Professional Documents
Culture Documents
Techniques in Sedimentology
Edited by
MAURICE
TUCKER
BSc, P h D
D e p a r t m e n t of Geological Sciences
University of D u r h a m
Durham D H 1 3LE
UK
MELBOURNE
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Contents
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Techniques in sedimentology.
1. Sedimentology Technique
I. Tucker, Maurice E.
551.3'04'028
QE471
MILLER
TREWIN
Library of Congress
Cataloging-in-Publication Data
References 3 5 5
Techniques in sedimentology.
Bibliography: p.
Includes index.
1. Sedimentology I. Tucker, Maurice E.
471 .T37 1988
552'.5
87-34120
ISBN 0-632-01361-3
ISBN 0-632-01372-9 (pbk.)
Index 3 8 7
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Cathodoluminescence microscopy 1 7 4
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Introduction 1
MAURICE
HENDRY,
MARTIN
Q U E S T and
List of contributors
IAN
FAIRCHILD
JOHN
GRAHAM
RON
HARDY
GILL
HARWOOD
GRAHAM
HENDRY
JOHN
MCMANUS
D e p a r t m e n t of Geology, T h e University, D u n d e e D D I 4 H N .
JOHN
MILLER
MARTIN
QUEST
N IAGUERLI CTER E T
WUI C
NK E R
M
D ee pp aa rr tt m
m ee nn tt of
of Geological
Geology and
Mineralogy,
T h e University,
b eD
r dHe e1 n3A
B .9 I A S .
D
Sciences,
T h e University,
D u r hA
am
LE
http://jurassic.ru/
iHiiiiM
Preface
e n v i r
whoi "^
n m e n t s of de
n g e of
. "
'
^ W o r W
Quite s o D h i s t i A l t h o u g h geologists have b e e n making field observations f
" d microsco '
two decades t h e r e have been many new approaches to the c o l i e ^ ^ ^00 years in"the last
d a t a . N e w sedimentary structures a n d relationships are stil) b e T '
Processi'n oilfield
studied rocks. T h e microscopic examination of sediments i
' ^ ^Und i 'classic' well
tion a n d interpretation of sediments, but there are ways to r n ^
tool in t h e ' d ' ^
slice of rock will yield. Chemical analyses a r e being increa*;., ?
e infr,r
"?~
r
j - .
t
A
i
j
n g l ,,<., " r m a t i o n a thin
o u t of sedimentary minerals a n d rocks a n d many of the analytj
P ' s e the stories
from o t h e r branches of the earth sciences or a r e m o r e f r e a u , ' P r o c e d u r e u
. ,
i
. u
^ n t l y . . . ^ u r e s have come
This b o o k aims to cover all t h e various techniques used '
^y other
rocks. It aims t o provide instructions a n d advice on the vari" ^
d y of sed' ^ t
examples of t h e information obtained a n d interpretations p o ^ ? ' P a c h e s a n d to ive
O n e chapter is concerned with t h e collection of field d a t ' .
,
,
.
.
/
,
- .
8 chanty , P " a s i s o n how
analyses, a n d grain size p a r a m e t e r s a n d their i n t e r p r e t
P r looks
microscopic studies: o n e being concerned with t h e p r o d u c t j
chapters deal with
slices, a n d t h e o t h e r with t h e description a n d interpretation
n ser..
, ' j
...
. ,
t,,
,
of s e d i ^ ^ " o n s , peels and
depositional and diagenetic textures. T h e now popular t e c h r , ;
enta.-v
,
i5 u
i l j j
.
.
t ii
t u v
q u e of ,
n e r a l s and
which can reveal hidden structures, follows. T h e X ^
t h o d o l u m i n i s c e n c e
bonates a n d cherts, providing information o n mineralogy .
n f
j
,
i_ a i_ *.
c
c i 4.
\t
com^
u d r o c k s , cars o m e d e p t h . A c h a p t e r o n Scanning E l e c t r o n Microscopy , . ""Position .
j u
i
i
.
.
A
A
A j . l w % h
> treated i n
and h o w samples a r e best p r e p a r e d a n d viewed, and then g j
w the machine works
soft-rock geology. A final c h a p t e r reviews t h e principles behi H
of S E M uses in
m e n t a r y rocks a n d discusses t h e collection a n d p r e p a r a t i ^
chernistr of sedi
techniques of electron b e a m microanalysis, X R F , A A S , T Q p
p l e s , followed b t6h e
M S . Sections a r e included o n analytical quality and the r e p o ' ^A.A
y is
concludes with examples of t h e application of chemcial anal,, ^ ^ &ults
,
a
r a
fieM.
0r
s a
S S e n t i a l
a x
1 1 2 et n
esc
d S l
lT
1 C a
u e
i U
s t u
Ss
S
W l t n
tr
i nn
t e
a t i o n
a t
g r a i n
s i z e
0n
6 a
ltn
n n i
m i
Ca
r a y
c t l
a
a n
e v
1 S
V e s
0 n
S a i l l
r t j
re
rm.- u ,
u
T
A
. i i 'ysis to A
d the chapter
This b o o k is a multi-authored volume a n d so naturally t h e
d i r n e n t o ,
u .u
u . .u . .
are ri;
a r y problems,
m e n t a n d emphasis t h r o u g h o u t t h e text.
e r e n t levels of treat
Techniques in Sedimentology
is written for final year under
to give t h e m information and ideas o n how t o deal with their ' ^
s a n d post
in t h e laboratory during dissertation and thesis research. Much
^
' d a n d s a " T'
is also provided which will b e relevant t o lecture courses Tu ,
ul backor^
,
c
i
A| . . . ' A * .
A
.
b o o t . , , 8 n n d material
to professional sedimentologists, in industry and c a d e m j
^ also b e invaluable
scientists, as a source book for t h e various techniques c o v e r s ' ' k e ,
.
'
.
.
,
.
,
,
e d and t
other earth
extracting information from sedimentary rocks.
" tor t i p
c
T
e o
l e n t
U l t t
r a
U a t e
t l l e
n e
U s e r
s a
n
Uu
Maurice Tucker
rhani,
March 1988
IX
http://jurassic.ru/
1
1.1
Introduction
MAURICE TUCKER
INTRODUCTION AND
RATIONALE
http://jurassic.ru/
Ill
M.E.TUCKER
1.2
1.3 G R A I N S I Z E D E T E R M I N A T I O N
AND INTERPRETATION:
CHAPTER 3
It is very i m p o r t a n t t o k n o w quite precisely what t h e
grain size distribution is in a sediment sample and
the procedures here are described by John McManus.
Sample preparation varies from t h e unnecessary to
having to break u p the rock into its constituent
grains, dissolve out t h e c e m e n t in acid, or m a k e a
thin section of the sample. Sieving, sedimentation
m e t h o d s and Coulter c o u n t e r analysis can be used
for unconsolidated or disaggregated samples, but
microscopic m e a s u r e m e n t s are required for fully
lithified sandstones and most limestones. With a
grain size analysis at h a n d , various statistical para
m e t e r s are calculated. F r o m these, with c a r e , it is
possible to m a k e deductions on t h e sediment's con
ditions and e n v i r o n m e n t of deposition.
