, E.D., McCave, LN.,
isotope composition of sea water over
the past 75 Myr: Nature, v.314, High Sedimentation-rate Basins c
O'Brien, J.J. and Steele, J.H. , eds., The
Sea, v. 6, Marine Modeling : John Wiley
p.526-528.
Savin, S.M., 1980, Oxygen and hydrogen Berner, R.A., 1980, Early diagenes is. A c
and Sons, New York, p. 695-738.
Lerman, A. and Lietzke, T.A., 1977, Fluxes
effects in low-temperature mineral-
water interactions, in Fritz, P. and
theoretical approach: Princeton Series
in Geochemistry: Princeton University
c
in a growing sediment layer: American
Journal of Science, v. 277, p. 25-37.
Fontes, J.C., eds., Handbook of Envi-
ronmental Isotope Geochemistry, v. 1:
Press, 241 p.
Claypool , G.E. and Kaplan , I.A. , 1974, The
e
Li, Y. and Gregory, S., 1974, Diffusion of ions
in seawater and in deep sea sediments :
Elsevier, Amsterdam, p. 283-327.
Sayles, F.L. and Manheim, F.T., 1975, Inter-
origin and distribution of methane in
marine sediments, in Kaplan, I.A., ed.,
c
Geochimica et Cosmochimica Acta, stitial solutions and diagenesis in deeply Natural Gases in Marine Sediments: (
v. 38, p. 703-714.
MacKenzie , F.T. and Garrels , R.M., 1966,
buried marine sediments : Results from
the Deep Sea Drilling Project: Geo-
Marine Science , v. 3, p. 99-140.
Claypool , G.E. and Kvenvolden, K.A., 1983, c
Silica-bicarbonate balance in the ocean chimica et Cosmochimica Acta, v. 39, Methane and other hydrocarbon gases
and early diagenesis: Journal of Sedi- p. 103-127. in marine sediment: Annual Reviews of
mentary Petrology, v. 36, p. 1075-1084. the Earth and Planetary Sciences, v. 11, (
p.299-327.
C
C
C
r
Early Diagenetic Pore Water/Sediment Interaction 313

Claypool , G.E. and Threlkeld, C.N., 1983, Harrison , W.E., Hesse, R. and Gieskes, J.M ., O'Neil , J.R., 1968, Hydrogen and oxygen
Anoxic diagenesis and methane genera- 1982,Relationship between sedimentary isotope fract ionation between ice and
tion in sediments of the Blake Outer facies and interstitial water chemistry in water : Journal of Physical Chemistry,
Ridge , DSDP Site 533, Leg 76, in Sher- slope, trench and Cocos plate sites from v. 72, p. 3683-3684 .
idan, R.E., Gradstein, EM ., et a/., Initial the Mid-America Trench transect , active Rosenfeld, W.O. and Silverman , S.A., 1959,
Reports of the Deep Sea Drill ing Project, margin off Guatemala . Leg 67, DSDP, in Carbon isotope fractionat ion in bacterial
r v. 76, p. 391-402: United States Govern- Von Huene, R., Aubouin, J., et a/., Initial production of methane: Science, v. 130,
ment Printing Office , Washington , D.C. Reports of the Deep Sea Drilling Project, p. 1658-1659.
Claypool , G.E., Threlkeld, C.N., Mankiewicz, v. 67, p. 603-614: United States Govern- Sackett, W.M. and Thompson, R.R., 1963,
P.N., Arthur, M.A. and Anderson , T.E , ment Printing Office, Washington, D.C. Isotopic organic carbon compositions of
r: 1985, Isotopic composition of interstitial Hesse, R., 1988, Pore-water anomalies in recent continental shelf derived clastic
fluids and origin of methane in slope sedi- gas-hydrate bearing sediments of the sediments of the Eastern Gulf Coast,
ment of the Middle America Trench, Deep deeper cont inental margins: Journal of Gulf of Mexico: American Association
Sea Drilling Project Leg 84, in Von Huene, Inclusion Phenomena, in press. of Petroleum Geologists, Bulletin, v. 47,
R., Aubouin , J., et a/., Initial Reports of Hesse, R. and Harrison , W.E., 1981, Gas- p.525-531.
r: the Deep Sea Drilling Project, v. 84 , hydrates (clathrates) causing pore-water Schoell, M., 1983, Genetic character ization
p. 683-691: United States Government freshening and oxygen isotope fractiona- of natural gases: American Association
Printing Office, Washington , D.C. tion in deep-water sedimentary sections of Petroleum Geologists, Bulletin, v.67,
[ Clayton, R.N. , Friedman, I., Graf, D.L., of the terrigenous continental margins: p. 2225-2238.
Mayeda, T.K., Meents, W.F. and Shimp, Earth and Planetary Science Letters, Shipley, T.H., Houston, M.H., Buftler, A.T.,
C N.E, 1966, The origin of saline formation v. 55, p. 453-462. Shaub, EJ ., McMillenik, J., Ladd, J.W.
r waters: 1. Isotopic composition: Journal Hesse, R., Lebel , J. and Gieskes, J.M ., 1985, and Worzel, J.L., 1979,Seismic evidence
of Geophysical Research, v. 71, p. 3869- Interstitial water chemistry of gas hydrate for widespread possible gas hydrate hori-
3882. bearing sections on the Middle-America zons on continental slopes and rises:
Curtis, C.D., Petrowski, C. and Oertel, G., Trench Slope Deep Sea Drilling Project, American Association of Petroleum Geo-
1972, Stable carbon isotope ratios within Leg 84, in Von Huene, R., Aubouin, J., logists, Bulletin, v. 63, p. 2204-2213.
carbonate concretions: a clue to place et a/., Initial Reports of the Deep Sea Dril- Suess, E., 1976, Porenlosunqen mariner
and time of formation: Nature, v. 235 , ling Project, v. 84 , p. 727·737: United Sedimente . Ihre chemische Zusammen-
p.98-100. States Government Pr inting Office, setzung als Ausdruck friihdiagenetischer
Davidson , D.W., Leaist, D.G. and Hesse, R., Washington , D.C. Vorgange, Habiliationsschrift, Universi-
1983, Oxygen-18 enrichment in the water Jenden, P.O.and Gieskes, J.M., 1983,Chem- tat Kiel, 193 p.
of a clathrate hydrate: Geochimica et ical and isotopic composition of intersti- Tucholke, B., Bryan, G.M. and Ewing, J.I.,
Cosmochimica Acta, v. 47, p. 2293-2295. tial water from Deep Sea Drilling Project 1977, Gas-hydrate horizons detected in
Froelich , P.N., Klinkhammer, G.P., Bender, sites 533 and 534 , in Sheridan , R.E., seismic profiler data from the western
M.L. , Luedtke, N.A., Heath, G.R., Cullen, Gradstein, F.M., et a/., Initial Reports of North Atlantic: American Association of
D., Dauphin, P., Hammond, D., Hartman, the Deep Sea Drilling Project, v. 76, Petroleum Geologists, Bulletin , v. 61,
B. and Maynard, v., 1979,Early oxidation p.453-461: United States Government p.698-707.
of organic matter in pelagic sediments of Printing Office, Washington, D.C.
the eastern equatorial Atlantic: suboxic Jenden, P.O. and Kaplan, LA. , 1986, Com- Lateral Pore-water Flow Along Fault Zones
diagenesis: Geochimica et Cosmochim- parison of microbial gases from the Mid-
ica Acta, v. 43, p. 1075-1090. dle America Trench and Scripps Subma- Bray, C.J. and Karig, D.E., 1986, Porosity of
Gieskes,J.M., Elderfield , H., Lawrence,J.R., rine Canyon: Implications for the origin of sediments in accretionary prisms and
Johnson, J., Meyers, B. and Campbell , natural gas: Applied Geochemistry, v. 1, some implications for dewatering pro-
A., 1982a, Geochemistry of interstitial p.631·646. cesses: Journal of Geophysical Re-
waters and sediments, Leg 64, Gulf of Manheim, F.T., 1967, Evidence for submarine search, v. 90, p. 768-778.
California, in Curray, J.R., Moore, D.G., discharge of water on the Atlantic con- Breen, N.A., Silver, E.A. and Hussong, D.M.,
r et a/.,Initial Reports ofthe Deep Sea Dril- tinental slope of the southern United 1986, Structural styles of an accretionary
ling Project, v. 64, part 2, p. 675-694: States, and suggestions for further wedge south ofthe island of Sumba,lndo-
United StatesGovernmentPrinting Office, search: New York Academy of Sciences, nesia revealed by Seamarc II side-scan
Washington, D.C. Transactions, Series II, v. 29, p. 839-853. sonar: Geological Society of America,
Gieskes, J.M., Johnston, K. and Boehm, M., Manheim, F:T. and Chan, K.M., 1974, Intersti- Bullet in, v. 97, p. 1250-1261.
1985, Interstitial water studies, Leg 66, tial waters of Black Sea sediments : New Carson, B., 1977, Tectonically induced defor-
in Huene, R., Aubouin, J., et a/., Initial data and review , in Degens, E.T. and mation of deep sea sediments off Wash-
Reports of the Deep Sea Drilling Project, Ross, D.A., eds., The Black Sea - geol- ington and northern Oregon : mechanical
v. 84, p. 961-967: United States Govern- ogy, chemistry and biology: American consolidation: Marine Geology, v. 24,
ment Printing Office , Washington, D.C. Association of Petroleum Geologists, p.289·307.
Goldhaber, M.B. and Kaplan, LA., 1974, The Memoir 20, p. 155-180. Carson, B., Jennwei, Y. and Myers, P.B.,
sulphur cycle, in Goldberg, E.D ., ed., The Manheim , F.T. and SChug, D.M., 1978, Inter- 1974, Initial deep-sea sediment deforma-
Sea, v. 5, Marine Chemistry: John Wiley stitial waters of Black Sea cores, in Ross, tion at the base of the Washington conti-
and Sons, New York, p. 569-655 . D.A., Neprochnov, Y.P., et el., Initial nental slope: Geology, v. 2, p. 561-564.
Goldhaber, M.B. and Kaplan, LA., 1980, Reports of the Deep Sea Drilling Project,
Mechanisms of sulfur incorporation and v.42, part II, p.637-651: United States
isotope fractionation during early diagen- Government Printing Office, Wash-
esis in sediments of the Gulf of California: ington, D.C.
Marine Chemistry, v. 9, p. 95-143.
(

