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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-
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indicated by arrows . Black indicates open
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sachusetts 01970, USA. 0·919216·40·4 $3 .00 + 0.00.
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ments during burial.
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CONTENTS
(
r
Preface. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . v
Introduction .
I.A. Mcllreath and D. W Morrow
r:
Limestones - Introduction .
N.P James and P W Choquette
~~1P~~~~~e;~~d ·I i<.·L~~~~~t~i~' 8
Aspects of the Diagenesis of Coarse-Grained Siliciclastic Rocks .. @
r
I.E. Hutcheon
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 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
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
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-
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
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,
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
. ;...
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
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" -,.{
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
*
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-
~'\'\~ 70 60
NORTH
50 40 30 20
LATITUDE
10 0 10 20 30
SOUTH
c
l
( Limestones - The Sea-Floor Diagenetic Environment 17
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)
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
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
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
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
(
(
(
..
il!.,_""""_~ ,,.r m lc robOnngs
roun ded groins
f ibrous or
rnrcrocr ystcltine
cement
r:
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-
..
Microcrystalline calcite. Finely
o crystalline calcite is extremely difficult
~
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
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 The question of whether seawater sence is easily inferred but proven with
Bathurst , R.G.C., 1986, Carbonate diagen-
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o isotopic composition has, indeed, var-
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The present is but a general guide to
. vation, destruction and creation of
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o carbonate cements and carbonate between periods when calcite was th p.1-24.
o mostly calcite.
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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-
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c
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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
METEORIC DIAGENESIS
CONTROLS SETTINGS -. C
INTRINSIC ;l"" fi ll
~ ~ : ~ : a / .' .
MINERALOGY
.~ • .,'-"<>.
ll";~I
GRAIN SIZE
POROSITY" PERMEABlUTY
ZONE
EXTRINSIC
.. ~ .
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
~ 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.
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
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
~.-.""'--'--'
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
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-
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",
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
r-
/
(
( Figure 15 Syngenetic phytokarst charac-
terized by sharp irregular cockling and
o numerous irregular pores in Pleistocene
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
,.
(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:
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 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
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
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
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
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
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 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.
(
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-
©
~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
,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-
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-
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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,
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 • _
--
--" '"" ------
_
....
<, ~
. . . ~--
--.. _-"'......, -
<,
~
, '>'
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
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 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 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.
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
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;
, 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-
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
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 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
( 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 '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
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 • Decrease in temperature
• Reduced porosity and permeability
• Increase in temperature
• Decrease in Pco,
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-
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
o OOZE-TO-CHALK-TO -
HYPOTHETICAL
D LIMESTONE CURVE
POROSITY vs DEPTH POROSITY-DEPTH
l MARINE PORE WATERS CURVES
r
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
(
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
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.
(
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.
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
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-
( 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.,
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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
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108 Diagenesis Geoscience Canada Reprint Series 4 c
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Dunham, R.J., 1969, Early vadose silt in
Townsend mound (reef), New Mexico, in
Hitchon, B., Bill ings, G.K. and Klovan, J.E.,
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proposed mechanism of fracturing, c
Friedman , G .M ., ed., Depositional
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tion waters in the western Canada sedi-
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chemical compos ition : Geochimica et
petroleum expulsion and dolomitization
in the Monterey Formation, California, in
Garrison RE ., Douglas, R.G., Pisciotto,
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Galloway, W.E. , 1985, Hydrogeologic
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chemistry and origin offormation waters
The Monterey Formation and Related
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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-
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Sayles, E.L. and Manheim, F.G., 1975,Inter-
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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
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et Cosmochimica Acta , v. 39, p. 103-127. r
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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,
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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
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Klosterman , M.J., 1981, Application of fluid
nal of Geology, v. 73, p. 391-403.
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Amer ican Journal of Science, v. 284 , inclusion techniques to burial diagene- solution alteration of carbonate rocks,
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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
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ing cyclic flow of salt water related to
geothermal heating in the Floridian
mentary rocks, in Young, A. and Galley,
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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
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Economic Geology of the Williston
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C
Basin : Montana, North Dakota, Sas-
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C
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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
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peratures and pressures: American Applied Carbonate Research Program, tions: Geological Society of America, (
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mine rals and hydrothermal solutions, in
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p.469-470.