1.4
M I C R O S C O P I C T E C H N I Q U E S I:
SLICES, SLIDES, STAINS AND
PEELS: CHAPTER 4
INTRODUCTION
production of the slide is not given t h o u g h t . J o h n
Miller explains how the best can be achieved by
double-polished thin sections and describes the vari
ous techniques of impregnating, staining and etching
to encourage the slide to give up more of its hidden
secrets. A c e t a t e peels are frequently m a d e of lime
stones and the manufacture of these is also discussed.
1.5
1.6
CATHODOLUMINESCENCE:
CHAPTER 6
1.7 X - R A Y D I F F R A C T I O N O F
SEDIMENTARY ROCKS:
CHAPTER 7
X-ray diffraction is a routine technique in the study
of m u d r o c k s and is frequently used with c a r b o n a t e
rocks t o o , and cherts. R o n H a r d y and Maurice
T u c k e r provide a brief general introduction to X R D ,
the theory and the instrument. X R D is t h e standard
technique for determining clay mineralogy and vari
ous procedures are a d o p t e d to separate t h e different
clay minerals. E x a m p l e s are given of how X R D data
from m u d s can be used to infer palaeoclimate, trans
port direction, conditions of deposition, and the
p a t t e r n of diagenesis. With carbonates, X R D is
mostly used to study the composition of m o d e r n
sediments, the Mg content of calcite, and t h e stoichiometry and ordering of dolomites. T h e proce
d u r e is relatively straightforward and the precision is
good, and much useful information is provided.
http://jurassic.ru/
1.8 S C A N N I N G E L E C T R O N
M I C R O S C O P Y IN
SEDIMENTOLOGY: CHAPTER 8
T h e S E M has b e c o m e p o p u l a r for studying fine
grained sedimentary rocks and for examining the
ultrastructure of grains, fossils and cements. Nigel
Trewin briefly describes the microscope and p r o
vides an account of how sedimentary materials are
p r e p a r e d for t h e machine. T h e S E M is a delicate
machine and often t h e picture on t h e screen or the
p h o t o g r a p h s may not be as good as expected. C o m
m e n t s are given on how such difficulties can be
o v e r c o m e or minimized. T h e S E M also has t h e
facility for attachments providing analysis, E D S and
E D A X , and these can be most useful when the
elemental composition of t h e specimen is n o t k n o w n .
A n S E M can also be adjusted to give a back-scattered
electron image and with m u d r o c k s this can reveal
t h e n a t u r e of t h e clay minerals themselves. T h e
S E M has b e e n applied to m a n y branches of sedi
mentology, particularly t h e study of the surface
textures of grains, both c a r b o n a t e and clastic. In
diagenetic studies, t h e S E M is extensively used with
sandstones, to look at t h e n a t u r e of clay cements,
evidence of grain dissolution and quartz over
growths. In c a r b o n a t e s t o o , the fine structure of ooids
and cements is only seen with S E M examination.
1.9
C H E M I C A L A N A L Y S I S OF
SEDIMENTARY ROCKS:
CHAPTER 9
M.E.TUCKER
1.10
2
2.1
JOHN GRAHAM
INTRODUCTION
Lithology:
Texture:
Beds:
Sedimentary
structures:
Fossil content:
Palaeocurrent
data:
In s o m e successions t h e r e will be an a b u n d a n c e of
information which must be recorded concisely and
objectively. R e c o r d s are normally p r o d u c e d in t h r e e
c o m p l e m e n t a r y forms and may be a u g m e n t e d by
data from samples collected for further laboratory
work. T h e s e are:
(i)
http://jurassic.ru/
mm*.
mmm
M.E.TUCKER
1.10
2.1
INTRODUCTION
Lithology:
Texture:
Beds:
Sedimentary
structures:
Fossil content:
Palaeocurrent
data:
In s o m e successions t h e r e will be an a b u n d a n c e of
information which must b e recorded concisely and
objectively. R e c o r d s are normally produced in t h r e e
c o m p l e m e n t a r y forms and may be a u g m e n t e d by
d a t a from samples collected for further laboratory
w o r k . T h e s e are:
(i)
http://jurassic.ru/
J.GRAHAM
2 . 2 R E C O R D I N G IN T H E F I E L D
2.2.1 Lithology identification and
description
T h e ability to recognize different sedimentary rock
types is e m b o d i e d in most geology courses and is
amply covered in texts such as T u c k e r (1981) and
Blatt (1982). Such identification is generally quicker
and m o r e reliable with increased experience in t h e
field, acquired initially u n d e r controlled conditions,
i.e. with supervision and laboratory back u p . Al
though t h e r e is a huge range of sedimentary rock
types, by far t h e majority of successions contain only
m u d r o c k s , sandstones, conglomerates, limestones
a n d dolomites, evaporites, and their admixtures.
T h u s s o m e c o m m e n t s are m a d e h e r e on t h e record
ing of these major rock types.
MUDROCKS
M u d r o c k s can b e subdivided in t h e field according to
a simple objective scheme such as t h e widely accep
ted o n e shown in T a b l e 2.1 ( I n g r a m , 1953). It in
volves only t h e a p p r o x i m a t e d e t e r m i n a t i o n of grain
size a n d fissility. Colour, which is also particularly
useful in m u d r o c k s , is generally e m p l o y e d as a
prefix. Application of m o r e sophisticated laboratory
techniques is necessary to obtain compositional in
formation ( C h a p t e r s 7, 8 and 9).
SANDSTONES
T h e lithology of sandstones, in terms of t h e grains/
matrix ratio, the main detrital constituents, and the
type of c e m e n t , can c o m m o n l y be identified in t h e
field, although detailed description and classification
require thin section analysis (Chapters 4 and 5). T h e
p r o b l e m of matrix p e r c e n t a g e and origin is difficult,
General terms
Non-fissile
Fissile
Silt + clay
S i l t clay
Clay silt
Mudrock
Siltrock
Clayrock
Mudstone
Siltstone
Claystone
Shale
Silt shale
Clay shale
Clast supported
bimodal
matrix well sorted
Clast supported
polymodal
matrix poorly sorted
Matrix supported
polymodal
Flow
Flow
2 Fabric
a (p) a (i)
a (t) b (i)
3 Stratification
O O O O O C O ) O
<0 o o
o o
.
.o
...
Inclined
. o
Q. O
\ .
o .
e>
CD
Unstratified
4 Grading
C ? 0
<=> o
O O O o
o CD
o
o
o
o o
. :.0'.0'o o
Ooooo
CD
Normal
O
o
O
Inverse
o'oo
o
oo
Ungraded
Fig. 2.1. Features used in a textural and structural classification of conglomerate (from Harms, Southard & Walker, 1982).
Under fabric, codes a and b refer to long and intermediate axes respectively; p = parallel to flow, t = transverse to flow,
i = imbricate. (Reproduced by permission of SEPM.)
http://jurassic.ru/
IIIHIHIIHHHW
o o
Horizontal
Polymict (petromict): a t e r m to describe conglomer
ates w h e r e several clast types are present.