314 Diagenesis Geoscience Canada Reprint Series 4 C


C
Kulm, L.D., Suess, E., Moore, J.C., Carson, Graf, D.L., 1982, Chemical osmosis, re- Waterman , L.S., Sayles, EL. and Manheim,
C
B., Lewis, B.T., Ritger, S.D., Kadko, D.C.,
Thornburg, T.M., Embley, R.W., Rugh,
verse chemical osmosis, and the origin
of subsurface brines: Geochimica et
F.T., 1972, Interstitial water samples on
small core samples, Leg 14, in Hayes,
C
W.D., Massoth, G.J., Langseth, M.G.,
Cochrane, G.R. and Scamman, R.L.,
Cosmochimica Acta, v.46, p. 1431-
1448.
D.E., Pimm, A.C. et el., Initial Reports of
the Deep Sea Drilling Project, v. 14,
C
1986,Oregon subduction zone: venting, Hanor, J.S., 1987, Kilometre-scale thermo- p. 753-762: United States Government (
fauna and carbonates: Science, v. 231, haline overturn of pore waters in the Printing Office , Washington, D.C.
p.561-566. Louisiana Gulf Coast: Nature, v. 327, C
Laubier, L., Ohta, S. and Sibuet, M., 1986,
Decouverte de cornmunautes animates
p.501-503.
Manheim, ET. and Horn, M.K., 1968, Com-
Early Diagenetic
Mineralization Reactions in High
C
profondes durant la campagne franco-
japonaise KAIKO des plonqses dans les
position of deeper subsurface waters
along the Atlantic continental margin:
Sedimentation-rate Basins C
fosses de subduction autour du Japon:
Comptes Rendues de L'Academie des
Southeastern Geology, v. 9, p. 215-236.
Manheim, ET., Sayles, EL., and Friedman,
Arthur, M.A., Anderson, T.E, Kaplan, LA.,
Veizer, J. and Land, L.S., 1983, Stable
C
Sciences Francals, Paris, Series 3, I., 1969, Interstitial water studies on Isotopes in Sedimentary Geology: C
v. 303, p. 25-29. small core samples, Deep Sea Drilling Society of Economic Paleontologists
ODP Leg 110 Scientific Party, 1987, Expul- Project, Leg 1,in Ewing, M., Worzel, J.L. and Mineralogists, Short Course Lec- C
sion offluids from depth along a subduc- et a/., Initial Reports of the Deep Sea
tion-zone decollement horizon: Nature, Drilling Project, v. 1, p. 403-407: United
ture Notes, v. 10, p. 1-151.
Baker, P.A. and Burns, S,J., 1985, Occur-
C
v. 326, p. 785-788.
Ohta, S. and Laubier, L., 1987, Deep biologi-
States Government Printing Office,
Washington, D.C.
rence and formation of dolomite in
organic-rich continental margin sedi-
C
cal communities in the subduction zone
of Japan : observations of bottom photo-
Manheim, F.T., Waterman, L.S., Woo, C.C.
and Sayles, F.L., 1974, Interstitial water
ments : American Association of Petro-
leum Geologists, Bulletin, v. 69, p. 1917-
C
graphs taken during Nautile dives in the studies on small core samples, leg 23 1930. C
KAIKO project: Earth and Planetary Sci- (Red Sea), in Whitmarsh, R.B., Ross, Baker, P.A. and Kastner, M., 1981, Con-
ence Letters, v. 83, p 329-342. D.A. at a/., Initial Reports of the Deep straints on the formation of sedimentary C
Westbrook, G.K. and Smith, M.J., 1983, Sea Drilling Project, v. 23, p. 955-967: dolomite: Science, v. 213, p. 214-216.
Long decollernents and mud volca- United States Government Printing Off- Baron, G. and Debyser, I., 1957, Sur la pre-
noes: evidence from the Barbados
Ridge complex for the role of high pore-
ice, Washington, D.C.
McDuff, R.E., Gieskes, J.M. and Lawrence,
sence dans des vases organiques de la
mer Baltique de sulfure manganeux-
c
water pressures in the development of
an accretionary complex: Geology, v. 11,
J.R., 1978,Interstitial water studies, Leg
42A, in HsO, K., Montadert, L. et aI.,
hexagonal: Comptes Rendues de l'Aca- c
p.279-283. Initial Reports of the Deep Sea Drilling
demie des Sciences Franyais, v. 245,
p. 1148-1150. c
Evaporite Dissolution and Hydrothermal
Project, v. 42, part 1, p. 561-568: United
States Government Printing Office,
Berner, R.A., 1967, Thermodynamic sta-
bility of sedimentary iron sulfides: c
Activity Washington, D.C.
Menzies, M. and Seyfried, W.E., 1979,
American Journal of Science, v. 265,
p.773-785. c
Couture, A., Miller, A.S. and Gieskes, J.M.,
1978, Interstitial water and mineralogi-
Basalt - seawater interaction: Trace
element and strontium isotope varia-
Berner, A.A., 1969, The synthesis of tram-
boidal pyrite: Economic Geology, v. 64,
c
cal studies, Leg 41, in Lancelot, V.,
Seibold, E. et el., Initial Reports of the
tions in experimentally altered glassy
basalt: Earth and Planetary Science
p.383-384.
Berner, A.A., 1980,Early Diagenesis. A the-
c
Deep Sea Drilling Project, v. 41, p. 907- Letters, v. 44, p. 463-472. oretical approach: Princeton University c
914:United States Government Printing
Office, WaShington, D.C.
MOiler, J. and Fabricius, E, 1978, Lune-
burgite in Upper Miocene sediments
Press, Princeton Series in Geochemis-
try, 241 p. c
Dickey, P.A., 1969, Increasing concentra-
tion of subsurface brines with depth:
of the eastern Mediterranean Sea, in
HsO, K., Montadert, L. et a/., Initial
Berner, A.A., 1984, Sedimentary pyrite for-
mation: an update: Geochimica et Cos- c
Chemical Geology, v. 4, p. 361-370.
Gieskes, J.M., 1983,The chemistry of inter-
Reports ofthe Deep Sea Drilling Project,
v. 42, p. 661-664: United States Govern-
mochimica Acta , v. 48, p. 605-615.
Beitz, A. and v. Rad, U., 1987, Authigenic Fe-
c
stitial waters of deep-sea sediments:
Interpretation of Deep Sea Drilling Data,
ment Printing Office, Washington, D.C.
Sayles, EL., Waterman, L.S. and Manheim ,
Mn carbonates in the Cretaceous and
Tertiary continental rise sediments of
c
in Riley,J.P. and Chester,A., eds .: Chemi- ET., 1972, Interstitial water studies on DSDP Site 603 off the eastern U.S.A., C
cal Oceanography, v. 8, p. 221-269. small core samples from the Mediterra- in Van Hinte, J.E., Wise, S.W., Jr. er a/.,
Gieskes, J.M., Graham, D. and Ellis, A., nean Sea, in Ryan, W.B.E, HsO, K.J. et Initial Reports of the Deep Sea Drilling l
1980, Interstitial-water studies, Deep a/., Initial Reports of the Deep Sea Drill- Project, v.93, p. 1061-1077: United
Sea Drilling Project sites 415and 416, in ing Project, v. 13, p, 801-808: United States Government Printing Office,
Lancelot, V., Winterer, E.L. et si., Initial States Government Printing Office, Washington, D.C.
Reports ofthe Deep Sea Drilling Project, Washington, D.C. Bramlette, M.N., 1946, The Monterey For-
v. 50, p. 691-693: United States Govern- Sotelo, V.and Gieskes , J.M., 1978, Intersti- mation of California and the origin of its (
ment Printing Office, Washington , D.C. tial water studies, Leg 40: Shipboard siliceous rocks: United States Geologi-
Gieskes , J.M ., Kastner, M., Einsele, G., studies, in Bolli , H.M ., Ryan, W.B.E et cal Survey, Professional Paper 212,
Kelts, K. and Niemitz, J., 1982b, Hydro- a/., Initial Reports of the Deep Sea Drill- 55 p.
thermal activity in the Guaymas Basin, ing Project, v. 40, p. 549-554: United Carroll, D., 1958,The role of clay minerals in
Gulf of California: A synthesis, in Curray, States Government Printing Office, the transportation of iron: Geochimica
J.R., Moore, D.G. eta/., Initial Reports of Washington, D.C. et Cosmochimica Acta, v. 14, p. 1·27.
the Deep Sea Drilling Project, v. 64,
p. 1159-1167: United States Government
Carstens, H., 1986, Displacive growth of
authigenic pyrite: Journal of Sedimen-
c
Printing Office, WaShington, D.C. tary Petrology, v. 56, p. 252-257. c
c
(
c
Early Diagenetic Pore Water/Sed iment Interaction 315
r>
'-
c Claypool , G.E., Threlkeld, C.N ., Man- Gautier, D.L., 1985, Interpretation of early Kelts, K. and McKenzie, J.A., 1982, Diage-
c kiewicz, P.N., Arthur, M.A. and Ander-
son, T.F., 1985, Isotopic composition of
diagenesis in ancient marine sediments,
in Gautier, D.L., Kharaka, Y.K. and Sur-
netic dolomite formation in Quaternary
anoxic diatomaceous muds of Deep Sea
c) interstitial fluids and origin of methane in
slope sediment of the Middle America
dam, R.C., Relationship of Organic Mat-
ter and Mineral Diagenesis: Society of
Drilling Project Leg 64, Gulf of Califor-
nia, in Curray, J.R., Moore, D.G. et et.,
r>
l. Trench, Deep Sea Drilling Project Leg Economic Paleontologists and Miner- Initial Reports of the Deep Sea Drilling
84 , in Von Huene, R., Aubouin, J. et el., alog ists, Short Course Lecture Notes, Project, v. 64, part 2, p. 553-569: United
( Initial Reports of the Deep Sea Drilling v. 17, p. 6-78. States Government Printing Off ice ,
Project , v. 84, p. 683-691: United States Gautier, D.L. and Claypool, G.E., 1984, Washington, D.C.
C Government Printing Office, Wash- Interpretation of methanic diagenesis in Kharaka, Y.K., Hull, R.W. and Carothers,
ington, D.C. ancient sediments by analogy with pro- W.W., 1985, Water-rock interactions in
Coleman , M.L. and Raiswell , R., 1981, Car- cesses in modern diagenetic environ- sedimentary basins , in Gautier, D.L.,
bon, oxygen and sulfur isotope varia- ments, in McDonald, D.A. and Surdam , Kharaka, Y.K. and Surdam, R.C., Rela-
tions in concretions from the Upper Lias R.C., eds., Clastic Diagenesis : Ameri- tionsh ip of organic matter and mineral
o of N.E. England: Geochimica et Cos- can Association Petroleum Geologists , diagenesis, Society of Economic Pale-

o mochimica Acta, v. 45, p. 329-340.


Compton, J.S. and Siever, R., 1986, Diffu-
Memoir 37, p. 111-123.
Gieskes, J.M., 1981, Deep sea drilling inter-
ontologists and Mineralogists, Short
Course Lecture Notes, v. 17, p. 79-176.

o sion and mass balance of Mg dur ing


early dolomite formation, Monterey For-
stitial-water studies: Implications for
chem ical alteration of the ocean crust ,
Kharaka, Y.K., Hull, a.w and Specht, D.J.,
1985b, SOLMNEQ II: Solution-mineral
c mation : Geochim ica et Cosmochimica
Acta, v. 50, p. 125-135.
Layers I and II, in Warme, J.E., Douglas,
R.G. and Winterer, E.L., eds., The Deep
equilibr ium computat ions : Un ited
States Geological Survey, Water Supply
o Curt is, C.D., 1967, Diagenetic iron minerals
in some British Carboniferous sedi-
Sea Drilling Project: A decade of pro-
gress : Society of Economic Paleontolo-
Paper, in review.
Kharaka, Y.K., Lico, M.S. and Carothers,
ments: Geochimica et Cosmochimica gists and Mineralogists, Special Publi- W.W., 1980, Predicted corrosion and

o Acta , v. 31, p. 2109-2123.


Curt is, C.D. and Coleman , M.L., 1986, Con-
cation 32, p. 149-167.
GoJdhaber, M.B., and Kaplan, LR., 1974,
scale-formation properties of geopres-
sured geothermal waters from the

o trols on the precipitation of early diage-


netic calcite, dolomite and siderite con-
The sulfur cycle, in Goldberg, E.D., ed.,
The Sea, v. 5, Marine Chemistry: John
Northern Gulf of Mexico Basin: Journal
of Petroleum Technology, v. 32, p. 319-
o cretions in complex depositional se-
quences, in Gautier, D.L., ed., Roles of
Wiley and Sons, New York, p. 569-655 .
Goldhaber, M.B., and Kaplan, LR., 1980,
324.
Kushnir, J. and Kastner, M., 1984,Twoforms
o Organic Matter in Sediment Diagenes is:
Society of Econom ic Paleontologists
Mechanisms of sulfur incorporation and
isotope fractionation during early dia-
of dolomite occurrences in the Monterey
Formation, California ; concretions and
and Mineralogists, Special Publication genesis in sediments of the Gulf of layers - a comparative mineralog ical,
no. 38, p. 23-33. California: Marine Chemistry, v.9, geochemical and isotopic study, in Gar-
Curtis, C.D., Petrowski , C. and Oertel , G., p.95-143. rison, R.E., Kastner, M. and Zenger,
1972, Stable carbon isotope ratios within Hein, J.R., O'Neil, J.R. and Jones, M.G., D.H., eds., Dolomites of the Monterey
carbonate concretions: a clue to place 1979b, Origin of authigenic carbonates Formation and Organ ic Rich Units:
o and time of format ion: Nature, v. 235,
p.98-100 .
in sediment from the deep Bering Sea:
Sedimentology, v. 27, p. 577-591.
Society of Economic Paleontologists
and Mineralogists, Pacific Section, Spe-
o DeLange, G.J., 1986, Early diagenetic re-
actions in interbedded pelagic and tur-
Hennessy, J. and Knauth, L.P., 1985, Iso-
topic variations in dolomite concretions
cial Publication no. 41, p. 171-183.
Lerman, A., 1977, Migrational processes
o biditic sediments in the Nares Abys-
sal Plain (western North Atlantic):
from the Monterey Formation, Califor-
nia: Journal of Sedimentary Petrology,
and chemical reactions in interstitial
waters,ln Goldberg, E.D., McCaye, LN.,
o Consequences for the composition of v. 55, p. 120-130. O'Brien J.J. and Steele, J.H., eds., The

o sediment and interstitial water: Geo-


chi mica et Cosmochimica Acta, v. 50,
Hudson , J.D., 1978, Concretions, isotopes ,
and the diagenetic history of the Oxford
Sea, v. 6: John Wiley and Sons, New
York, p. 695-738.
p. 2543-2561, Clay (Jurassic) of central England: Sedi- Matsumoto, R., 1983, Mineralogy and geo-
Eder, F.W., 1970,Genese riff-naher Detritus- mentology, v. 25, p. 339-370. chemistry of carbonate diagenesis of
Kalke bei Balve im Rheinischen Schie- Irwin, H., Curtis, C.D. and Coleman, M., the Pliocene and Pleistocene hemi-
fergebirge (Garbecker Kalk): Verhand- 1977, Isotopic evidence for source of pelagic mud on the Blake Outer Ridge,
lungen der Geologischen Bundes-An- diagenetic carbonates formed dur ing Site 533, Leg 76, In Sher idan, R.E.,

o stalt, Vienna, Jg. 1970, p. 551-569.


Farrand, M., 1970, Framboidal sulfides
precipitated synthetically: Mineralium
bur ial of organic-rich sediments: Na-
ture, v. 269, p. 209-213.
Islam, S., 1981, Thermal maturation pat-
Gradstein, EM. et a/., Initial Reports of
the Deep Sea Drilling Project, v. 76,
p. 411-427: United States Government
(; Deposita, v. 5, p. 237-247. terns in Cambro-Ordovician flysch sedi- Printing Office, Washington, D.C.
Froelich, P.N., Kim, K.H. , Jahnke, R., ments of the Taconic Belt, Gaspe-Penin- MOiler,P.J., 1977, C/N ratios in Pacific deep-
b Burnett, W.C., Soutar, A. and Deakin , sula , unpublished M.Sc. Thesis , McGill sea sediments : Effect of inorganic
M., 1983, Pore water fluoride in Peru University, 191 p. ammonium and organic nitrogen com-
continental margin sediments : Uptake Itihara, Y. and Honma, H., 1979,Ammonium pounds sorbed by clays: Geochimica et
from seawater: Geochimica et Cosmo- in biot ite from metamorphic and granitic Cosmochimica Acta, v. 41, p. 765-776.
chimica Acta, v. 47, p. 1605-1612. rocks of Japan: Geochimica et Cosmo- Oertel , G. and Curtis, C.D., 1972, Clays-
Garrison, R.E., Kastner, M. and Zenger, chimica Acta, v. 43, p. 503-509. tone-ironstone concretion preserving
D.H., 1984, eds., Dolomites of the Mon- fabrics due to progressive compaction :
terey Formation and organic-rich units: Geological Society of America, Bulletin,
Society of Economic Paleontologists v. 83, p. 2597-2606.
and Mineralogists, Pacific Section, Spe-
cial Publication No. 41, 215 p.
c
316 Diagenesis Geoscience Canada Reprint Series 4 c
c
Okada, H., 1980, Pebbles and carbonate
c
nodules from Deep Sea Drilling Project
Aitger, S., Carson, B. and Suess, E., 1987,
Methane-derived authigen ic carbon-
Tasse, N. and Hesse, A., 1984, Origin and
significance of complex authigenic car- c
Leg 56 cores, in Honza, E. et aI., Initial
Aeports of the Deep Sea Drilling Pro-
ates formed by subduction-induced
pore water expulsion along the Oregonl
bonates in Cretaceous black shales of
the Western Alps: Journal of Sedimen- c
ject, v. 56-57, p. 1089-1105: United States
Government Printing Office, Wash-
Washington margin: Geological Society
of America, Bulletin, v. 98, p. 147-156.
tary Petrology, v. 54, p. 1012-1027.
Wada, H., Niitsuma, N., Nagasawa, K. and c
ington, D.C.
Pisciotto, K.A. and Mahoney,J.J ., 1981, Iso-
Aussell, K.L., Deffeyes, K.S., Fowler, G.A.
and Lloyd, A.M., 1967, Marine dolomite
Okada, H., 1981, Deep sea carbonate
nodules from the Middle America trench
c
topic survey of diagenetic carbonates ,
Deep Sea Drilling Project Leg 63, in
of unusual isotopic compos ition : Sci-
ence, v. 155, p. 189-191.
area off Mexico, Deep Sea Drilling Pro-
ject Leg 66, in Watkins, J.S., Moore,
c
Yeats, A.S., Haq, B.U. et el., Initial Schwarcz, H.P. and Burnie, S.W., 1973, J.C. et a/., Initial Aeports of the Deep c
Aeports of the Deep Sea Drilling
Project, v. 63, p. 595-609: United States
Influence of sedimentary environments
on sulfur isotope ratios in clastic rocks:
Sea Drilling Project, v. 66, p. 453-474:
United States Government Printing Off- c
Government Printing Office, Washing-
ton, D.C.
a review: Mineralium Deposita, v. 8,
p.264-277.
ice, Washington, D.C.
c
Aaiswell, A., 1982, Pyrite texture, isotopic
composition and the availability of iron:
Sholkovitz, E., 1973,lnterstitialwaterchem-
istry of the Santa Barbara Basin sedi- c
American Journal of Science, v. 282,
p. 1244-1263.
ments: Geochimica et Cosmochimica
Acta, v. 37, p. 2043-2073.
c
Aaiswell, A. and Berner, A.A., 1985, Pyrite
formation in euxinic and semi-euxinic
Suess, E., 1979, Mineral phases formed in
anoxic sediments by microbial decom-
Originally published in
Geoscience Canada v. 13 Number 3
c
sediments: Amer ican Journal of Sci- position of organic matter: Geochimica (September 1986) c
ence, v. 285, p. 710-724. et Cosmochimica Acta, v. 43, p. 339-
352.
Revised 1989
c
c
c
c
c
c
c
c
c
c
c
~
c
c
c
C
l
e
(
(
l
C
(