Fairchild, I.J., 1983, Chemical controls of
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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:
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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
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Hitchon, B., 1969b, Fluid flow in the western
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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,
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April 1966 (unpublished). Machel , H.G., 1985, Cathodoluminescence
in calcite and dolomite and its chemical
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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 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
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,
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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
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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-
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
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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
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
-condition.
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
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
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Fanning, K.A., Byrne , R.H., Breland, JA, c
Recent Developments in Carbonate
Sedimentology in Central Europe :
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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-
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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-
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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-
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gists and Mineralogists, Special Pub-
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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
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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 v. 6, p. 77-80.
Samoilov, O.Y., 1965, Structure of aqueous
and capillary pressure : American Asso-
ciation of Petroleum Geologists, Bul-
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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
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( 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 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
---
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.
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
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
.-...
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
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
( netic history of the sabkha in Abu Dhabi, mitization model-application to the Beales, F.W. and Hardy, J.L., 1980,Criteria
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 75-1 B, p. 261-266.
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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-
(
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
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
C·
(
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
--
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: 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
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
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
(
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-
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 .
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.
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
c REFERENCES
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'-"'
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in evaporites , in Schreiber, B.C., ed.,
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Criteria for the recognition of salt-pan
c
p. 11-39.
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c
halite, B.Sc. thesis, University of p.95-101. Mayrhofer, H., 1985, World reserves of c
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Eugster, H.P., 1980, Evaporation of sea
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Meijer Drees, N.C., 1986, Evaporitic depos-
c
1971, Geochemistry and origin of forma-
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c
mentary basin - III. Factors controlling ciety of Amer ica , Spec ial Paper 88 , Mossop, G.D., 1979, The evaporites of the c
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Kuhn, R. and Roth, H., 1979, Beitrage zur
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Holland, H.D., 1972, The geologic history of
sea water - an attempt to solve the pro-
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logical Survey of Canada, Bulletin No.
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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-
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1986, Evolution of the atmosphere and
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m .,
isotopic history of ocean water and the
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Holser, 1963, Chemistry of brine inclu-
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Petroleum Geologists, Bullet in, v. 70,
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Muller, W.H., Schmid, S.M. and Briegel, U.,
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Holser, W.T. , 1966, Diagenetic polyhalite in
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anhydrite rocks of different grain sizes:
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recent salt from Baja California: Ameri-
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Lobanova, V.V. , 1953, On the genesis of the
langbeinite in the Sub-Carpathian pot-
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Nahnybida , C., Hutcheon, I. and Kirker, J.,
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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.,
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and the orig in of late stage cements:
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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-
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Holwerda, J.G. and Hutchinson, RW., 1968,
Potash·bearing evaporites in the Danakil
mentation and environments, Shark
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Hovorka, S.D., 1987, Depositional environ- Lowenstein, T.K., 1982, Primary features in Models: American Association of Petro- c
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Depositional and Diagenetic Spectra of
Parea, G.C. and Ricchi-Lucch i, F., 1972,
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Ingerson, E., 1968, Deposition and geo- Mineralogists, Core Workshop No.3, Coastal evaporite and tidal-flat sedi-
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Calgary, Canada, 1982, p. 276-304 . ments of the Upper Clear Fork and
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c
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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,
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United States Geological Survey, Pro-
fessional Paper 440-'(, 53 p.
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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
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
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
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
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 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
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e
siderations: American Journal of Sci- of the Illinois Sedimenta ry Basin: Amer- and Schluger. P.R., eds., AspectsofDia- (
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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
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
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
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
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
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
~><--
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
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
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-
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
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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.
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porosity development: Mineralogical
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staffe, F.J., ed., Clays and the Resource
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tologists and Mineralogists, Special
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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-
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Annual Review of Earth and Planetary
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C
eralogical and geochemical transfor-
mation of clays during catagenesis and
Longstaffe, F.J., 1983, Stable isotope stud-
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Tissot, B. and Welte, D.H., 1978,Petroleum
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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) ,
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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,
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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-
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of hydrothermally altered rocks of the
e
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Hedberg, H.D., 1936, Gravitational com-
ments: American Association of Petro-
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Chake-Broadlands, New Zealand geo-
thermal area: American Journal of Sci-
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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
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
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 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
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-
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~ ...