Or
OCxZ>&
Unordered fabric
J . GRAHAM
(a) Criteria used for low sinuosity and glaciofluvial stream deposits (modified
from Miall, 1977)
Code
Lithofacies
Gms
Code
Sedimentary structures
Lithofacies
Sedimentary structures
Dmm(c)
Dmm(s)
Matrix-rupported,
massive, sheared
Dms
Matrix-supported,
stratified diamict
Dms(r)
Dms(c)
Dmg
Matrix-supported,
None
Horizontal bedding, imbrication
Trough crossbeds
Planar crossbeds
Solitary (theta) or grouped (pi) trough
crossbeds
Solitary (alpha) or grouped (omicron)
planar crossbeds
Ripple marks of all types
Horizontal lamination, parting or
streaming lineation
Low angle (10) crossbeds
Crude crossbedding
Broad, shallow scours including eta
cross-stratification
Analogous to Ss, Sh, Sp
Fine lamination, very small ripples
Laminated to massive
Massive with freshwater molluscs
Massive, dessication cracks
Rootlet traces
Plants, mud films
Pedogenic features
Lithofacies
Description
Dmm
Matrix-supported,
massive
Dmm with evidence of
resedimentation
Structureless mud/sandVpebble
admixture
Initially appears structureless but
careful cleaning, macro-sectioning, or
X-ray photography reveals subtle
textural variability ahd fine structure
(e.g. silt or clay stringers with small
flow noses). Stratification less than
10% of unit thickness
graded
Dmm(r)
Dmg(r)
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10
J . GRAHAM
11
Composition
Clasts in
conglomerate
Carboniferous Lavas;
\ / Lava
/V/>l|
Sandstone
petrography
Lithic-arenites
derived from
local lavas
Sub-arkosic
^ Q u a r t z
f xarenite
Dalradian
clasts
Sub-lithic
.arenite
o
c
CO
"co
Q
c
CD
>
Lava s
\'\
\ ^ i V
OVX/^
i '
100
200
300
400
500
O
i
Q_
O
Lithic
arenite
si
100
0
w
GO
100
Fig. 2.3. Diagram to show changes in clast composition with time for the Midland Valley of Scotland (from Bluck, 1984).
GS = greenschist, G = granite, O = other. (Reproduced by permission of the Royal Society, Edinburgh.)
Clast size (mm)
Fig. 2.2. Plot of percentage clast types versus grain size for
one locality for a Lower Devonian fluvial conglomerate
(diagram kindly supplied by Peter Haughton, University of
Glasgow). Key to clast types: GS = greenschist, LA =
lithic arenite, VQ = vein quartz, G = granite, Vv =
vesicular volcanics, V = other volcanics, O = other.
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12
J . GRAHAM
2.2.2 Texture
GRAIN SIZE
B e c a u s e t h e determination of grain size is basic to
sedimentological fieldwork, it is fortunate that the
grade scale proposed by W e n t w o r t h (1922) is now
internationally accepted as a standard (see C h a p t e r
3 and T a b l e 3.4). H o w e v e r , the choice of what to
m e a s u r e can be somewhat different for different
parts of the grade scale. For conglomerates it is
commonly m a x i m u m clast size that is m e a s u r e d ,
although it is advisable" to estimate modal size(s) as
well. Techniques for measuring m a x i m u m clast size
have varied considerably a m o n g different w o r k e r s ,
as shown in T a b l e 2.3. In t h e absence of an accepted
standard it is thus necessary to state how the mea
s u r e m e n t was m a d e . T h e maximum size of clasts is
used as a p a r a m e t e r partly because the measure
m e n t is easily m a d e but also because of its known
relationship to flow c o m p e t e n c e .
5 km
Contour interval = 4%
Based on 110 pebble counts,
100 pebbles per count
Author
Bluck (1967)
Steel et al.
(1977)
Heward (1978)
Surlyk (1978)
Allen (1981)
Transparent tape
3 mm
2 mm
Fig. 2.4. Regional distribution of gabbro pebbles in the Solund Conglomerate, Devonian, Norway (from Nilsen, 1968).
(Reproduced by permission of Norges Geologiske Undersokelse.)
0-1 <b
1.0-0.50 mm
1-2 cb
0.50-0.25 mm
Coarse
sand
Medium
sand
EVAPORITES
Evaporites are chemical sediments that have been
precipitated from water following t h e evaporative
concentration of dissolved salts. W h e r e these rocks
are preserved at o u t c r o p there is little difficulty in
field description and preliminary identification (see
Kendall, 1984 for a recent review). H o w e v e r , be
cause of their soluble n a t u r e , evaporites are fre
quently dissolved or replaced in the subsurface. It is
thus important to be aware of t h e typical pseudom o r p h s of evaporites which can be recognized, e.g.
cubic halite crystals. R e p l a c e m e n t is commonly by
2-3 <b
0.250.125 mm
3-4 cb
0.1250.063 mm
4-5 <b
0.0630.031 mm
Very fine
sand
Coarse
silt
MIXED LITHOLOGIES
Lithologies which are essentially mixtures of o t h e r
rock types a r e frequent in s o m e successions. A t
present there seems to be little a g r e e m e n t on the
n o m e n c l a t u r e of admixtures. A n objective and con
sistent p r o c e d u r e of labelling these rocks whilst
identifying t h e main and admixing lithologies is
necessary. T h e c o m m o n e s t admixtures are of siliciclastic and c a r b o n a t e sediments and a textural and
compositional classification for these has recently
been proposed by M o u n t (1985).
30 mm
Fig. 2.5. Construction of simple grain size comparator for field use in (a) sectional and (b) plan views (after Blatt, 1982).
(Reproduced by permission of Freeman.)
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13
14
J.GRAHAM
Equant
(spherical)
Bladed
Prolate
(roller,
rod-like)
0.2
Fig. 2.6. Graph for determining the size of sedimentary grains (from Chilingar, 1982). Sand grains (or rock particles) are
placed in the central part of the circle light particles in the left chart and dark particles in the right chart and compared
with those on the graph using a hand lens. The numbers are used for notebook reading. (Reproduced by permission of the
American Geological Institute.)
GRAIN SHAPE
S h a p e of sedimentary particles is a complex pro
perty such that t h e r e are even differences of opinion
as to what constitutes s h a p e . It is t a k e n h e r e in t h e
sense of Barrett (1980) as comprising form, r o u n d
ness and surface texture. Only aspects of t h e first
two are normally observable in the field.
R o u n d n e s s is generally described by m e a n s of
comparison to standard images which can be readily
taped into t h e field n o t e b o o k . It has been shown that
there is considerable o p e r a t o r variation with these
FABRIC
Fabric refers to t h e mutual a r r a n g e m e n t of grains
within a rock, i.e. their orientation and packing.