(
( .
c Fluid Geothermometry in Sedimentary Systems 317

c.
c the temperatures of fluids particularly if thermometer that relies on the Na/K
( deep wells are available for sampling. ratio in the aqueous solution. Mariner
The techniques discussed also are and Kharaka (1988) have summarized
c useful to monitor temperatures during
thermal recovery of hydrocarbons.
the data for a number of aqueous geo-
thermometers.
( Although the " equilibrium" model for Temperatures measured from fluid
sedimentary systems is questioned by chemistry are useful in thermal recov-
C' some workers, most fluid geothermom- ery projects because down-hole meas-
C eters (the Na/K fluid geothermometer, urements typically are not possible.

o Fluid Geothermometry
for example) are based on empirical
correlations between observed flu id
Fluid geothermometers thus provide a
means of monitoring how tempera-
o in Sedimentary
compositions and measured tempera-
tures. The sil ica geothermometer is
tures change during the production of
a hot fluid from initially cold surrounding
( Systems also useful and is based on the equilib- rocks. In examining the diagenesis of a

o rium solubility of silica species. We


have tested these models in our own
sedimentary system subject to active
burial, fluid geothermometry is a pre-
o Ian Hutcheon
Hugh Abercrombie
research on thermal pilots and find
them to be effective.
cursor to examination of the stability
of waterswith respectto diagenetic min-
c David Gardner There are a multitude of methods that erals. Drill-stem test temperature

o The Department of Geology and


Geophysics
rely on the compositions or physical
properties of minerals, for example iso-
measurementsare alsosubject to errors
related to fluid circulation time. Forma-
o The University of Calgary
Calgary, Alberta
topic compositions of minerals , fluid
inclusion homogenization or mineral
tion water, rapidly retrieved from the
rocks, should retain an accurate forma-
o compositions (Walshe, 1986; Cathelin- tion temperature. Paleo-temperatures

o SUMMARY
Fluid geothermometers have demon-
eau and Nieva, 1985). Fluid inclusion
analysis and methods that utilize min-
during diagenesis are particularly dif-
ficult to estimate and methods such
o strated their utility in the geothermal in-
dustry, but have seen limited applica-
erai compositions are powerful, but the
temperatures measured must be inter-
as fluid inclusions, fission track dating
combined with burial history and
o tion to sediment diagenesis. If dia-
genesis is viewed as an active process,
preted in terms of the diagenetic history
ofthe rock. Forexample, fluid inclusions
vitrinite reflectance can be employed.
These methods are not discussed in
fluid geothermometry is a tool to ob- form at a certain stage of growth of a this paper.
serve active analogues to diagenetic crystal and represent the conditions at Mineral equilibria are intimately

o processes. Understanding active pro-


cesses should help to unravel dia-
genetic histories. Measurement of tem-
that stage of diagenesis. Not only is it
difficult to interpret when, in the burial
history, the event in question occurred ,
related to the fluid geothermometers
mentioned above, butthe reader should
be aware that these methods are use-
peratures in well bores can be done by it is difficult to see through subsequent ful only to determine the present condi-
mechanical means, but chemical and processes of recrystallization or altera- tion of sedimentary systems in the sub-
tion. The same difficulties are encoun- surface and do not contain information
o isotopic geothermometers can be more
useful in some circumstances. Fluid tered in methods that employ chemical regarding the past diagenetic history.
( geothermometers are based on chemi- or isotopic compositions of minerals. The methods are still useful because
calor isotopic equilibria among gas- Direct measurements of temperature examination of drill core samples from
eous or aqueous species. Although gas in modern diagenetic environments are deeper wells indicates that diagenesis
geothermometers have not been uti- difficult. Temperatures can be meas- is an "active" process in these environ-
lized to estimate temperatures of pro- ured in oil wells by down-hole logging ments (801es, 1982).As such, an under-
duced fluids from oil and gas wells, they tools, but this is complicated because standing of present-day conditions is
have some promise. temperatures normally are measured useful to the petrologist studying dia-
Geothermometers based on the com- during drilling and the injection of fluid genesis in the same way that modern
position of aqueous fluids are used in during drilling upsets the thermal analogues are useful to sedimentolo-
geothermal applications and less so regime, complicating the interpretation gists studying ancient depositional
( with fluids produced from oil and gas oftemperature measurements. Produc- systems.
wells. The Na/K and chalcedony geo- ing wells are ideal candidates for tem- Geothermal systems are recognized
thermometers give the most consis- perature measurements, but rarely are throughout the world as economic
( tent results with fluids obtained from temperature probes inserted in produc- sources of energy and this has led to
thermal recovery pilot sites, but other ing wells. Fluid geothermometers have extensivesubsurface geothermal explo-
geothermometers hold promise. been developed, largely as a tool in the ration in many countries (Ellis, 1979a).
geothermal industry, to determine the These present-day hydrothermal sys-
INTRODUCTION heat content, and thus the value, of tems provide direct measurements
This paper discusses geothermome- geothermal resources. The pioneering of temperature and gas and water
,~.
ters based on the chemical or isotopic papers of White (1965),Ellis and Mahon compositions. They also provide a
compositions of fluids, water or gas. (1967) and Fournier and Truesdell(1973) good analogy for the rock-water inter-
These methods are useful to determine present an empirically calibrated geo- action processes which accompany
'-..
(
318 Diagenesis Geoscience Canada Reprint Series 4 (

diagenesis and thermal enhanced re- experimental or empirical methods. can be calculated from the free energy c
covery. Thermal recovery, both steam The gas reaction used most often for change of the reaction (~G r) at a num- c
injection and in-situ combustion, also
provide an opportunity to obtain fluid
gas-reaction equilibria is based on the
Fisher-Tropsch reaction (Nehring and
ber of different temperatures and ,
assuming ideal mixing of ideal gases, c
samples and relate their composition to
temperature.
D'Amore, 1984): is dependent on the gas species as
follows:
c
The reader is cautioned that the sam-
CO2 + 4H 2 = CH 4 + 2H20
Figure 1 shows the partial pressure of
(1)
K = PC02(PH)4/PCH4(PH20)2 (2) c
pling, preservation and analysis of flu-
ids is not a trivial procedure and unless
CO2 in geothermal waters from Iceland In geothermal systems, temperatures c
the details of sampling are subject to
careful control, the interpretation of
as a function of temperature (from
Arn6rsson et a/., 1983). The obvious
are high and pressures are relatively
low, a situation thatfavours the assump- c
analytical results can be equivocal. The
relationship between CO 2 concentra-
tion and temperature suggests the pos-
tion of ideal gases mixing ideally. In real
systems, the gas fugacities should be
c
techniques discussed here should be
applied with caution to samples of un-
sible use of CO 2 as a geothermometer. used and the mixing coefficients deter- c
certain derivation. Lico et at. (1982) pro-
vide documentation of methods for
The upper stability limit of calcite,
approximately 300°C, is the upper limit
mined from van der Waals equation
(Redlich-Kwong, for example) or a virial c
the sampling of oil field and geother-
of applicability.
The equilibria between ammonia
equation of state.
Giggenbach (1980) plotted log K
c
mal waters.
nitrogen and hydrogen (Ellis, 1979b) against 11T, with temperature (T) in kel- c
GAS GEOTHERMOMETERS
Gas equilibrium in geothermal dis-
and the reaction of water with carbon to
produce hydrogen and CO 2 (D'Amore
vin, and derived the following equation:
log K = 10.76 - 93231T (3) c
charge has been used by many workers
and Panichi, 1980) have also been
employed in geothermal systems. For
Because PH20 generally is not meas-
ured in a gas-producing well and most
c
to estimate fluid temperatures at depth
(Giggenbach, 1980; D'Amore and Pani-
reaction (1) the equilibrium constant (I<) sedimentary and geothermal systems c
chi, 1980; Arn6rsson et a/., 1983a). Geo- I I c
- c
thermometers based on gas composi-
tion either can be calculated from

- c
thermodynamic and experimental data
or devised empirically. Typically, a num-
-
ber of assumptions are made which un- c
doubtedly are not valid for all geother-
mal or thermal oil recovery systems. ....-.. c
Obtaining representative water, steam
and gas samples from geothermal sys-
tems is a difficult problem and well
en
..0
ca
••
• - -
c
c
sampling and tubing has been stand-
ardized (Ellis and Mahon, 1977; Arn6rs-
son et a/., 1978). The more prevalent
gases in hot springs and geothermal
brines include CO 2, CH4 , H2S, S02 and
en
~

ca
..0
10-1


- c
c
c
H2. Smaller concentrations of NH 3 , N2 "'-'"
C\J • c
and O2 are also common and consid-
ered to be of geological interest. Inves- o 10-3 I- ~. - c
tigations of heavy oil pilots show CO 2,
CH 4 and H2S to be the most commonly
produced gases.
The relative abundance of CO 2, CH 4
o
a.. .-
-"- c
c
and H 2S in gases, depends on tempera-
ture and can be used as a geothermom- ) .-
c
eter in hydrothermal systems. These 10-5
methods have not been applied to oil
field systems, but, considering their
1-- e
successful application to geothermal
systems, they warrant serious consid-
I I I c
eration. Arn6rsson et at. (1982), Giggen-
100 200 300 L
bach (1980), Arn6rsson et at. (1983a),
and D'Amore and Panichi (1980) have
C
formulated a number of simple equa- Temperature (OC) (
tions which relate gas composition to
temperature . The geothermometers Figure 1 The partial pressure of CO2 in geothermal waters from Iceland. (After Arn6rsson C
have been calibrated using either at al., 1983). (.
(
(
( 319
(

(
are a mixture of liquid water and vapour, temperature of the underlying geother- The basic requirements for geother-
( the useful form of the equation is more mal system (Ragnarsdottir and Walther mometers that involve an aqueous
complicated: 1983).White (1965) and Ellis and Maho~ phase are (Fournier et st., 1974; Ellis,
( logXC02 + 410gXH2 - logXCH 4 (1967) published empirically derived 1979b):
( '" - 5.4398 - 13419/T + O.01959T (4) curves relating the Na/K ratio in thermal 1. The elements, isotopes, or species
waters to temperatures. involved are present within the water-
where Xi refers to the mole fraction of
C gaseous species in the vapour.
These and other geothermometers rock system.
have been used extensively to estimate 2. Chemical or isotopic equilibrium is
( Gas geothermometers are most attained in the time the fluid is present
temperatures at depth in natural ther-
accurate between 200° and 300°C, but at the depth of interest.
( empirical gas geothermometers may
mal water systems, particularly in geo-
3. Solution re-equilibration rates are
o extend this range. Gas geothermome-
ters have not been applied to hydrocar-
thermal exploration and exploitation.
Outside of these fields, the potential of slow enough that the equilibrium con-

c bon wells to our knowledge, but their


geothermometry using the chemical
and isotopic composition of fluids has
centrations at depth remain essentially
unaltered during migration of the fluid
o use could be developed as a tool in
exploration and production of gas and
received little attention. The abundance
of chemical analyses of produced
to the surface.
Some additional considerations include
oil reservoirs. ensuring that geothermometers involv-
waters and gases in both conventional
and unconventional petroleum recov- ing equilibrium between fluid and min-
AQUEOUS GEOTHERMOMETRV erai are applied to rocks that contain
ery invites application of chemical geo-
o Numerous chemical and isotopic geo-
thermometers capable of remote de-
thermometers for remote temperature that mineral. Also, the gain or loss of

o termination of deep temperatures in


measurement. More particularly, the
range of temperatures encountered in
fluid components through mixing or
steam flashing must be considered.

o thermal water systems have been pro-


posed over the past forty years. Earliest
work involved determination of the sys-
water or steam injection for heavy oil
recovery techniques closely parallels
Reaction kinetics will dictate whether
equilibrium distributions of chemical
the 25°-300°C temperature range and isotopic species can be achieved
tematic variations with temperature in
o the fractionation of light stable isotopes
observed for natural thermal and geo-
thermal waters.
under reservoir conditions and be main-
tained under surface conditions once

o between co-existing minerals, fluids,


and gases (Urey, 1947; Urey et a/., 1951;
The equilibrium concentration of chem- the sample is collected. In addition
many reactions chosen for use as geo~
o Epstein et a/., 1951; Craig, 1953). These
same methods have been used to esti-
ical and isotopic species varies with
changing temperature and, to a lesser thermometers, particularly isotopic and

o mate paleotemperatures in the ocean extent, pressure. In theory, chemical


and isotopic geothermometers can be
gas-gas reactions, show significant
variations in reaction rate with tempera-
o from fossil shells and diagenetic tem-
peratures from cements. Investigations calibrated using thermochemical data.
ture, pH and fluid composition.
Silica.
o of lcelandicqeotharrnal waters by Bod-
varsson (1960)and Bodvarsson and Pal-
In practise, existing thermochemical
data are not adequate to allow accurate
In natural water systems, silica may be

o mason (1961) led these workers to con- calibrations, necessitating empirical or


present as amorphous silica (gelatinous
silica, opal, sinter), chalcedony(a micro-
o clude that the concentration of silica in
thermal waters could be related to the
experimental calibration of these
geothermometers.
crystalline, fibrous variety of quartz),
alpha-quartz, or cristobalite. Although
o -1.0 metastable, amorphous silica and chal-

o cedony commonly are present in ther-


mal water systems at temperatures
o -2.0
less than 180°C (Arn6rsson, 1975;Ellis,
1979b; Arn6rsson et et., 1983a). In
o C\I thermal waters at temperatures above

o 0
U5
180°C, alpha-quartz is the stable silica
phase.
C) n1
C>
-3.0 The silica geothermometer is based
upon the variation with temperature of
l 0
.....J
~he solubility of quartz or chalcedony
In water. This is represented by the
l -4.0 reaction:
(
Si0 2 (qz,Ch) + 4H 20 = H4Si04 (aq) (5)
where Si0 2 (qz ,c h) refers to quartz
-5.0 or chalcedony. Above a pH of 9.0, this
o 100 200 300 geothermometer must be corrected
for the ionization of H 4Si04 (aq) to
. TEMPERATURE (OC) H 3Si04(aq) (Ragnarsdottir and Wal-
Figure 2 The solubility of amorphous silica, chalcedony and quartz as a function of ther, 1983). Figure 2 shows the solubili-
temperature. ties of amorphous silica, chalcedony and
'-..