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
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
-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
.
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
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
(
(
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
'-
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.
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
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,
,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~
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
c Class
Optical
Technique
- vitrinite reflectance
Analysis Required
- microscopic
Precision
- excellent (standard)
Range of Application
- complete range of
diagenesis
- up to R. = 2.4"10
o - Palynomorph color -
- Conodont color
- microscopic
- microscop ic
- moderate
- moderate - complete range of
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-
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+
•
CATAGENESIS
Rele ••• ot:
~
S2~
zo!!
IU.
~~
EOGENESIS
8s.ci hound DPEP - - - - . . . Bound C 27 - 34 ETIO 5~
... -
' ;.
C 32 - 36 Ni DPEP and ETIO
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,
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
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 %
(
o
D·
-.::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
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c Determining Levels of Organic Diagenesis 223
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Originally publlshed in
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logic time as factors in coalification: Conoco well 15/30-1 , central North Sea:
(March 1985)
Revised 1988
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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 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
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
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
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-
(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
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·
c (0) (b)
c -1.0 ,...---r---r--,.---,----,---r--....,...~ 5000
_ -1.5
-
~
tT
-2.0
2000
1000
500_
N
-
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 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
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
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-
J[
A'
:"~lA ~
QUARTZ
b
C·
.~
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)
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 ~.:
)~~~~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 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 ~ 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
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 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 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 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 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
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
. d .
\
c· Origin of Inorganic and Replacement Cherts 257
c
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
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,-
'-- 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-
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
".
(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 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)
C'
C discovery has already been referred to related to soil-forming and/or weather- Silcrete Fabrics.
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
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
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
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 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-
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c
274 Diagenesis Geoscience Canada Reprint Series 4 c
(
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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,
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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
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Heavy Metal Deposits in the Red Sea:
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Journal of Science, v. 283, p. 861-875.
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Genesis of sulphide deposits, ochre and
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c
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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.
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
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
;~: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·
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-
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-
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 .
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
o ,~ ty.....,..,,0:--~=-30
.-=-~. '~'
o
,
51015 0510'5200.40.60.81 .03.05.0".00.'0+3.0
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
••
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-180 - 160
i i
-80
•••
,
,\ i ,
-60 - 40
i • •
-20
i
0
,
••
•
•
•
- 20
, ,-40, 0
i
20
i .'
•
, 60
••
•
40
•
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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
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
(,
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 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
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
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
:=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 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 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 ° 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
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 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
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
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-
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.
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.
c
310 Diagenesis Geoscience Canada Reprint Series 4 c
c
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3882. bearing sections on the Middle-America zons on continental slopes and rises:
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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.
(
(
( .
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 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
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-
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
o --~ A. NalK
• Chalcedony
and H2S. High concentrations of dis-
solved salt in produced geothermal flu-
• •• •
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
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Aggarwal, P.K. and Gunter, W.O., 1986,
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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 ,
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 • • ••
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
••• • •••• • • ••• •• • ••
Chlorite 0 • 0 0 0 181
0 ••• •• 0 ••••• •••• •• • 0 0 ••• 0 0 Markers
Definition Geochemical fossils . 0 0 4 • • • •••• • ••••• • •••• 0 •• •
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.
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
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 •
o and precipitation
Dolomite . . 0• . . . 0.. 0. 0... •.. 113-123,125-139
Carbon preference index
Organic diagenesis 00. .. .•. . • • • . • . . • 216
Diagenetic classification 2 0 ••
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
(
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 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
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
Vadose 35 Diagenesis 1
Water-controlled 43 Meteoric
Sea-floor diagenesis Diagenesis
o Biological alteration
Cementation styles
21
18
Diagenetic environments
Setting
9
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
(
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
(
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 Environments
Pore water profiles -type 2
Mid-ocean ridges 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
'--.'
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 Silcrete
Pedogenic cherts 268
Siliciclastic sediments
Authigenic cementation 168
o Precambrian cherts
Silica
270,271 Burial alteration
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
~"
(
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
(