Fabrics may be produced during sedimentation or
by later tectonic processes. Careful m e a s u r e m e n t
will generally allow this distinction. T h e commonest
fabrics are those p r o d u c e d by the orientation of
elongate particles such as fossils in limestones, discs,
blades and rods in conglomerates. This alignment
may define bedding or may provide evidence of
palaeocurrent direction as in imbrication (Section
2.3.2; P o t t e r & Pettijohn, 1977). Fabrics also occur
in finer-grained sedimentary rocks but are n o t always
observable in t h e field.
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fff* +
I
_l
SORTING
In the field degrees of sorting are most commonly
d e t e r m i n e d for sandstones, usually by visual com
parison with a n u m b e r of standard images which can
b e taped into t h e field n o t e b o o k (Fig. 2.9). Field
estimation of sorting in mudrocks is generally not
possible. W h e n studying limestones and conglomer
ates t h e presence of clast or matrix support is impor
tant in description and classification, e.g. in the
application of t h e D u n h a m n o m e n c l a t u r e .
15
0.2
0.4
~Ii l_l i
0.6 %
i
L_
0.8
Cfs
di
Fig. 2.7. Major shape classes of sedimentary particles _
(after Zingg, 1935). d , a\, d = shortest, intermediate and
longest diameters respectively.
s
2.2.3 Colour
This can an i m p o r t a n t attribute in t h e description of
many sedimentary rocks. T h e r e are basically two
m e t h o d s of description. By far t h e most rapid and
simple is t h e subjective impression of t h e geologist
in t h e field. Whilst this may be a d e q u a t e for s o m e
general surveys it does lack objectivity, for colour
perception is known t o vary considerably a m o n g
w o r k e r s . M o r e objective is t h e use of a standard
colour chart such as that published by t h e Geological
Society of A m e r i c a ( G o d d a r d et al., 1975) based on
t h e Munsell Colour System. T h e form and arrange
m e n t of t h e colour system a r e shown in Fig. 2.10.
T h e first step is to d e t e r m i n e t h e h u e of the rock.
T h e r e a r e 10 major hues (Fig. 2.10), each o n e
divided into 10 divisions. T h u s 5P would refer t o t h e
mid-point of t h e purple h u e , 10P to a hue mid-way
b e t w e e n purple and purple-blue and 7.5P to a hue
mid-way b e t w e e n these two. N u m b e r i n g is clock
wise as shown in Fig. 2.10. After this a value is selec
t e d from 1 to 9 with 1 being t h e darkest and 9 the
16
J . GRAHAM
17
Fig. 2.10. The form and arrangement of the Munsell Colour System (from Goddard et al., 1975). See text for explanation.
(Reproduced by permission of the Geological Society of America.)
lightest (black to white when there is n o h u e ) . Also
selected is a chroma which is a degree of colour
saturation. T h e s e are given values from O (no colour
saturation) t o 6 for t h e most vivid colours. T h u s a
colour can be represented by a code such as 5P4/2 as
well as a n a m e greyish-purple. Several standard
colours are arranged o n sheets in a small booklet
which is taken into the field and then visually com
p a r e d with the rocks. Intermediates are estimated.
Extremely hard:
Well
sorted
Very well
sorted
1
Moderately
sorted
Very poorly
sorted
Poorly
sorted
Hard:
Fig. 2.9. Sorting images and standard terms (from Compton, 1962). The numbers indicate the number of size classes
included by c. 80% of the material. The drawings represent sandstones seen with a hand lens. (Reproduced by permission
ofWiley.)
Very hard:
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Loose.
Crumbles easily between fingers.
Rubbing with fingers frees numerous
grains. Gentle blow with hammer
disintegrates sample.
Grains can be separated from sample
with a steel probe. Breaks easily when hit
with hammer.
Grains are difficult to separate with a
steel probe. Difficult to break with a
hammer.
2.2.5 Bedding
In descriptive t e r m s , a b e d is a layer that is suffi
ciently distinct from adjoining layers. In genetic
terms, a bed represents a depositional episode during
which conditions were relatively uniform. T h e main
problem is that these two definitions d o not always
coincide, leading to s o m e contention over exactly
what constitutes a bed.
Campbell (1967) stated that distinction of beds
d e p e n d s o n recognition of bedding surfaces pro
duced during periods of non-deposition or by an
a b r u p t change of conditions. This is t h e concept of
the 'sedimentation unit' ( O t t o , 1938) which has been
J . GRAHAM
L_
Ico
18
3
2
Beds
Very thick bed
1000
Thick bed
Laminae
300
Medium bed
Very thick
lamina
30
100
Thin bed
10
Very thin bed
IEf 10
Thick lamina
Medium lamina
v> 3
Thin lamina
m
CO
1 Very thin
lamina
3, h e m i p e l a g i c m u d
I
2,turbidite m u d
\ .
1, turbidite s a n d
0-5
3. West Mull
0-15
0-1 h
0-05
Fig. 2.14. Plots of maximum particle size (vertical axis)
against bed thickness (horizontal axis) showing differences
between different processes (from Steel, 1974) in the New .
Red Sandstone of western Scotland. Locality: 1 mudflow
units, 2stream flood conglomerates, 3 braided
stream conglomerates. All measurements in metres.
(Reproduced by permission of SEPM.)
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19
0
0-5
20
J. GRAHAM
BED GEOMETRY
Lithological changes
and/or sedimentary
structures absent
Different lithologies
Fig. 2.15. Complexity of depositional units (beds) and bedding parallel weathering surfaces in limestones from the Lower
Carboniferous of South Wales (from Simpson, 1985).
21
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"HIIII!
22
J . GRAHAM
0.5 m
Fig. 2.16. Block diagram showing the main features of hummocky cross stratification (HCS) (from Harms et al., 1982).
Current directions unknown.
23
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"'lllll
24
J. GRAHAM
Seilacher
Bed
Martinsson
1-5m
Full relief
Exichnia
Semirelief (epirelief)
Epichnia
(top of bed B)
Full relief
g .
(a)
Endichnia
(interior of bed B)
Semirelief (hyporelief)
Hypichnia
Fig. 2.17. A toponomic classification
(bottom of bed B)
Full relief
Exichnia
(outside bed B)
rftrac
Strike of
beds
fossils
for
u s e j n t h e
field
Line of
measurement
AC=AB cos a
Horizontal
ilane^
Fig. 2.20. Use of the Jacob staff for measuring sections (from Kottlowski, 1965).
(a) Setting dip on clinometer of Abney hand level used with a Jacob staff.
(b) Measuring stratigraphic thickness AB.
(c) Measuring a unit with thickness less than the length of a Jacob staff.
(Reproduced by permission of CBS.)
Thickness
(b)
25
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26
J.GRAHAM
Thickness (cm)
Rock type
Type
O "O CD
III
Structures
CD (Q
0)
Current direction
"O
CD -<
CD
Coarse
Fine
Coarse
Medium
Fine
Silt
Very sandy
Sandy
Silty
Clayey
Gravel
Sand
Pelite
c
CD
Pelite
O
O
CO
Carbonates
Supplementary data
Fossils
Induration
Colour
Number of layer
Units
Remarks
PRESENTATION OF G R A P H I C LOGS
G r a p h i c logs are used in a large proportion of
publications dealing with sedimentary rock succes
sions b u t for a p p r o p r i a t e reasons t h e r e is n o stan
dardization. Information must be presented on a
variety of scales, and for a wide variety of facies
associations. E v e n the basic unit of the logs may
vary from being the bed or bedset to 'facies' which
are defined either on the basis of a detailed field log
or during a pilot study. A n a t t e m p t to provide a
comprehensive scheme of notation and symbols to
cover all eventualities may be either too limiting for
very detailed studies or t o o complex. Nevertheless
t h e r e are m a n y conventions which m a k e comparison
of different logs easier.