'--
(
320 Diagenesis Geoscience Canada Reprint Series 4 C
C
quartz as a function of temperature. the Na/K ratio of fluids, produced from a K-feldspar, therefore the activities of C
Appropriate corrections are discussed
by Arnorsson et al. (1983a).
heavy oil pilot site during steam injec-
tion and recovery, with respect to the
Na- and K-feldspar can be assumed to
be unity. Indilute waters, the equilibrium
C
The chalcedony geothermometer exchange reaction (6) and a similar constant for reaction (6) is thus the ana- C
has been experimentally calibrated by reaction between illite and Na-smec- Iytical Na/K ratio, hence temperatures
Fournier (1973, 1977). Arnorsson et al. tite. The analyses of produced fluids can be calculated. Above 250°C, at high C
(1983a) have empirically calibrated the
chalcedony geothermometer by corre-
from this pilot fall closest to the phase
boundary between albite and K-feld-
sulphate levels, and in saline waters
with more than 5000 rnq- L-1 chloride,
C
lating measured drill-hole temperatures spar, suggesting that reactions among activities and activity ratios must be C
with calculated H4Si04(aq) molalities in clay minerals may not control the Na/K calculated and then related to the equi-
geothermal fluids from Iceland. Agree- geothermometer. Hutcheon et et. librium constant (Arnorsson, 1983a). C
ment between the Fournier(1973, 1977)
solubility curves and the empirical cal-
(1988) note that the Na content of pro-
duced fluids from this pilot is control-
Various computer programs, such as
SOLMNEQ (Kharaka and Barnes, 1973)
C
ibration of Arnorsson et a/. (1983a) is led by mixing of condensed steam and or SOLMNEQF (Aggarwal and Gunter, C
formation water and that the K concen- 1986) can be used for this calculation.
good in the range 0°-180°C.
Numerous studies of quartz solubility tration is in equilibrium with the K-feld- The Na/K geothermometer hasfound
C
as a function of temperature have been spar-illite phase boundary. Clearly the
Na/K geothermometer may be medi-
wide use in geothermal studies at a
temperature range between about 100°
C
carried out, but results are not consis-
tent. Ragnarsdottir and Walther (1983) ated by more than one mineral reaction. and 300°C (Fournier and Truesdell, C
For waters at temperatures less than 1973; Ellis and Mahon, 1977; Ellis,
combined measured quartz solubility
with data from Dickson (1982), Crerar 180°C and containing high amounts of 1979b). Arnorsson et al. (1983a) have
C
and Anderson (1971) and Fleming and calcium, the Na-K geothermometer
may give anomalous temperatures
extended this range with two tempera- C
Crerar (1982), to calibrate a pressure- ture functions, one from 25° to 250°C
sensitive silica (quartz) geothermome- (Fournier and Truesdell, 1973; Ellis, and the second from 250° to 350°C . C
ter. This geothermometer is valid for
solutions in equilibrium with quartz in
1979b). For this reason, Fournier and
Truesdell (1973) proposed the empi-
Bojes and Wright (1986)have applied
the Na/K geothermometer to thermal
C
the temperature range 180°-340°C and rical Na-K-Ca geothermometer, which recovery, but the technique has not C
fluid pressures from water saturation to accounts for the participation of Ca in seen wide usage. Figure 4 shows esti-
500 bars. aluminosilicate reactions. Arnorsson et mated temperatures using the Na/K C
Application of the quartz geother- al. (1983a) suggest that the Na-K-Ca
geothermometer is less rigorous than
and silica geothermometers for a ther-
mal recovery pilot after Hutcheon et a/.
C
mometer to heavy oil recovery is limi-
ted. Detrital quartz is the most abun- the Na/K, because the former does not (1988). The correspondence of Na/K C
dant mineral in the majoroil sand depos- require equilibrium with a particular and chalcedony temperature estimates
its in Alberta and its dissolution during mineral assemblage and does not ac- implies that the chalcedony geother- C
heavy oil recovery is well known (Boon, count for the possibility of Ca-Ioss
through calcite precipitation upon flash-
mometer is effective in this temperature
range (80°-180°C). The rocks from the
C
1977a,b; Reed, 1980). Applying the
quartz geothermometer requires that ing of water to steam as pressure drops. steam pilot sites in the Cold Lake area C
At low temperatures, there is little typically are lithiclastic and contain vol-
quartz dissolution under recovery con-
ditions be an equilibrium process. mutual solid solution of albite and canic fragments , chert and opaline sil- C
This requirement is commonly assumed,
5.0 C
either implicitly or explicitly (Hutcheon,
1984). C
Na/K and Na-K-ea.
In contrast to the silica geothermome-
ter, which is related to mineral solubility, ---
+~
4.0
c
the Na/K and Na-K-Ca geothermome-
ters are dependent upon the tempera-
ctS
+ctS 3.0
'- c
ture variation in the partitioning ofthese c
-
elements between the fluid and mineral Z
phases (Ellis, 1979b). The Na/K ratio in
ctS <..
2.0
natural thermal fluids is believed to be
controlled by the exchange reaction
0>
0 e
(Ellis and Mahon, 1977):
K + + Na-feldspar = K-feldspar + Na + (6)
--I
1.0 c
<..
requiring the presence of Na- and
K-feldspar in the reservoir. At low tem-
peratures, it would seem more likely
0 c
0 100 200 300 (
that the Na/K ratio is controlled by reac-
tions among clay minerals. This sug-
TEMPERATURE (DC) <..
gestion can be tested using data from
Hutcheon et al. (1988). Figure 3 shows Figure 3 The Na/K ratio of waters from a thermal pilot as a function of temperature. (
c
(
(
(
Fluid Geothermometry in Sedimentary Systems 321
(

c ica. Hutcheon at al. (1988) have also perature, an ion activity product, Q, is perature data. In areas of active explo-
c sampled produced fluids from a steam
pilot dominated by quartz sandstones.
calculated for each of the minerals that
could possible be present. The calcu-
ration, particularly in basins with a
relatively continuous history of burial,
c Over the same temperature range, the lated values of Q are then compared aqueous geothermometers could be
( silica concentration is apparently con- with the equilibrium constants, K, for used to extend the geographic and
trolled by quartz saturation, rather than each mineral and the function 10g(Q/K), stratigraphic range of temperature
( chalcedony saturation . commonly referred to as the mineral information . It would be necessary to
One complication of the direct appli- saturation index, is computed. Mineral compare fluid temperatures estimated
C' cation of the Na/K geothermometer is saturation is achieved when Q equals K, from aqueousgeothermometers to drill-
( the role played by the Na-smectite hence 10g(Q/K) = O. stem temperatures to verify that they
(beidellite) component of smectites that Theoretically, by examining all pos- gave reasonableestimates. If variations
( are known to form during heavy oil re- sible equilibria, the MSt geothermome- between drill-stem temperatures and

o covery (Perry and Gillott, 1979; Sedi-


mentology Research Group, 1981).
ter should provide more accurate esti-
mates of temperature than chemical
fluid temperatures were systematic,the
fluid temperatures could still be used
o Weissburg and Wilson (1977) have dis-
cussed this problem as it applies to geo-
geothermometers that relyon one chem-
ical equilibrium. However, the MSJ geo-
to extend the temperature data base.
In overpressured zones (regions in
o thermal exploration .
Mineral Saturation Index
thermometer suffers the disadvantage
of being totally dependent upon
which fluid pressures are higher than
hydrostatic pressure), temperature is
Geothermometer. the thermodynamic data base selected, observed to increase more rapidly with
o The silica and Na/K geothermometers
are based on control of the fluid phase
which, as discussed by Arn6rsson et al.
(1983b), may be inadequate for chemical
depth. Aqueous geothermometers
might provide a method of delineating
o composition by equilibrium with astable geothermometry. Geothermometers overpressured zones in areas of active
o silica phase in the former case, and Na-
and K-feldspar in the latter. The mineral
that are based upon particular fluid-
mineral equilibria and have been cali-
exploration .
It should be emphasized that the
o saturation index (MSI)geothermometer
is similar in that it incorporates equilib-
brated with measured temperatures,
such as silica and Na/K geothermome-
accuracy of temperature estimates is
directly related to the quality of water
o rium between the fluid and all minerals ters, offer the distinct advantage of samples. The procedures for obtaining
o that could conceivably be present
(Reed and Spycher, 1983).
being independent of errors in thermo-
dynamic data. Other disadvantages of
useful water samples from geothermal
and hydrocarbon wells are summarized
o The MSI geothermometer, like all the MSJ geothermometer are the re- in Lico et a/. (1982).

c geothermometers, requires accurately


measured fluid compositions and pH
quirement for high-quality fluid ana-
lyses, including accurate AI determina- CONCLUSIONS
o values. The MSI geothermometer uses
existing geochemical models such as
tion, and the cost of multiple computer
runs to calculate a single temperature .
A number of geothermometers based
on equilibria among gaseous species
o SOLMNEQ(Kharakaand Barnes, 1973; Possible Applications to Reservoir
Diagenesis.
have been developed for usein geother-

o Aggarwal and Gunter,1986)or SOLVEQ


(Reed, 1982)to calculate ion activities at Aqueous geothermometers provide a
mal systems and may potentially be
useful in sedimentary systems. These
o various temperatures. At each tem- means of extending subsurface tem- geothermometers are dependent on
the concentration of different gas spe-
o 220 I I I I I
cies, including CH4 , CO2 , H2 , NH3 , N2

o
o --~ A. NalK
• Chalcedony
and H2S. High concentrations of dis-
solved salt in produced geothermal flu-

-- - ids and fluids from thermal and con-


180 I-
A. A.A. ventional oil recovery havebeen shown

• •• •
o Q)
A.
• Wellhead to effect these calculations to varying

o "-
~
-.. tt -
degrees . Although gas geothermome-
ters have not been utilized to estimate
o rn 140
"-
I-
temperatures of produced fluids from

C: Q)
a. •I oil and gas wells, they have some
promise.

• •• • ••
A. Geothermometers basedonthe com-
b E 100 -
Q) •• I - position of aqueous fluids have been
C ~
• used extensively in geothermal applica-
tions and less so with fluids produced
from oil and gas wells. The Na/K and
I I I I I
60 chalcedony geothermometers give the
0 30 60 90 120 150 180 most consistent results with fluids
obtained from thermal recovery pilot
, . Days sites, but other geothermometers hold
Figure 4 The temperatures of produced fluids from a thermal recovery pilot estimated using promise. Of the many versions of the
" the Na/K (triangles) and silica geothermometers. Na/K geothermometer, the equations
c
322 Diagenesis Geoscience Canada Reprint Series 4 c
c
developed byArn6rsson (1983) produce Bojes, J.M. and Wright, G.B., 1986,Applica- Fournier, R.O., 1977, Chem ical geother-
c
temperatures that best agree with other tion of fluid analyses to the operation mometers and mixing models for geo- (
available temperature estimates.
Aqueous geothermometers have
of an in situ combustion pilot: Annual
Technical Meeting, Petroleum Society
thermal systems: Geothermics, v. 5,
p.41-50. c
demonstrated their utility in the geo- of CIM, paper 86-37-61, p. 315-349.
Boles, J.A., 1982,Active albitization of Gulf
Fournier, A.O. and Truesdell,A.H., 1973,An
empirical Na-K-Ca geothermometer for c
thermal industry, but have been ne-
glected in applications to sediment dia-
Coast Tertiary: American Journal of Sci-
ence, v. 282, p. 165-180.
natural waters: Geochimica et Cosmo-
chimica Acta, v. 37, p. 1255-1275.
c
genesis. Although there is some discus-
sion, there is evidence that diagenesis,
Boon, J.A., 1977a, Mass transfer of silica Fournier, A.O., White, D.E. and Truesdell, c
when viewed from the perspective of
during steam injection: Proceedings
2nd International Symposium on Water-
A.H., 1974, Geochemical indicators of
subsurface temperatures - Part 1,basic c
water-rock interaction, is an active pro-
cess. Fluid geothermometry is then a
Rock Interaction, Strasbourg, France,
p.199-206.
assumptions: United States Geolog-
ical Survey, Journal of Research, v. 2, c
tool to observe active analogues to dia-
genetic processes. Understanding ac-
Boon, J.A., 1977b, Fluid-rock interactions
during steam injection, in Redford, D.A.
p.259-262.
Giggenbach, W.F., 1980, Geothermal gas c
tive processes, should help to unravel and Wlnestock, A.G ., eds., The Oil
Sands of Canada - Venezuela 1977:
equilibria: Geochimica et Cosmochim-
ica Acta, v. 44, p. 2021-2032.
c
diagenetic histories.
CIMM, Toronto, p. 133-138. Heald, E.F.,Naughton,J.J. and Barnes,l.L., c
ACKNOWLEDGEMENTS
The data on thermal recovery were
Cathelineau, M. and Nieva, D., 1985,A chlo-
rite solid solution geothermometer, The
1963, The chemistry of volcanic gases:
Journal of Geophysical Research, v. 68, c
obtained through the co-operation of
Los Azufres (Mexico) geothermal sys-
tem: Contributions to Mineralogy and
p.539-557.
Hutcheon, I.E., 1984, A review of artificial c
Husky Oil Operations Limited under a
research agreement with the Alberta
Petrology, v. 91, p. 235-244.
Crerar, D.A. and Anderson, G.M., 1971, Sol-
diagenesis during thermally enhanced
recovery, in McDonald, D.A. and Sur- c
Oil Sands TechnologyResearchAuthor-
ity. The assistance of Peter Putnam ,
ubility and solvation reactions of quartz
in dilute hydrothermal solutions: Chemi-
dam, R.C., eds ., Clastic Diagenesis:
American Association of Petroleum
c
Andrew Bau and Ken Applegate was cal Geology, v. 8, p. 107-122. Geologists, Memoir 37, p. 413·429.
Craig, H., 1953,The geochemistry of stable
invaluable.
carbon isotopes: Geochimica et Cos-
Hutcheon, I., Abercrombie, H., Shevalier,
M. amd Nahnybidia, C., 1989, A com- c
REFERENCES mochimlca Acta, v. 3, p. 53-92.
D'Amore , F. and Panichi, C., 1980, Evalua-
parison of formation waters in quartz-
rich and quartz-poor reservoirs during c
Aggarwal, P.K. and Gunter, W.O., 1986,
SOLMNEQF: A FORTRAN-77 version of
tion of deep temperatures of hydro-
thermal systems by a new gas geother-
steam assisted recovery, in Meyer, A.F.
and Wiggins , E.J., eds., Proceedings of c
SOLMNEQ: ARC/AOSTRA Joint agree-
mometer: Geochimica et Cosmochim-
Ica Acta, v. 44, p. 549-566.
the UNITAR/UNDP Fourth International
Conference on Heavy Crude and Tar
c
ment report 8687-4.
Arn6rsson ,S., 1975,Application ofthe silica
Dickson, F.W.,1982,Kinetics of quartz reac-
tion with H2 0 at 200°C and 120 bars
Sands, Edmonton, v. 2, p. 447-459.
Kharaka, Y.K. and Barnes, I., 1973, Solu-
c
geothermometer in low temperature hy-
drothermal areas in Iceland: American
(abstr): EOS, v. 63, p. 1128. tion mineral equilibrium computations : c
Journal of Science, v. 275, p. 763-784 .
Arnorsson, A., Gronvold, K. and Sigurds-
Ellis, A.J., 1957, Chemical equilibrium in
magmatic gases: American Journal of
United States Geological Survey, NTIS
Document PB 215 899. c
son, S., 1978, Aquifer chemistry of four
Science, v. 255, p. 416-431,
Ellis, A.J., 1979a, Explored geothermal
Kharaka, Y.K. and Mariner, A.H ., 1989,
Chemical geothermometers and their c
high·temperature geothermal systems
in Iceland: Geochimica et Cosmochim-
ica Acta, v. 42, p. 523-536.
systems , in Barnes, H.L., ed., Geo-
chemistry of Hydrothermal Ore De-
application to formation waters from
sedimentary basins, in Naeser, N.D. c
Arn6rsson, 5 ., Sigurdsson , S. and Svavars-
posits , Second Edition: John Wiley and and McCulloh, T.H.,ed., Thermal History (
Sons, New York, p. 632-683. of Sedimentary Basins: methods and
son, H., 1982,The chemistry of geother-
mal waters in Iceland. I. Calculation of
Ellis , A.J., 1979b,Chemical geothermome- casehistories: Springer-Verlag, NewYork, c
aqueous speciation from 0° to 370°C:
Geochimica et Cosmochimica Acta ,
try in geothermal systems: Chemical
Geology, v. 25, p. 219-226.
p.99-117.
Lico, M.S., Kharaka, Y.K., Carothers , W.W. c
v. 46, p. 1513-1532.
Arn6rsson, S., Gunnlaugsson, E. and
Ellis, A.J. and Mahon, W.A.J., 1967, Natural
hydrothermal systems and experimen-
and Wright, VA , 1982, Methods of col-
lection and analysis of geopressured c
Svavarsson, H., 1983,The chemistry of
geothermal waters in Iceland. III. Chemi-
tal hot water-rock interaction: Geo-
chimica et Cosmochimica Acta, v. 31,
geothermal and oil field waters: United
States Geological Survey, Water Supply c
cal geothermometry in geothermal
p.519-531,
Ellis, A.J. and Mahon, W.A.J., 1977, Chemis-
Paper 2194, 21 p.
Nehring, N.L. and D'Amore, F.D., 1984,Gas
C
investigation: Geochimica et Cos-
moch imica Acta, v. 47, p. 567-577.
try and Geothermal Systems : Academic
Press, New York, 392 p.
chemistry and thermometry of the Cerro
Prieto, Mexico, Geothermal Field: Geo-
E
Bodvarsson, G., 1960, Exploration and
exploitation of natural heat in Iceland:
Epstein,S., Buchsbaum, R., Lowenstam , therm ics, v. 13, p. 75-89. C
H.A. and Urey, H.C., 1951, Carbonate- Perry, C. and Gillott, J.E., 1979, The forma-
Bulletin Volcanologique, v. 23, p. 567-
water isotopic scale: Geological Society tion and behaviour of montmorillonite
578.
Bodvarsson , G. and Palmason, G., 1961,
of America , Bulletin, v. 62, p. 417-425.
Fleming, B.A. and Crerar, D.A., 1982,Silicic
during the use of wet forward combus-
tion in the Alberta oil sand deposits: c
Exploration of subsurface temperatures
in Iceland : Proceedings U.N. Confer-
acid ionization and calculation of silica
solubility at elevated temperature and
Bulletin of Canadian Petroleum Geol-
ogy, v. 27, p. 314.
c
ence, New Sources of Energy G/24 ,
p. 82-90, Rome.
pH: application to geothermal fluid pro-
cessing and reinjection: Geothermics,
c
v. 11, p. 15-29. C
l.
C
c
r:
\ Fluid Geothermometry in Sedimentary Systems 323
I

(
Ragnarsdottir, K.V. and Walther, J.V., 1983, Sedimentology Research Group, 1981, The Weissburg , B.C. and Wilson , P.T., 1977,
( Pressure sensitive "silica geothermom- effects of in situ steam injection on Cold Montmorillonite and the Na/K geother-
eter" determined from quartz solubility Lake oil sands: Bulletin of Canadian Pe- mometer, in Ellis, A.J., ed., Geochemis-
( experiments at 250°C: Geoch imica et troleum Geology, v. 29, p. 447-478. try : New Zealand Department of Sci-
Cosmochimica Acta, v. 47, p. 941-946. Urey, H.C., 1947, The thermodynamic prop- ence and Industrial Research, BUlletin,
C Reed, M.G., 1980, Gravel pack and forma- erties of isotopic substances : Journal of v. 218, p. 31-34.
tion sandstone dissolution during steam the Chemical Society, p. 562-581. White , D.E., 1965, Saline waters of sedi-
(, injection: Journal of Petroleum Technol- Urey, H.C., Lowenstam, H.A., Epstein, S. mentary rocks, in Young, A. and Galley,
ogy, June , 1980, p. 941·949. and McKinney, C.R., 1951, Measure- J.E., eds., Fluids in Subsurface Environ-
C Reed, M., 1982, Calculation of multicompo- ment of paleotemperatures and temper- ments -A Symposium: American Asso-
C nent chemical equilibria and reaction
processes in systems involving miner-
atures of upper Cretaceous of England,
Denmark and the southeastern United
ciation of Petroleum Geologists, Memoir
4, p. 342-366.
( als, gases and an aqueous phase: Geo- States: Geological Society of America ,

o chimica et Cosmochimica Acta, v. 46,


p.513·528.
Bulletin, v. 62, p. 399-416.
Walshe, J.L. 1986,A six-component chlorite

o Reed, M. and Spycher, N., 1983, Calculated


pH at high temperature in hydrothermal
waters with applications to geother-
solid solution model and the conditions
of chlorite formation in hydrothermal
and geothermal systems: Economic
(
mometry: 4th International Symposium Geology, v. 81, p. 681-703. Accepted 1988
c on Water-Rock Interaction, Misasa,
Japan , p. 401-408.
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
o
l
l
(

324 Diagenesis Geoscience Canada Reprint Series 4 C


C
C
C
C
C
C
(
C
C
C
C
C
C
C
C
C

c
c
c
c
c
c
c
c
c
~
c
SEM photomicrograph of a K-feldspar overgrowth remaining after leaching of the core of the grain. Infiltration by low-salinity
c
groundwater may have caused dissolution offeldspars. The sample is from the Cretaceous Sparky interval in the Aberfeldy heavy oil c
site, Lloydminster area, Saskatchewan. Photograph courtesy of I. Hutcheon and R. Lefebvre (University of Calgary).
c
C
E
C
l
l
C
C
<....

l
(
325

( Index
(
Abercrombie, H. Bacterial sulphate reduction
( Geothermometry in sedimentary systems .. . . . 317-323 Microbial metabolism 0 ••••• 191,193 0 0 ••••• 0 •••• 0 • •

c Albandite
Sulphide precipitation
Barnes, M.A.
Organic diagenesis 205-226
c Manganese sulphide 304 Organic matter 0 • • 189-204
• • • 0 0 • ••• • • •• • • • ••

c Amorphous
Inorganic gels
Argillaceous sedimentary rocks (clay minerals) .. . 182
Barnes, WoC.
Organic diagenesis
Organic matter
205-226
189-204
0 • • ••

( 0 • 0 ••• 0 ••••• 0 0 •• 0 ••••

Silica 227 Basinal burial domain


o
0 •••••••

Aqueous geothermometry 319 0 •••••• • • • •• • • ••• Limestones - Burial diagenetic environment . . 99 0 0 ••• •

o Fluid geothermometry
Mineral saturation index geothermometer 321
Beaches
Strand line diagenesis 0 ••••• 21 ••• 0 • •• • • ••• • • • •• ••

o Na smectite (beidellite)
Na/K and Na/K-Ca .
321
320 0 •• •••••• •••••• • ••••• 0 •
Beidellite
Aqueous geothermometry
Reservoir diagenesis . . . 321 0 • • • • • • •• •• •• • • •• 0 • Na smectite (beidellite) 321
Silica .. 319 Biogenic pelagic carbonates
( Aragonite
0 • • • • ••• • • • • • • • • • • •• • • • • • • • • • • •• •

Recrystallization
Crusts Pore water profiles . . 0 291,293
••• • •••• • • ••• •• • ••

Coniatites 22 0 ••••••••••••••••••• Biogenic siliceous sediments


Strand line diagenesis . 22 0 • • 0 ••••••••••••••• 0 •• Burial diagenesis
Seas Stages 231 0 • •• • • 0 •• • • • ••••••

Carbonate petrology . . 28 0 • • • • • 0 0 ••••• 0 •••• 0 • • • Chert


Argillaceous Depositional environments 228 0 0 •• • • 0 • •••• 0 • • • ••

Chert Formation of bedded chert 231


Lydite . . . . . 0 227
. 0 ••• • ••••• 0 •••••••••••• •• Ophiolite-associated chert 231 0 ••••• ••••• 0 • • • • • •

Sedimentary rocks Shallow water 231 0 • • • • • • • 0 •••

Foscolos, A.E. 177-187 0 •••••••••• Deep-sea environments . . 241


0 •• 0 ••• •• •••• 0 •• • • • • •

Pelitic sediments .. 178 0 0 •••• 0 0 • • • • • 0 • • • • • • • Diagenetic grade


Burial alteration Host rock lithology 242
Clays 0 •••••••••• o 179,180 •••••• • •••• Opal·CT deep-sea environment 241 0. 0 ••••

Mineral transportation in pelitic sediments . 178 0 • Silica phases


Mixed layer system 180 0 • ••• • • • • • • • • • • • •• Characteristics 231 0 • •

Silicates 178 0 ••• 0 • 0 0 •••••• •• Terminology 0 0 •••• 227 0 0 ••••• 0 • • • • 0 0 • • ••

Clay minerals Biological


Amorphous inorganic gels .. . 182 0 •••• 0 • • • 0 • • • Alteration
Carbonates . 0 183
••• 0 0 • • 0 •• 0 • • • • • • • • • • • • • • • Limestones - Sea-floor diagenesis 21 0 ••••• 0 • ••• 0 0

Chlorite 0 • 0 0 0 181
0 ••• •• 0 ••••• •••• •• • 0 0 ••• 0 0 Markers
Definition Geochemical fossils . 0 0 4 • • • •••• • ••••• • •••• 0 •• •

Illite 0 .0. 0 180


0 •• 0 . 00 ••••• 0 ••••• 0 ••• •••• Bittern salts
Diagenesis, organic matter and cementation . 184 Potash deposits 155
Kaolinite 181 0 •••• •• Burial
Aromatic compounds Cements
Organic matter Deeper burial
Burial diagenesis . 200,205,211 0 0 0 • 0 0 0 0 0 •• 0 0 0 0 Limestones - Burial diagenetic environment .. 89 0 •

Authigenic Shallow burial marine


Carbonates Limestones - Burial diagenetic environment . ... 88
Calcite and siderite Compaction Model
Early diagenetic pore water/sediment Dolomitization models ... 128,132,134,135 0 • 0 ••• 0 •

interact ion . 0 304 • • ••• •• • ••• • • • ••••• • •• ••• • Diagenesis


Cementation Schematic figure 2 0 ••• • •• ••••••••••••••

Siliciclastic sediments ... . 168 0 0 •• • • 0 0 • • • ••• 0 Stages


Dolomite Biogenic siliceous sediments .. .. 231 0 ••• 0 ••• 0 0

Deep sea dolomite Diagenetic models


Early diagenetic pore water/sediment Limestones 0 • • 990 • • •••• •• 0 •• 0 • • • • • • • • •

interaction . . 3050 ••• •• 0 • ••• • •••••• • 0 • 0 0 ••• Bustin, A.M.