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27
2.3 P A L A E O C U R R E N T
DATA
2.3.1 Introduction
Palaeocurrent d a t a are those which provide infor
m a t i o n o n t h e direction(s) of sediment transport in
the past. A s such they are an important part of
sedimentological analysis on a variety of scales from
individual bedforms to the whole sedimentary basin.
T h e main categories of interpretation which may
result from analysis of palaeocurrent data are direc
tion of palaeoslope, patterns of sediment dispersal,
relationship of palaeocurrent direction to lithosome
( K r u m b e i n & Sloss, 1963, p . 300) geometry and
location of source area. Such interpretations may
have economic as well as academic applications when
dealing with p h e n o m e n a such as washouts in coal
fields or placer deposits.
T h e subject of palaeocurrents and basin analysis
has been exhaustively treated by Potter & Pettijohn
(1977). T h e y emphasized that a variety of observa
tions can contribute palaeocurrent data and these
may be grouped into two classes:
(a) Properties which acquire directional significance
only when m a p p e d regionally. T h e s e consist of:
28
J.GRAHAM
Basic rock types
[W
Sa
Sandstone
facies
Large-scale cross-stratified
sandstone (bulk sand content
95-100%)
Guide to
reading of the logs
to
C
O <
c
<ll Herringbone
Low angle
cross-stratification
Structures not
detectable
\ Sc
i i To
oiAenJ)m
i-
Small-scale cross-laminated
sandstone
(bulk sand content 95-100%)
240 f
Heterolithic
facies
Hc1
Sand-lensed mud
(bulk sand content 10-50%)
Hc2
Sand-streaked mud
(bulk sand content 10-50%)
wave-ripples
shale-flakes
^,
Mudstone
(bulk sand content 0-10%)
downcutting surface
flaser bedding, wave-ripples observed
cross-laminated sandstone, structure at base
not determinable
-scouring surface
scouring surface with
=-parallel infill
Mudstone _
facies
2001- ^-""
- downcutting surface
180
Mudcracks
Slumping
Loadcasting
Sandballs
Concretions
Channel of small size (width up
to a few metres) filled with sand
or mud-flakes
Channel of small size with
fine grained infill
Local unconformities
within heterolithic unit
Rock types in
Plant remains
(a)
regular alternation
Fossiliferous
Reddish colours
Strongly tectonized
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30
J . GRAHAM
(0
Locality
Section log
Location
from
Sheet no.
to
Geologist
from
= X-bedded
Flat bedding
= X-laminated
Laminated bedding
= Trough
v_/
Parting lineation
= Tabular
/ / / /
Cumthick
Lithology
W\J
= Mud cracks
= Convoluted bedding
= Channel
= Imbrication
Continues f r o m .
Erosive
| to
AA/\
Gradational
M a p sheet no.
Sharp, non-erosive
v v
J
Sheets
Grid co-ordinates
Altitude
Massive bedding
31
Fossils,
trace
fossils
Sample
Cum
thick
Unit
thick
Rock
type
Structures
L.B.S.
if erosional)
Undulating
Not seen
Locality no.
D = dull
Remarks ( + comp. of
coarse clasts)
PSL
number
clsls
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LINEAR STRUCTURES
In this category are structures in which it is n o t
possible to distinguish between o n e ' e n d ' of a struc
ture and t h e o t h e r , e.g. primary current lineation,
striae, groove m a r k s , gutter casts, channels, s o m e
oriented elongate fossils and symmetrical ripple
crests. T h e orientation of t h e lineation is recorded as
a pitch on inclined strata or in horizontal beds as a
direction. Techniques for u n a m b i g u o u s recording of
32
J.GRAHAM
COLLECTION AND ANALYSIS OF FIELD DATA 3 3
Station number
B
100
200
00
300
400
__30
2_
500
600
700
800
900
70
SO
90
_ 8 _
7 _
40
4
10
20
_ 30
_ 40 ^
4
50
60
'
70
80
8 _
Legend
MUOROCK
coarse SANDY siltrock
sandstone
Sheet number
-.90
Tabular cross-bedding
Trough cross-bedding
-. .
El
intraclasts
Horizontal lamination
=:!:=
0
00
i
|
.:?-.
EXPOSED
M.SL
C.SL
GRAD
SHP
SMTH
.9.
.A
-0
00
VF.SS
F.SS_
SCR
TOOL
EXPOSED
M.SL
C.SL
VF.SS
GRAD
SHP
SMTH
SCR
-3
9..
0
:~=
00
EXPOSED
VF.SS
F.SS
SCR
TOOL
3 _
-3
?. .
PEBBLY
00
NO
(M)
LIN
_RED
P.RD
^GN_
OTHER
NO DIR
M.SS
C.SS
VC.SS
TR.FOS
1
MKS.
-9.X.
CON
MD.CR
TR.FOS.
PEBBLY
RIPPLES
00
NO
-5
LIN
RED
P.RD
GN
GY
M.SS
C.SS^
VC.SS
CON
MD.CR
TR.FOS
Thick
(M)
PEBBLY
RIPPLES
DOL
FLAT
10
20
30
FOSSILS
40
CaCO.1
ROCK
10
20
30
CEM
cco3
?S5
CONCR- C 0
2 DIR
1 DIR
00
10
20
K
:
30
STUBSPEC
NO
-6
-7
LIN
CEM
CaC0 ,
3
ROCK
-zzz:
TR.X
VERT
OTHR
TR
100
200
300
50
60
70
80
90
SPARE
CANC'L
FLAT
SY.P
AS.R
PL.X
TR.X
NO
VERT
OTHR
TR
000
100
200
300
70
80
FOSSILS
40
50
RESTART
f?i
OR STUB
FLAT
FOSSILS
60
SPARE
SY.P
AS.R
=!,
PL.X
fc-r-Ij
fine lamination
AND / OR BIOTURBATION
NO
VERT
OTHR
TR
000
100
200
300
60
70
80
SPARE
FLAT
SY.P
AS.R
PL.X
TR.X
NO
VERT
OTHR
TR
10H
90
CANC'L
25-
20-
0
(b)
111111 1
ffl ' i n c n) at to
sand
10-+
Fig. 2.24. Examples of presentation styles of graphic logs.
(a) Representative logs of the coarse grained fluvial facies
of the Upper Devonian Munster Basin, Ireland showing
variation between proximal (A) and more distal (B) types.
Lithology and structures are shown separately (from
Graham, 1983).
(b) Log of marginal marine sediments from the Tertiary of
South England displaying inferred sequential organization
as well as data on structures and trace fossils (from Plint,
1983).
(a)
http://jurassic.ru/
Mill!
m.
35-
20-
CROSS-STRATIFICATION
f Bedding
15
Fig. 2.23. Example of a machine readable field recording form (from Alexander-Marrack etal., 1970). This form was used
for recording thick, relatively monotonous fluvial successions in East Greenland (Friend et al., 1976) where fieldwork was
expensive, time very limited and compatability among records from different investigators was important.
Marks are made on the form with soft pencil and each form has an accompanying stub on which additional notes can be
made. (Reproduced by permission of Academic Press.)
Flaser
TR.X
50
FOSSILS
j2^|
90
40
DOL
cross beoding
CANC'L
RESTART
CONCR-C0 OR STUf3
3
PL.X
NO
DIR
NO DIR
DOL
:::::
AS.R
"00
RESTART
CEM
SY.P
CONCR - C 0 O R S T U B
STUB- -SPEC
OTHER
DEF
CaC0
ROCK
STUB-SPEC
(M)
C.SL
0N
RIPPLES
Thick
SMTH
VC.SS
SHP
==-.:=
C.SS
LIN
CEM
MD CR
:::::
M.SL
__1.
M_SS
OTHER
_6_
TOOL | MKS
COVERED
9
_GY_
MKS
F.SS
F.SL
F\RD
Thick
GRAD
_RED
COVERED
F.SL
. A .
(M)
COVERED
F.SL
.. .-
Thick
NO
n i t e
Low-angle lamination
[ =| flat beoding
4
Convolute bedding
Mud clasts
i'sms Flint pebbles
''
k'9
' * Roots
6
Plant debris
J
Ophiomorpha
~JT Burrows
mm
m
55-
Intraclast
36 cm x 31 cm
Intraclast
24 cm
50-
45-
S6
40-
. 'Above
BedZ
"77-22
Green Foresets
35-
Green Foresets
^
Euestheria minuta Von Zeiten
Vj|B ppssiblyhere
Many Green,,,,.
Foresets \
B
Fig. 2.25. A plane table map of an Upper Old Red Sandstone sand body from central Scotland and accompanying section.
Both lateral and vertical relations of bedforms are well demonstrated. CI, C2 etc. refer to lithofacies described in text, a, b,
c refer to zones of facies interfingering and d to an area of soft sediment deformation (from Bluck, 1981). (Reproduced
by permission of IAS.)
fc
30-
25-
20-
15-
10-
fiSi*
(c)
Fig. 2.26. Field sketches of extensive motorway cuttings in shallowly dipping strata which demonstrate lateral relationships
within multistorey conglomerate channel bodies. Numbers refer to storeys: dense stipple - overbank sandstones and
mudstones; blank channel sandstone and wings; diffuse stipple conglomerate; SB 1 to 5 sidebar units (from Allen
et al., 1983). (Reproduced by permission of the Geological Society of London.)
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HIHIHIimiHimiHIHIHIWffllHIl
o
E
00
a
o
D.
o
a E
8
Q "a 3
- 3 3
U
a c "
a- S
3 a
S = 2
E
u
3
13
O O
O S gO <
T3
c -
S- <^>
E "
E o 1
1I
s
S E
O -5
^ 2 "S
9cd oo
CL Ov
a
5
5
.2
>
o a
-c o
a
M
j2 5
o
oo
D. _T
2 U
M 2
00
s -3
o
a
- _ <u a
- oo ^
o
a> o
a
~ O ^ .
e5 h
3 oo
_ -o
o
^ -a 3 2
. S |
b i S S
en , J2
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37
38
J . GRAHAM
Sample size
50
30
10
-iii^
PERCENT
Distribution of
clasts in one
typical example
Plan view
orientation
W
Distribution of
vector means of
Vector mean individual examples
Clasts parallel
to bedding
Fig. 2.30. Block diagram showing clast orientation in plan view (face A), imbrication (face B) and clasts parallel to bedding
(face C). Solid rose diagrams show the distribution of vector means of individual examples and stippled rose diagrams show
distribution of individual clast orientations in a typical example. Data are from the Cap Enrage Formation (deep water
Cambro-Ordovician) of Quebec (from Davies & Walker, 1974). (Reproduced by permission of SEPM.)
FLUTE MARKS
Flute m a r k s are found predominantly but not exclu
sively in turbidite successions. T h e origin of these
39
SLUMP FOLDS
Slump folds are p r o d u c e d when unconsolidated
sediments resting on a slope b e c o m e unstable and
move downslope u n d e r t h e influence of gravity.
T h u s if t h e direction of that m o v e m e n t could be
estimated a m e a n s of determining palaeoslope is
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iHimimiHiiHummiinHiifm
i
o
o
40
J.GRAHAM
Cwm-y-bont
C w m Blithus
(b) W E S T E R N M A R G I N
Ring Hole
Fold axes
s
</
X
n
RQ ""*"--*-AaL-
"axes
Fig. 2.32. Use of vergence and facing to determine palaeoslope direction in slump folds from Silurian strata in Wales. The
facing direction is a line within the axial surface, locally perpendicular to the fold hinge. The tick indicates the facing sense.
A similar convention is used to indicate fold vergence (from Woodcock, 1976b). (Reproduced by permission of the
Geologists' Association.)
enforced sample such t h a t every available m e a s u r e
m e n t must be taken. Designed sampling can only
occur w h e r e there is a surfeit of d a t a and may be
d e t e r m i n e d by cost (time + access) or for purely
analytical reasons.
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41
G2=137
42
J.GRAHAM
43
4
North-east
region
North region
n = 120
n = 258
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R = (v +
L
0
n
x
R
L
R
=
=
=
=
=
=
=
/2
wy ,
(R/n). 100,
individual azimuth,
n u m b e r of readings,
vector m e a n ,
magnitude of resultant vector,
magnitude of resultant vector ( % ) .
R/n
44
J . GRAHAM
x = 1/2 arctan WIV,
R = (w V)',
L = (Rlri). 100.
45
1 2
c o s
( x _ e )
1 0
20
50
100
200
400
2000
4000
6000
10,000
20,000
Number of observations, n
Fig. 2.38. Rayleigh test of significance. The graph plots the probability of a given vector magnitude (L) occurring by
chance for varying numbers of observations. A significance level is chosen, commonly p < 0.05, at which the hypothesis of a
random distribution of orientations is rejected (from Curray, 1956). (Reproduced by permission of University of Chicago
Press.)