Autocementation Organic diagenesis . . 0 0 ••••205·226 0 •••••••••• 0 • 0 0

Liquid hydrocarbons ~ . . .. 88,92 0 • •• • •••• •• • •• • • • • • Organic matter 189-204


(

326 C
C
Calcareous Cement
C
Sinter (speleothems) Authigenic cementation C
Karst, subsurface 50 Siliciclast ic sediments 168
Tufa Petrography
C
Karst, subsurface 50 Fibrous calcites 26 C
Calcite Fibrous cements 26
Bladed-prismatic Spherulitic cements 26 . C
Sea-floor lithification
Seas
Limestones - Burial diagenesis 89
Epitaxial cement 26
C
Carbonate petrology 28 Fibrous calcites 26 (
Calcium zeolite Isotopic signature 26
Chert - diagenetic silica transformations 246 Microcrystalline calcite 26 C
Caliche Scalenohedral cement 26 (
Rhizoconcretions 44,45 Spherulitic calcite 26
(calcrete or duricrust) Stromatactis 26 (
Definition 43 Stratigraphy
Facies Carbonate precipitate 13,16,17 C
Water-controlled, rock-air interface
Litholog ies
43 Cementat ion C
Definition 52
Petrography 44 (
Cements
Nodules
Glaebules 44
Evaporites C
Syndepositional features 146
Carbon
Isotope studies
Cavity cements 153 C
Geochemistry of kerogen '" 217 Chalcedony C
Preference index Silica 227,254,255
Definition 216 Geothermometer C
Carbonate Fluid geothermometry 320
C
Compensation depth Changes with depth
Definition 14 Porosity-depth curves 96,98 C
Diagenesis
Cathodoluminescence 10
Chemical
Compaction
C
Diagenesis Definition 83 C
Diagenetic environments 9 Composition
Dissolution Dolomite 113 C
Dissolution
Petrology
14 Signatures
Isotopic composition of precipitates 17,20
C
Aragonite seas 28 Structure C
Petrology Hydrocarbon generation 196
Calcite seas 28 Chert C
Caliche
Lublinite 45,50
Biogenic siliceous sediments
Diagenesis
C
Microcodium 45 Physical 247 C
Precipitate Burial diagenesis
Cement stratigraphy 13,16,17 Opal-A C
Sediments
Porosity ranges 96,97,98
Physical characteristics
Opal-CT
232 C
Water-controlled precipitation 50 Mineralogic phases 236 C
Carbonates
and carbonate sandstones
Opal-CT
Physical characteristics 234
c
Chertification
Argillaceous sedimentary rocks (clay minerals)
253
183
Definition
Depositional environments
227 e
Catagenesis Biogenic siliceous sediments 228 (
Definition 1,1n ,195 Modern ocean floor
Kerogen Biogenic siliceous oozes 228
Organ ic matter - burial diagenesis 195 Tectonics 230 c
Cathodoluminescence
Carbonate diagenesis .... . . . ... . . .. . .. .• ... .• . 10
Diagenetic silica transformations
Calcium zeolite 246 c
C
l.
C
C
('.
(
\. 327

c
C Diagenet ic grade Pelagic stratigraphy
r. Opal-A to Opal-CT Siliceous sediments 229
Rate-controlling factors 241,242 Chloride comp lexes
C Temperature and time 241 Metal comp lexes 3
C. Opal-CT
Rate-controlling facto rs
Chlor ite
Argillaceous sedimentary rocks (clay minerals) ... .. 181
c Precipitation . . . 244 Choquette , P.w.

r Opa l-CT to quartz transformation


Silica stability fields
245
246
Limestones ................ .
- Burial diagenetic environment
9-111
75-111
( Transformat ional mechanisms 237 - Meteoric diagenet ic environment 35-73
Flint Formation - Sea-floor diagenetic environment 13-34
o Geochemistry 263 Clay minerals

o Formation of bedded chert


Biogenic siliceous sediments 231
Argillaceous sedimentary rocks
Burial alteration 179,180
o Inorgan ic and replacement cherts
Silica diagenesis 253
Climate
Geologic time variation
Origin Limestones - Meteoric diagenesis 64,65
( Hesse, R. 227-251 Compaction Model (burial)
Petrography Dolomitization models 128,132,134
o Evaporites . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . 265 Complex authigenic carbonates

o Shallow water
Biogenic siliceous sediments 231
Early diagenetic pore water/sediment interaction .. . 306
Coniatites
o Silica phases
Solubility diagrams 233
Aragonite crusts
Connate water
22

o -replacing evaporites
Chertification 265
·Definition
Pore water diagenesis
2n
2n
Chertification Continental margin environments
o Carbonates and carbonate sandstones
Chert-replacing evaporites
253
265
Pore water profiles - type 4
Controls, processes and products
294

o Carbonates
Quartz fabrics
Limestones - Burial diagenetic environment
Deep burial 75,76
(
Replacement 257 Convective pore-water circulation flanks
o Select ive replacement
Void filling
258
257
Mid-ocean ridges
Pore water profiles - type 1 288
o Silica fabric Coorong Model (sabkha)

c Equigranular
Fibrous 254,255
254 Dolomitization models
Correlation chart
127,131,133,134

o Silica sources
Silicification
260 Organic diagenetic indicators
Organic maturation indices
206
206
o Chalk
Tim ing 259 Corrosion
Dissolution and precipitation
Paramoudra structure 263 Biogenic 39
o
r
Limestones
Knauth 's Geochemical Model 261
Hydrostatic
Mixing
39
39
Cherts Simple 39
Inorganic and replacement
o Geothermal silica
Hesse , R.
269
253-275
Cristabolite
Silica 227
D Hydrothermal and volcanogenic cherts
Criteria for bur ial alteration features
Evaporites 147
Environments 268
Geothe rmal areas 269 Crystal structure
Submarine exhalations 269 Kinetic effects
Lagoona l and lacustrine cherts 267,268 Dolomite 113,117
,
~. Magadi-type cherts . . . . . . . . . . . . 267 Crystalline framework fabrics
Pedogenic cherts 268 Evaporites
Precambrian cherts 270 Syndeposit ional features 143
* see also chertification 263-275 Crystallites
Silicification of wood 253 Precipitated particles 18
Volcanogenic cherts 268 Whitings 18
c
328
(
C
Darcy's Law Indicators
C
Water movement 36 Organic matter 218 C
Deep burial diagenesis Organic matter and cementation
Diagenetic environments . . . . . . . . . . . . . . . . . . . . . . . 10 Argillaceous sedimentary rocks (clay minerals) ... 184
C
Deep phreatic zone
Limestones - Meteoric setting 39
Physical
Chert
C
Deep-sea environments Biogenic siliceous sediments 247 C
Biogenic siliceous sediments
Definition
241 Siliciclastic sediments
Fluid flow 171
C
Argillaceous sedimentary rocks (clay minerals) 180 Geological controls . . . . . . . . . . . . . . . . . . . . . . . . 170 C
Caliche (calcrete or duricrust) 43 Heavy oil and tar sands 171
Carbon preference index 216 Hydrocarbon reservoirs 171 C
Carbonate compensation depth
Catagenesis " 1,1n,195
14 Diagenetic
Classification
C
Cementation 52 Eogenesis 2 C
Chemical compaction 83 Mesogenesis 2
Chert 227 Telogenesis 2 C
Connate water 2n Cycle C
Diagenesis 1 Controls and products 5
Dolomitization reaction 115,116 Processes C
Early diagenesis 308 Porosity 3
Evaporites Pressure solution 3 C
Primary depositional
Secondary diagenetic
141,142
141,142
Environments
Carbonate diagenesis 9
C
Fluid geothermometry 317 Deep-burial diagenesis . . . . . . . . . . . . . . . . . . . . . . 10 C
Humin 193 Meteoric diagenesis 9
Karst, surface 45 Sea-floor diagenesis 9
C
Limestones
Burial diagenetic environment
Grade
Host rock lithology
C
Pressure solution 83 Biogenic siliceous sediments 242 C
Deep burial 75 Opal-A to Opal-CT rate-controlling factors
Metagenesis 1,199 Chert - diagenetic silica transformations ... 241-242
C
Neomorphism 10 Opal-A to Opal-GT, temperature and time C
Organic matter Chert - diagenetic silica transformations ..... 241
Eogenesis 189 Opal-CT - deep-sea environment C
Pelagic stratigraphy
Phreatic cements
229
53
Biogenic siliceous sediments
Opal-CT - mineralogic phases
241
241
C
Silica 227 Opal-CT rate-controlling factors, precipitation C
Silicon, dissolved 227 Chert - diagenetic silica transformations ..... 244
Steinmann trinity 230 Opal-GT to quartz transformation C
Telogenesis 199 Chert - diagenetic silica transformations 245 <;
Vadose cements 52 Models
Vadose zone Organic matter 218 C
Zone of gravity percolation 36 Pathways 10
Zone of infiltration 36 Signature C
Deformation features
Evaporites
Fluid composition
Transport mechanism
9 C
Burial alteration features 148 Diffusion C
Detrital framework textures Organic matter oxidation 285
Evaporites Low to intermediate sedimentation rate
C
Syndepositional features . . . . . . . . . . . . . . . . . . . . 143
Devonian Prairie Formation
Organic matter oxidation 286 E
Pore water profiles 286
Potash evaporites 157 Diatom ooze l
Diagenesis Siliceous ooze 227
and porosity Diffusion-controlled
C
Siliciclastic sediments Gradient C
Burial alteration 166 Pore water profiles - type 2 290
C
C
C
l
C
(
329

(
Pore-water trends Dolostones
( Pore water profiles - type 2 288 Dolomite 0 0 0 113-123,125-139
Disruption and destruction of sedimentary structures Ancient
( Evaporites Dolomicrite 0 0.. 0.. 131,133
( Burial alteration features 148 Dolomitization . 0. • . . 0. 0•. 00•.. 0. . . • •. . . . • . 130
Dissolution Megacrystalline white dolomite .. 0 132
( Carbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 Dorag Model
Fabric selective 20
( Dolomitization models 113,261
Limestones - Burial diagenetic environment 93
Dripstone
( and precipitation
Sinter . 0 00 0 0 0 0 0.. 50
Corrosion
Biogenic 0 • • • • 390 •• •
Early diagenesis
Hydrostatic . 0 0 0 39 Definition 0 0 00 00 308
Mixing 0 0 0• . • . . • . 00. 00 0. 0.39 Organic matter oxidation
o Simple 0 00 0" 0. 0.. 0" 0 0 39 Carbonate reduction zone . . 0. 0. . . . . 00... 281,283
Fermentation zone 00. 0... 0. . 000. . . . • . . . . . . 283
o Incongruent dissoution
Limestones - Meteoric setting
Dissolution-reprecipitation
00... . •... 00 42
390 • • 0
Nitrate reduction zone 0. . . . . . . . . • . . . . 0. . 282 ,283
Oxidation zone 000.. • 00.. 00 00 00 0281
( Sulphate reduction zone 281,283
features
o Evaporites Thermocatalytic reaction zone '" 00 00 00283

o Syndepositional features
Mechanism
144 Pore water/sediment interaction
Authigenic carbonates

o Opal-CT - mineralogic phases . . 0. . . . •. . .. .• . 237


Dolomicrite
Calcite and siderite . . . 000. . . • . . 0. • . . . . . 0304
Authigenic dolomite
Dolostones, ancient 0 131,133 Deep sea dolomite 00......... •... 000... . 305
Dolomite Complex authigenic carbonates 306 0 ••• • •

Chemical composition . 000.. 0... • 0........•• 0. 113 Hesse, R. 0...• 0 000. 0. . 0 2n-316
o Crystal structure
Kinetic effects . 0. . . . . .... 0.... 0.... 0.. 0113,117
High sedimentation rate basins . . ..
Reactions .. 00... 0.... 00. 0. 00... • 0. 00• . 301
0294•• • • • • • 0 •

Dolomitization Sulphide precipitation . . .. . 0.. .. . 0 0302


Chemistry and precipitation . . . . . 0• 113-123,125-139 Ion exchange reactions and adsorption . 00 0306
Dolostones 0 0... • . •. . . . . . . . .. 113-123,125-139 Rock-water interaction 9,2n
o Morrow, DoW.
Natural environment
0" 0 0 113-123,125-139 Sulphide precipitation
Framboidal pyrite . 0 0.... 0. . . . 0. . 302,303
o Stability
Dolomitization
0. ... •. . . . •.... 0 00. . 115 Iron monosulphides 0
Manganese sulphide
00. 0.. • . . . . 0... • . 302
304
Factors for process 0. . • 0 0. • . . 125 Electron paramagnetic resonance
o Ancient dolostones 00..• 0
Sucrosic or secondary replacement
0.. 0. •.... 0. . 130
131,132
Geochemistry of kerogen 0... • 0... •. 217
Eogenesis
Chemistry
and catagenesis
o Sulphate ions
Volume problem .. 00
0. .• •. . 0. 0• 0119
0. . 0. 0.... •... 00. 0120
Porphyrins and isoprenoids . .... 0..... ... . . • 213

o and precipitation
Dolomite . . 0• . . . 0.. 0. 0... •.. 113-123,125-139
Carbon preference index
Organic diagenesis 00. .. .•. . • • • . • . . • 216
Diagenetic classification 2 0 ••

Models ... 0.... •. 00. •.... • .. . 00. 0.. 0. 0. 125-139


Organic matter
Burial compaction . 00. . 0....•... 128,132,134,135
Diagenesis 0 0.. 0 189,191,211
Coorong 0..• 00" .. 0 0 00 127,131
Dorag 0. .. . • . 0. 113,261 Evaporative pumping
Evaporite pumping . 0..• • 0. • 0. 0.. 0. 0. . . . • . . 113 Sabkha Model 0 • • • •• • • • • • • • • • • • 127
Hydrothermal convection 129,132 Evaporites
( Mixed-water or Dorag 0. 0. 128,131,132,134,135 Burial alteration
Organogenic sea floor 0.. 0. 00. 0• . • . . . . 129 Features
Recognition factors Criteria 0 • 147
r: Ancient dolostones . 0.. 0. . . . . 0. . . . . . . . . . . 130 Deformation features . 0. 00 0. . . . . . 148
Reflux. 0 0 00 o' 125,130,132 Disruption and destruction of sedimentary
Solution-Cannibalization 000. 0 0.•. 0. . 129,130 structures 0...• 0 148
Reaction Intersediment growth of nodules 151
Definition 0. 0 0• . . 0 115,116 Polygonal mosaic textures 0. .. 00 0 0. 148

r:
c
330
(
C
(
Textures Flowstone
Fluid inclus ions 154 Sinter 50 (
Intrasediment growth Fluid composition
of euhedra 149 Diagenetic signature 9 C
of nodules 151 Fluid geothermometry (
Secondary replacement Aqueous geothermometry 319
Pseudomorph 151 Mineral saturation index geothermometer 321 (
Dehydration pair 151 Na smectite (beidellite) 321
Na/K and Na/K-Ca 320
(
Non-reaction pair 151,153
Chert
Petrography 265
Reservoir diagenesis
Silica
321
319
C
Definition 141 Chalcedony geothermometer 320 C
Primary deposition 142 Definition 317
Secondary diagenetic . . . . . . . . . . . . . . . . . . . . . . 142 Geothermal systems 317
C
Dissolution at depth Geothermometry in sedimentary systems 317-323 C
Pore water profiles - type 8 301 Mineral equilibria 317
Lowenstein, T.K 141-163 Fluid inclusions C
Evaporites
Potash deposits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Primary versus secondary features 141 Burial textures 154
C
Pumping model Fluorescence microscopy C
Dolomitization models 113 Organic diagenesis
Spencer, R.J 141-163 Methods of quantifying 206 C
Texture
Foam structure . .. .. . .. .... .• . . .. . .... . .. . 148
Formation water
Pore water diagenesis
C
Polygonal mosaic 148 Terminology 278 C
Syndepositional features Foscolos, A.E.
Cements 146 Argillaceous sedimentary rocks 177-187 C
Cavity cements
Crystalline framework fabrics
153
143
Fossil fuel resources
Organic matter 189-204
C
Detrital framework textures . . . . . . . . . . . . . . . . . . 143 Fossil record C
Dissolution-reprecipitation features 144 Sea-floor lithification 23
Sedimentary structures 142 Frittenkarren C
Exokarst Solution grooves
Gardner, D.
46 C
Karst 45
Fabric selective dissolution Geothermometry in sedimentary systems . .. .. 317-323 C
Dissolution 20 Gas hydrates
Factors Pore water profiles - type 5
C
for process Isotope fractionation 296 C
Dolomitization 125 Salt fractionation 296
Limestones - Burial diagenetic environment Geochemical C
Deep burial diagenesis
Extrinsic factors 77
Aspects
Limestones - Meteoric diagenesis 60
C
Intrinsic factors 76 Cathodoluminesence 60 C
Pressure solution 87 Minor elements 60,61
Burial depth 87 Minor elements CL zones 61 C
Clay mineralogy
Early dolomitization
87
88
Minor elements strontium
Stable carbonate (calcite) sediments
60
63
C
Liquid hydrocarbons 88 Stable isotopes 61 C
Metastable mineralogy 87 Classification of early diagenetic environments
Pore water composition 87 Geochemistry 307 <...
Fibrous calcites Criteria e
Cement petrography
Fibrous cements
Cement petrography
26

26
Ancient dolomitization recognition factors
Fossils
Biological markers
133

4
c
Flachkarren Methods
Karren 48 Organic diagenesis
Flint Methods of quantifying
Siliceous sediments 227 Biological markers 211 l

<...

l
(
o
-,
r: 331
(

c Carbon preference index 216 Siliciclast ic rocks . . . . 165-176


c Extractable organic compounds
Light hydrocarbon analysis
211,216
216
Hydration shell
Magnesium-bearing carbonate 117
C' Total extractable organic matter 216 Hydrocarbon generation
c Geochemistry
Chert
Chemical structure
Hydrogen index
196

( Flint Formation 263 Geochemistry of kerogen 217

c Geochemical classification of early diagenetic


environments . . . . . .
Kerogen
307
216
Hydrothermal
Activity and intrusion igneous dykes and sills
( Pore water profiles - type 9 301
Pyrolysis 216 and volcanogen ic cherts
( Carbon isotope studies 217 Inorganic and replacement cherts
o Electron paramagnetic resonance
Hydrogen index
217
217
Environments
Geother mal areas
268
269
o Infrared spectroscopy
Oxygen index
217
217
Submarine exhalations 269

o Proximate analysis 218


Convection Model
Dolomitization Models 129,132
o Ultimate analysis
Silicification
217 Smokers
Pore water profiles 288
o Cow Head Group
Geochronology
265 Illite

o Kerogen
Definition
Argillaceous sedimentary rocks (clay minerals) ' " 180
o Carbon isotope studies
Knauth's Geochemical Model
217
261
Incongruent dissoution

o Geothermal
Silica
Dissolution and precip itation
Infrared spectroscopy
. 42

o Inorganic and replacement cherts 269


Geochemistry of kerogen
Inside grains and skeletons
217

o Systems
Fluid geothermometry 317
Limestones
Sea-floor cementation styles . . . . . . . . . . . . . . . . . . 18
Geothermometry in sedimentary systems
Abercromb ie, H. . 317-323 Intersediment growth of nodules
o Fluid geothermometry 317-323 Evaporites
Burial alterat ion features 151
o Gardner, D
Hutcheon, I.
317-323
317-323 Interstitial waters
o Ghyben-Herzberg princ iple Pore water diagenesis
Terminology 278
o Water table
Glaebules
37,39
Intrasediment growth

o Caliche nodules
Gulf Coast fluid redistr ibution model
44 of euhedra
Evaporites
o Argillaceous sedimentary rocks 177 Burial textu res
of nodules
149

o Hesse, R.
Chert Evaporites

o Origin
Inorganic and replacement cherts
227-251
253-275
Burial textures
Ion exchange reactions and adsorption
151

o Diagenesis of biogen ic siliceous sediments 227-251 Early diagenet ic pore water/sediment interaction . .. 306

o Early diagenetic pore water/sediment interaction 277-316


High sedimentation rate reactions
Isotopes
Oxygen and carbon
( Basins Ancient dolomitization recognition factors 135
Early diagenetic pore water/sediment Isotopic composition of precipitates
l; interaction 294,301 Chemical signatures 17,20
r Sulphide precipitation Platform carbonates 17,20
Early diagenetic pore water/sediment James, N.P.
c interaction . . . . . . . . 302 Limestones 9-12

c. Humin
Definition
Hutcheon , I.
193
- Burial diagenetic environment
- Meteoric diagenetic environment
- Sea-floor diagenetic environment . . ,
75-111
35-73
13-34
Geothermometry in sedimentary systems ... .. 317-323 Jasper
Sandstone diagenesis . . . . . . . . . . . . . . . . . . . . . 165-176 Siliceous sediments 227
c
(
332
C
C
Kamenitza
Solution basins 46
Limestones
Choquette, P.w. 9-111 c
Kaolinite James, N.P 9-111
Argillaceous sedimentary rocks (clay minerals) .. ... 181 Burial cements C
Karren
Flachkarren 48
Origin
Autocementation 93
C
Klutkarren 48 Hydrocarbons . . . . . . . 93 C
Rundkarren 48 Passive cementation 92
Solution sculpture 46 Burial diagenesis
C
Karst Calcite C
Exokarst . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45 Bladed-prismatic calcite . . . 89
Subsurface Models 99 C
Calcareous sinter (speleothems) 50
Calcareous tufa 50
Origin of burial cements
Passive cementation 92
C
Lenticular zone processes
Dissolution 50,51
Autocementation 92 C
Burial diagenetic env ironment
Paleokarst 51 Basinal burial domain 99 C
Speleothems 50
Syngenetic karst . . . . . . . . . 51
Bur ial cements
Deeper burial 89
C
Vadose zone 48
Water table zone
Shallow burial marine 88 C
Choquette, P.w. 75-111
and phreatic zone 49
Deep burial C
Processes
Dissolution 49 Controls , processes and products
Definition
75,76
75
C
Precipitation 49
Surface Factors
Definition 45 Extrinsic factors
Intrinsic factors
n
76
c
Facies
Water-controlled rock-air interface 43 Mesogenetic realm
Phreatic
75
75
c
Landforms
Solution sculpture
48
46 Thermobaric realm 75 c
Kerogen Dissolution
James, N.P.
93
75-111
c
Colouration
Organic diagenesis Origin of burial cements 92 c
Methods of quantifying
Thermal alteration index . . . "
207
207
Pressure solution
Definition 83 c
Geochemistry
Geochronology
216 Factors
Burial depth 87
c
Carbon isotope studies . . . . .
Organic matter
217 Clay mineralogy 87 c
Catagenesis stage 195,196
Early dolomitization
Liquid hydrocarbons
88
88 c
Van Krevelen diagrams 4,217
Klutkarren
Metastable mineralogy 87 ~
Pore water composition 87
Karren 48 Processes c
Knauth's Geochemical Model
Chertification
Chemical compaction
Physical compaction
83
79 c
Limestones
Geochronology
261
261
Pressure solution . 83 c
Lagoonal and lacustrine cherts
Products
Recognition of burial cements
76,79,99
90 c
Inorganic and replacement cherts
Lapies
267,268 Isotopic composition
Salinity
91
91
c
Solution sculpture
Lead-zinc deposits
46 Temperature
Shelf/platform burial domain
90
100
e
Megacrystalline white dolomite 132 Meteoric diagenesis
Lenticular zone
Meteoric setting 37
Choquette, P.W
Climate
35-73
c
Processes Geologic time variation
Geochemical aspects
64,65
60
c
Dissolution
Subsurface Karst 50,51 Cathodoluminesence 60
l
l
l.
(
(\
(
333
c
c Lydite
( Minor elements 60,61 Argillaceous chert 227
( . CL zones 61 Lysocline
Strontium 60 Vertical zonation 14
C Stable carbonate (calcite) sediments 63 Magadi-type cherts
Stable isotopes 61 Inorganic and replacement cherts 267
Ct James, N.P. 35-73 Magadilite
( . Mineral-eontrolled cementation processes 52 Silica 227,266,267
Alteration Magnesium-bearing carbonate
( of calcite 57 Hydration shell . . . . • . . . . . . . . . . . . . .. ... . .... . . 117
of magnesium 54 Mcllreath, I.A.
( Cement stratigraphy 54 Introduction 1-7
o Diagenesis
Freshwater-seawater mixing 59
Megacrystalline white dolomite
Dolostones, ancient 132
o Vadose versus phreatic settings 57 Lead-zinc deposits 132

o Phreatic
Vadose
53
52
Mesogenesis
Diagenetic classification 2
Original mineralogy 35 Mesogenetic realm

o Recognition of products
Setting
63 Limestones - Deep-burial diagenetic environment . . . 75
Metagenesis

o Deep phreatic zone


Dissolution and precipitation .... .. . .. . .. . . • 39
39 Definition ... . .. •.•. . ... ........... ..... ... 1,199
Metal complexes
o Mixing zone . . . .• . . . . . . . . . . . . . .. . . . .. . . . 37
Phreatic 35
Chloride complexes
Metamorphism
3

Vadose 35 Diagenesis 1
Water-controlled 43 Meteoric
Sea-floor diagenesis Diagenesis
o Biological alteration
Cementation styles
21
18
Diagenetic environments
Setting
9

Between particles-platform 18,19 Lenticular zone ....... ... ............. •.... 37


o Inside grains and skeletons
Neomorphism
18
20
Limestones
Phreatic ..• .• .. . . .. .. . . . .. .. . . . . . . • ... . 35
o Shallow enclosed basin 19 Vadose 35

o Slope and deep basin


Choquette,P.W
19
13-34
Water table
Water
36

o James, N.P.
Lithification
13-34 Influx
Pore water
* see also Sea-floor lithification 23 Diagenesis

o Strandline diagenesis
Zonation
21 Terminology
Profiles - type 6
278
300
c. Deep water
Latitude
13
14
Methods of quantifying

o Shallow 13
Organic diagenesis
Microbial metabolism
205

o Vertical .... . ... • • •..... ... . . ........ . . • 13


Liquid hydrocarbons
Bacterial sulphate reduction 191,193

o Autocementation 88,92 Microcodium


Carbonate petrology
o Lithification
* see also Sea-floor lithification Caliche 45

o
(
Limestones - Sea-floor diagenesis
Lowenstein, T.K. .-
23 Mineral-eontrolled cementation processes
Limestones - Meteoric diagenesis
Evaporites 141-163 Alteration of calcite 57
Lublinite Alteration of magnesium-calcite .......... . . •.. 54
l Carbonate petrology Cement stratigraphy 54
Caliche . ..... . . .• • .. . . . .. . . . . . ... .. .. .. 45,50 Diagenesis
l Lussatite Freshwater-seawater .. . . ... . .... .. . . . .. •• 59
1'-
~. Silica 234 Vadose versus Phreatic 57
r' Lutecite Phreatic ............................. •.... 53
Silica ....•......... •................... 227,255 Vadose 52
(
334 C
(