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46
J . GRAHAM
0.1 0.2 0.3 0.4 6.5 0.6 0.7 0.8 0.9 1.0
Length of mean vector R
10 15
integrated system
47
order one
order two
Channel-form
Point bar
Large-scale ripples
Small-scale ripples
Channel-form
order three
It has long been realized that sedimentary structures
show an hierarchical a r r a n g e m e n t such that n o o n e
sedimentary structure fully specifies a complex flow
system. Such a specification can only be m a d e after
sampling all types of structure g e n e r a t e d within the
limits of preservation. T h e concept of bedform hier
archies was formalized by Allen (1966), Bluck (1974)
and Miall (1974) by w h o m parts of a fluvial system
were given orders or r a n k s (Figs 2.41 and 2.42). In a
general sense, t h e smaller structures in the hierarchy
tend to be m o r e variable because t h e currents form
ing t h e m are controlled both by t h e overall transport
direction and also by local deviations caused by
larger bedforms. This p h e n o m e n o n is particularly
well known from fluvial systems (Collinson, 1968,
order four
Legend
Small-scale
ripples
Channel-form
Point bar
Large-scale
ripples
rrfc
rrr
1
Large-scale ripple
crestlines
Small-scale ripple
crestlines
Flow direction within
flow-vector field
Fig. 2.41. Hierarchical organizational of flow-vector fields in a fluvial system illustrating the dependence of currentdirectional data on rank of bedform (from Allen, 1966). (Reproduced by permission of Elsevier.)
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1UJIM1
lit
48
J . GRAHAM
49
Variability of orientation
Fig. 2.42. Illustration of the possible relationships between flow stage, variability in orientation of structures and the kind
of sedimentary structures in a fluvial system. Ripples are often an exception because they tend to be caught in major
channel troughs and orientated along them (from Bluck, 1974).
U S E O F V A R I A B I L I T Y IN
ENVIRONMENTAL INTERPRETATION
It can be seen from t h e above section that the
a m o u n t of variability, even in a predominantly uni
directional transport system, will d e p e n d in part on
t h e level of bedform hierarchy which is sampled.
Much of our knowledge of palaeocurrent variability
comes from specific m o d e r n e n v i r o n m e n t s (Allen,
1967; Miall, 1974). A t t e m p t s to distinguish environ
m e n t s by m e a n s of the variance of their palaeocur
rent p a t t e r n have been m a d e by Potter & Pettijohn
(1977) and Long & Y o u n g (1978) w h o tabulated
large a m o u n t s of d a t a from case histories. H o w e v e r ,
it should be r e m e m b e r e d that m o d e r n e n v i r o n m e n t s
record variability over a very short time period
w h e r e a s most geological studies have data bases that
are fundamentally different because the strata ac
cumulated with an appreciable time dimension such
that the grouping of data over a longer time interval
might be expected to increase variance. M o r e im-
Fig. 2.43. An example of hierarchical sampling of palaeocurrent data from the Upper Carboniferous of South Wales. The
map shows vector mean cross-stratal azimuths and 95% confidence limits for sectors and regions within the study area
(from Kelling, 1969). (Reproduced by permission of SEPM.)
RELATIONSHIP OF SEDIMENTARY
STRUCTURES TO ENVIRONMENT
PALAEOCURRENT PATTERNS
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ll!!ll!!ll!!ll!!l!HIHIl!lllHlllltl
50
J.GRAHAM
51
Mean
ripple-crest
orientation
o
OJ
Trough X-beds
Convergent
Divergent
Curvelinear
Random
Rotary
(D
Hummocky beds
Fig. 2.44. Comparison of dip direction (arrows) and dip angle of trough cross-beds and hummocky beds in the Cape
Sebastian Sandstone, Cretaceous, Oregon. Dots are poles to cross bedding; dots within the small circle represent dips less
than 15 (from Bourgeois, 1980). (Reproduced by permission of SEPM.)
Parallel
2.4 S E D I M E N T A R Y F A C I E S A N D
SEQUENCE ANALYSIS
2.4.1 Erection and use of facies
Much of t h e field recording of sedimentary rocks is
aimed at classifying t h e strata being investigated into
recurrent units and attempting to detect an o r d e r in
t h e vertical and lateral a r r a n g e m e n t of those units.
Reversing
Fig. 2.45. Seven basic palaeocurrent patterns based on geometry (from Potter & Pettijohn, 1977). (Reproduced by
permission of Springer.)
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52
J.GRAHAM
LATERAL RELATIONSHIPS
Lateral relationships are in s o m e cases directly o b
servable and d o not rely on an inferential step from
the application of Walther's Law (Middleton, 1973)
to a vertical sequence. H o w e v e r , t h e limited physical
size of most exposures m e a n s that such situations
are u n c o m m o n and require favourable circum
stances. Such exposures are valuable in the descrip
tion of t h e larger scale geometry of facies which is
also seldom possible with limited vertical sections.
For example H o m e et al. (1978) gave s o m e excellent
examples of interpretative block diagrams con
structed from laterally extensive road cuts through
deltaic successions w h e r e exposure levels are be
tween 60 and 9 5 % over 1 0 2 - 1 0 3 m .
Spectacular examples of lateral facies changes on
a large scale are given by Bosellini (1984) for Triassic
c a r b o n a t e platform margins in the A l p s , by H u r s t &
Surlyk (1984) for Silurian carbonate platform mar
gins in N o r t h G r e e n l a n d , by Newell et al. (1953) for
t h e Permian reef complex of Texas and N e w Mexico,
by Playford (1980) for the D e v o n i a n reef complex of
t h e Canning Basin, W e s t e r n Australia, and by Ricci
Lucchi (1975b) for t h e Miocene turbidites of the
A p e n n i n e s . In these and o t h e r cases unusually large
natural exposures allow lateral relationships of
mega-units such as c a r b o n a t e platforms and slope
complexes t o be observed. O n a smaller scale lateral
tracing can, for e x a m p l e , illustrate the position of
levee deposits in both submarine fan valleys (Ricci
Lucchi, 1981) and in river systems ( H o m e et al.,
1978, fig. 7; Stewart, 1981), t h e geometry of fluvial
channel sandstones (Friend, Slater & Williams,
53
. Burrowed horizon
- L Major sandstonez
VERTICAL RELATIONSHIPS
V e r y extensive studies have been m a d e of vertical
sequences of facies from almost every e n v i r o n m e n t .
This is largely because sections with appreciable
vertical thickness but limited lateral extent are the
most c o m m o n d a t a sources. T h e r e is probably also
s o m e element of tradition in this emphasis in that
t h e simplest pictorial representation of such d a t a
resembles a stratigraphic c o l u m n . It is often possible
from such diagrams to see r e p e a t e d patterns of
facies or changes with time by simple inspection.
H o w e v e r , not all observers will have the same in>
pression of a succession, and thus it is necessary to
present and analyse t h e d a t a as objectively as poss
ible. T h e recognition of r e p e a t e d patterns of facies
(facies sequences, cycles) has proven to be a most
powerful tool in environmental interpretation
( R e a d i n g , 1978a).
For any given succession t h e r e are two simple
techniques which will normally form the first stage
of any analysis. T h e first is to present a graphic log
of t h e succession (see Section 2.2.7), and the second
is to p r o d u c e a facies relationship diagram ( F R D ) to
s u m m a r i z e t h e observed vertical sequence of facies
(Fig. 2.46a). In Fig. 2.46(a) the basic d a t a are still
accessible but have been arranged in an o r d e r sug
gested by visual inspection of the graphic logs; the
accompanying pictorial representation (Fig. 2.46b)
helps to summarize the information.