Physical characteristics
C
Mineral equilibria
Fluid geothermometry 317 Chert C
Mineral transportation in pelitic sediments Burial diagenesis 234
Argillaceous sedimentary rocks Ophiolite-associated chert
C
Burial alteration 178 Biogenic siliceous sediments 231 C
Mineralogy of precipitates
Platform carbonates 15,16 Ophiolite suite C
Steinmann tr inity 230
Mixed layer system
Argillaceous sedimentary rocks
C
Organic
Buri~atteration 180 Diagenesis C
Mixed-water or Dorag Model Barnes, M.A. 205-226
Dolomitization models 128,131,132,134,135 Barnes , W.C 205-226 C
Mixing zone
Limestones - Meteoric setting 37
Bustin , A.M
Eogenes is
205-226 C
Models and catagenesis C
Diagenesis models Isoprenoids 213
Organic matter 218 Porphyrins 213 C
Dolomitization models
Solution-film model
125-139
88
Carbon preference index
Methods of quantifying
216
205
C
Modern offshore basins Fluoresence microscopy
Geochemical methods
206 C
Pore-fluid evolution
Diagenesis regimes 279 Biological markers 211 C
Carbon preference index 216
Morrow, D.W.
113-123,125-139
Extractable organ ic compounds 211,216 C
Dolomite
Light hydrocarbon analysis 216
Introduction 1-7
Natural environment stability
Dolomite 115
Total extractable organic matter
Kerogen colouration
216
207 c
Neomorphism
Vitrinite reflectance
Porphyrins . . . . . . . . . . . . . . . . . . . . . . . . . . . .
205
213 c
Definition
Limestones - Sea-floor diagenesis
10 Diagenetic indicators
Correlation chart 206
c
Cementation styles 20 Matter c
Novaculite
Siliceous sediments 227
Barnes , M.A.
Barnes, W.C. .
189-204
189-204 c
Numerical models
Graphical methods
Bustin, A.M. .
Burial diagenesis
189-204
c
Oceans
Organic matter diagenesis 219 Aromatic compounds
Catagenesis
200 ,205,211
195
c
Dissolved silica Metagenesis
Telogenesis
199
199
c
Silica budget 228
Oil window Diagenesis C
Organic matter
Catagenesis stage . . . . . . . . . . . . . . . . . . . . . . . . . 197
Catagenesis
Kerogen 195,196
E
Oligocene Rhine Graben Oil window "
Eogenesis .. ...... .......•.... ... 189,191,211
197 C
Potash evaporites . . . . . . . . . . 156
Opal
Definition 189 C
Indicators . . .. .... .. .. ... .. ..... .. . •... 218
Silica 227,232,254
Models 218 C
Opal-A
Physical characteristics
Numerical models
Graph ical methods 219
C
Chert
Burial diagenesis 232
Paleogeothermal gradients . . . . . . . . . . . . . 219 c
Opal-CT
Mineralogic phases
Sources
Terminology
191
190 e
Fossil fuel resources 189-204 (
Chert Oxidation
Burial diagenesis
Diagenetic grade
236
241
Diagenetic transport mechanism l
Diffusion 285
Dissolution-reprecipitation mechanism 237 Low to intermediate sedimentation 286 C
Quartz transformation 237 Early diagenetic
Transformation mechanisms 237 Carbonate reduction zone 281,283 l
C
(.
(
c
c 335
(

c Fermentat ion zone 283 Platform carbonates


( Nitrate reduction zone 282,283 Precipitates
Oxidation zone 281 Isotopic compos ition 17,20
C.I Sulphate reduct ion zone 281,283 Mineralogy 15,16
C Thermocatalyt ic reaction zone . .
Maturation indices
283 Petrography
of aragonite 17
c.. Correlation chart 206 of magnesium calcite 16

c Organogenic Sea-Floor Model


Dolomitization Models 129
Polygonal mosaic textu res
Evaporites
( Origin
Burial alteration features 148
of bur ial cements
( Hydrocarbons 93 Porcelanite
() Limestones - Burial diagenetic environment 92 Siliceous sediments 227

o Passive cementation
Autocementation
92
93 Pore water
Diagenesis
Original mineralogy
Limestones - Meteoric diagenetic environment . .. . 35 Connate water 2n
Sources of data 278
Ostwald processes
Terminology 2n
o Ostwald ripening
Quartz transformation
238,246
238,246
Format ion water 278

o Oxygen index
Interstitial wate rs
Meteoric waters
278
278
o Geochemistry of kerogen . . . .
Paleogeothermal gradients
217 Saline waters
Profiles
278

o Organ ic matter diagenes is "


Paleokarst
219 Biogenic pelagic carbonates
Recrystallization 291,293
(1 Subsu rface karst 51 Diagenetic transport mechan ism
o Paramoud ra structure
Chertification of chalk 263
Low to intermediate sedimentat ion
High sedimentation rate
286

o Pedogenic cherts Pelagic environments 291,294

c Inorganic and replacement cherts 268


Silcrete . .. . . . . . • . .. . . . . . . . . . . . . . . . . . . .. . . . . 268
Hydrothermal smokers
- type 1
288

o Pelagic Convective pore-water circulation flanks

o Environments
Pore water profiles -type 2
Mid-ocean ridges 288

o High sedimentation rate


Stratigraphy
291,294 Diffusion-controlled
Gradient 290
o Definition 229
- type 3
Pore-water trends 288

o Pelitic sediments
Argillaceous sedimentary rocks 178 Reaction-controlled, in subox ic pelagic 291
r -type 4
Permian Salado Formation
Continental margin environments 294
o Potash evaporites
Petrographic and textural criteria
157
-type 5

o Anc ient dolomitization recognition factors 131


Gas hydrates
Isotope fractionation 296
o Petrography
Caliche lithologies 44 -type 6
Salt fract ionation 296

(1 of precipitates Meteoric wate r influx 300


(
Aragonite - type 7
Platform carbonates . . . . . . . . . . . . . . . . . . . . . . 17 Thrust faulted sections
e Magnesium calcite
Platform carbonates . . . . . . . . . . . . . . . . . . . . . . 16 -type 8
Active lateral pore-water flow 300

Phreatic Evaporite dissolution at depth 301


, Cements - type 9
Definition . . . . . . . . . . . . . . . . 53 Hydrothermal activity and intrusion
,-' Limestones - Deep-burial diagenetic environment 75 Igneous dykes and sills 301
Phytokarst Sedimentation
Solution sculpture 46 • see also Early diagenetic pore water
,-
'-.'

'--.'
r-
c
336
c
Recognition
c
Pore-fluid evolution
Diagenesis regimes Factors c
Modern offshore basins
Porosity
279 Ancient dolomitization
Geochemical criteria 133 c
Depth curves Oxygen and carbon isotopes 135 c
Changes with depth
Ranges
Carbonate sediments
96,98

96,97,98
Petrographic and textural criteria
Stratigraphic and facies criteria
Trace elements
131
130
134
c
Secondary porosity Ancient dolostones
Siliciclastic sediments
Porphyrins
170 Dolomitization Models 130 c
Organic diagenesis 213
of burial cements
Limestones - Burial diagenetic environment 90 c
Potash deposits
Bittern salts 155
Isotopic composition . . . . . . . . . . . . . . . .
Salinity
91
91
c
Evaporites 155 Temperature 90 c
Precambrian cherts
Inorganic and replacement cherts
Silcrete
270
270,271
of products
Limestones - Meteoric diagenetic environment . . . 63 c
Reflux Model
Precipitated particles Dolomitization models 125,130,132
Crystallites 18 Seepage Refluxion 125,131,133 c
Pressure solution and quartz overgrowths
Siliciclastic sediments 166
Rhizoconcretions
Caliche 44,45 c
Stylolites
Primary versus secondary features
167 Rillenkarren
Solution flutes 46
c
Definition Rimstone (
Evaporites
Processes
141 Sinter
Rinnenkarren
50
c
Diagenetic cycle
Porosity
2,3
3
Solution grooves
Rock-water interaction
46 c
Pressure solution 3 Early diagenetic pore water/sediment interaction •. 9,277 c
Limestones - Burial diagenetic environment
Chemical compaction 83
Rundkarren
Karren 48
c
Physical compaction
Pressure solution
79
83
Sabkha Model (Coorong Model) c
Products
Proximate analysis
76,79,99
Evaporative pumping
Saline waters
127,133,134
c
Geochemistry of kerogen 218
Pore water diagenesis
Terminology 278
c
Pyrolysis
Geochemistry of kerogen 216
Sandstone diagenesis c
Quartz
Hutcheon, I.
Sea floor
165-176
c
Crystallinity index
Silicification 253
Diagenetic environments
Lithification
9
c
Fabrics
Replacement
Cement petrography c
Chertification of carbonates
Selective replacement
257 Epitaxial cement
Fibrous calcites
26
26 c
Chertification of carbonates 258 Isotopic signature 26 c
Void filling
Chertification of carbonates 257
Microcrystalline calcite
Scalenohedral cement
26
26 c
Transformation
Opal-CT
Spherulitic calcite
Stromatactis
26
26 c
Mineralogic phases
Ostwald processes
237
238,246
Fossil record
Secondary
23 e
Quartzine Porosity l
Silica 227,255 Siliciclastic sediments 170 (
Radiolarian ooze Replacement
Siliceous ooze 227 Pseudomorph dehydration pair (
Reaction-controlled pore-water profiles in suboxic pelagic Evaporites
Pore water profiles - type 3 291 Burial textures 151 (
C
(
r
o
c 337
(
c"
o Pseudomorph non-reaction pair
Evaporites
Diagenesis
Hesse, R. . 227-251
() Burial textures 151,153 Diatom ooze 227
Sedimentary structures Radiolarian ooze 227
C Evaporites Sponge (spicule) ooze 227,253
Syndepositional features 142 Porcelanite 227
( 1 Seepage refluxion Silica sources of non-detrital silica 227
( Reflux Model 125,131,133 Silicification
Shallow enclosed basin of wood
Limestones - Sea-floor diagenetic environment Inorganic and replacement cherts 253

r Cementation styles
Shelf/platform burial domain
19 Quartz crystallinity index
Timing
253

o Limestones - Burial diagenetic environment 100 Chertification of carbonates .. 259

o Silcrete
Pedogenic cherts 268
Siliciclastic sediments
Authigenic cementation 168
o Precambrian cherts
Silica
270,271 Burial alteration

o Amorphous silica 227


Diagenesis and porosity
Diagenesis
166

o Chalcedony
Cristabolite
227,254,255
227
Fluid flow
Geological controls
171
170
o Definition
Lussatite
227
234
Heavy oil and tar sands 171

o Lutecite
Magadilite
227,255
227,266,267
Hydrocarbon reservoirs
Pressure solution and quartz overgrowths
Sandstones
171
166
166,167
Opal 227,232,254 Secondary porosity 170
o Quartzine
Tridymite
227,255
227
Silicon, dissolved
Definition 227
Silica budget
Sinter
o Oceans
Dissolved silica 228 Dripstone 50

o
r:
Diagenesis
Inorganic and replacement cherts 253
Flowstone
Rimstone
50
50
Fabric Slope and deep basin

o Chertification of carbonates
Equigranular 254
Limestones - Sea-floor diagenetic environment
Cementation styles 19
o Phases
Fibrous 254,255 Solubility diagrams
Silica phases
o Characteristics Chert : 233
o Sources
Biogenic siliceous sediments 231 Solution
Basins
o Chertification of carbonates 260 Kamenitza 46
o of non-detrital silica
Siliceous sediments 227
Surface Karst
Flutes
46

o Stability fields
Diagenetic silica transformations
Rillenkarren
Grooves
46

Chert 246 Frittenkarren 46


r Silicates Rinnenkarren 46
Argillaceous sedimentary rocks Sculpture
Burial alteration 178 Karren 46
Siliceous sediments Lapies '" 46
Flint 227 Phytokarst . . . . . 46
Jasper 227 Surface Karst 46
Mud 227
Solution-cannibalization Model
Novaculite 227
Dolomitization models 129,130
Ooze
Biogenic Solution-film Model 88
'--"
Depositional environments Speleothems
Modern ocean floor 228 Subsurface Karst 50

~"
(
338
(
C
Spencer, A.J. Tridym ite
C
Evapor ites , 141-163 Silica 227 C
Spherulitic cements Vadose
Cement petrography 26 Cements C
Sponge (spicule) ooze
Siliceous ooze 227 , Zone
Definition , . . 52 C
Steinmann trinity of gravity percolation
(
Definition 230 Definition 36
Strandline diagenesis of infiltration
C
Aragonite crusts 22 Definition 36 C
Beaches 21 Subsurface karst 48
Limestones - Sea-tloor diagenesis 21 Van Krevelen diag rams C
Tidal flats
Stratigraphic and facies criteria
22 Kerogen
Vertical zonation
4,217
C
Ancient dolomitization recognition factors 130 Lysocline , 14 C
Stratigraphy Thermocline 13
Pelagic Vitrinite reflectance C
Siliceous sediments
Cherts 229
Organic diagenesis
Methods of quantifying 205
C
Stylolites Volcanogenic cherts C
Pressure solution and quartz overgrowths 167 Inorganic and replacement cherts 268
Sucrosic or secondary replacement Water-eontrolled C
Dolomitization
Ancient dolostones • . . . . . . .. . . . . . .. . . . . . . 131,132
Precipitation
Carbonate sediments 50
C
Sulphate ions Rock-air interface C
Dolomitization chemistry 119 Caliche facies 43
Sulphide precipitation Surface karst facies 43
C
Early diagenetic pore water/sediment interaction
Framboidal pyrite 302,303
Water movement
Darcy's Law 36
C
Iron monosufphides 302 Water table C
Manganese sulphlde
Albandite 304
Ghyben-Herzberg principle
Meteoric setting
37,39
36
C
Syngenetic karst Zone C
Subsurface karst 51 and phreatic zone
Tectonics Subsurface karst 49 C
Chert Processes (
Depositional environments 230 Dissolution
Telogenesis Subsurface karst 49 C
Definition 2,199 Precipitation
Thermal alteration index Subsurface karst 49 C
Kerogen colouration
Thermobaric realm
207 Whitings
Crystallites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
C
Limestones - Deep-burial diagenetic environment . .. 75 Zonation C
Thermocline Limestones - Sea-floor diagenesis
Vertical zonation 13 Deep water 13 C
Thrust-faulted sect ions
Active lateral pore-water flow
Latitude
Shallow
14
13
C
Pore water profiles - type 7 300 Vertical 13 C
Tidal flats
Strandline diagenesis 22
Zone I: zone of precipitation
Warm shallow water platform carbonates
15
15
c
Trace elements
Ancient dolomitization recognition factors 134
Zone II: zone of dissolution/precipitation
Temperate water shelves, tropical carbonate
15,20 e
Transformation mechanisms slopes ' 20 (
Opal-GT
Mineralogic phases 237
Zone III: zone of active dissolution
Deep basinal environments
15
20
c
Chert Zone IV: zone of no carbonate 15 l
Diagenetic silica transformations 237 Deep basinal environments 20
C
C
C
(

You might also like