A. Black mudstone
\
/ '
* K
* V
\\
/ L . Majorsandstones\\
,1
!^\\f
_9b^8
Tl~ T D . S i l t y streak
1 i
a.o-o
it,
Q. Oscillatory 2
'
e"o: e
Q.'s
So
-.D"0: tOa
;
6 ' - e . P o ee.B'.e.
F. Oscillatory 1:
B. Silty
mudstone
F. Oscillatory 1
C. Turbidite
A. Black mudstone
- A . Black mudstone-
(b)
(a)
Fig. 2.46. (a) A facies relationship diagram for the Upper Carboniferous Abbotsham Formation of SW England showing
both number and type of facies boundaries.
(b) Pictorial representation of (a) and suggested sedimentary 'cycle'. (From Reading, 1978b after De Raaf etal., 1965.)
http://jurassic.ru/
54
J . GRAHAM
21
20
1
42
37
25
14
76
LIG
LS
Total
3
41
2
14
0
16
42
76
45
16
179
1
45
0.28
0.44
0.06
0.88
0.56
0.88
0.07
0.54
0.06
0.41
0.31
0.26
0.55
0.57 .
0.47
0.33
0.43
0.27
LS
0.05
0.18
0.00
SS
MS
LIG
LS
Total
23.3
31.0
14.1
4.1
49.2
25.5
7.5
56.3
13.8
33.2
4.4
51.4
+0.33
-0.13
+0.13
-0.20
-0.01
+0.41
-0.07
+0.02
-0.12
-0.21
-0.26
+0.11
31.38
34.06
10.06
76.00
8.17
34.05
2.78
45.00
E(n ) = a b ,
u
ii= j
= 0,
i=j
The iterative procedure for calculating a, and b, under the model is as follows:
First iteration
a,' = n /(m
- 1)
i+
bj = n+j/'Zai'
1
31.28
8.17
2.56
42.01
LS
2.56
10.66
2.78
16.00
i = 1, 2,
y = 1,2,
/th iteration
a? = n j'2bf'- )
i = l,2,
b,' =
a'
7=1,2,
42.01
75.99
45.01
16.00
f)
1
Beginning with a, as the average of the rth row entries provides a useful
starting point. Iteration is continued until:
| a / - a , < ) | < 0.01 a / for / = 1,
m
/-1
0.12
0.16
0.12
4.9
11.8
5.4
22.0
SS
MS
LIG
LS
SS
MS
LIG
LS
1 S
and
/ _ 1
|b/-i/
)|<0.01b/
for
y=l,
When a, and b are the final values of a/ and b / then the estimated expected
frequencies are given by = a,b, for i i= j . For example consider the data from
Table 2.7(a). On the first iteration:
y
/;
SS
MS
LIG
LS
-0.13
+0.26
-0.10
+0.14
-0.20
+0.21
-0.13
+0.09
-0.11
-0.01
+0.04
-0.06
ai = n l(m
3+
ft, =
Total
b
m e t h o d illustrated in T a b l e 2.8 using Gingerich's
d a t a as calculated by Powers & Easterling (1982).
This model of quasi-independence can b e tested
using a chi-square statistic which has (m l ) m
degrees of freedom. A comparison of the expected
transition frequencies derived by quasi-independence
and by the Gingerich m e t h o d is given by T a b l e
2.7(d, f ) . Testing for goodness of fit of t h e quasii n d e p e n d e n c e model yields % = 35.7 (cf. 42.3 for
t h e Gingerich m e t h o d ) , which rejects t h e assump
tion of quasi-independence. In this case, t h e earlier
m e t h o d of Gingerich would have given a similar
conclusion but t h e strata w e r e deliberately chosen to
d e m o n s t r a t e o r d e r and in o t h e r cases t h e conclu
sions would be different.
n /al
1+
a = n l(m
2
2+
- 1) = 76/3 = 25.33
4+
2
2
= 34.23
2
3
= 13.16
a/ = 3.86
2
2
= 2.62
2
3
= 0.90
2
4
= 0.27
A n alternative m e t h o d h a s b e e n p r o p o s e d , al
though not widely used, to avoid p r o b l e m s caused
by e m b e d d e d matrices. This is to sample at regular
intervals such that t h e r e a r e n o structural zeros (e.g.
E t h i e r , 1975). H o w e v e r , this also creates m a n y
d, = 10.22
d = 42.61
a = 11.12
a = 3.48
bi = 0.73
b = 3.06
b = 0.80
b = 0.25
http://jurassic.ru/
mam
- 1) = 42/3 = 14.0
l+
42.0
76.0
45.0
16.0
55
56
J. GRAHAM
E )IEJ .
n
^Mudstone
* Lignite
LIG
LS
+ 1.02
-1.84
+4.14
-0.98
-1.81
+ 1.19
-0.35
+ 1.02
-1.67
-1.07
-1.55
+ 1.02
Sandstone
MS
SS
SS
MS
LIG
LS
Z,j = {Oij -
57
Limestone
Fig. 2.48. Tree diagram constructed from the positive
elements of the differences matrix (Table 2.8d) (after
Gingerich, 1969). (Reproduced by permission of SEPM.)
D*~ A *
Bo
B -*- D
3
D A B
Fig. 2.47. Tree diagrams for Devonian fluvial sediments which show upward facies transition probabilities >0.15.
Arbitrary selection of this value is used to imply order of sequence (from Allen, 1970). (Reproduced by permission
ofSEPM.)
http://jurassic.ru/
Conglomerate
Red sandstone
Red siltstone
Red limestone
Grey sandstone
Grey siltstone
Grey limestone
1
2
3
4
5
6
7
0.00
0.33
0.19
0.20
0.03
-0.20
-0.21
0.25
0.00
-0.23
-0.23
-0.15
-0.12
-0.17
0.02
-0.03
0.00
-0.02
0.00
-0.02
-0.02
=d,j
Fan cycle C
58
J . GRAHAM
Battery point
model s e q u e n c e
Sharp
Gradational
Facies
SS
G
Palaeoflow
V
\
F
D
Channel
floor
Vertical
accretion
Bar
top
i
C
D
C
C
O
Vertical
accretion
fssj
o
c
In-channel
A
(b)
SS
Channel
floor
(c)
Fig. 2.50. Summary of vertical facies relationships for the Battery Point Formation, Devonian, Canada (after Cant &
Walker, 1976).
(a) Facies relationship diagram which displays the basic field data (cf. Fig. 2.46a)
(b) Preferred facies relationships based on data from a difference matrix. Higher values in the difference matrix are given
greater emphasis; thus, heavy solid arrows >0.30, light solid arrows 0.100.30, dotted arrows 0.05-0.10. A
generalized environmental interpretation has been added.
(c) A representation of (b) in the form of a vertical log with average facies thicknesses and palaeocurrents taken from the
field data. (Reproduced by permission of Canadian Journal of Earth Sciences.)
Conglomerates
illllM
60
J. GRAHAM
200
Sandstone
300
Bed
400
Thickness ( n
200
Sandstone
Bed
300
400
500
T h Ick ness t m m )
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moving average
61
sequences
62
J . GRAHAM
2.4.4 Non-Markov t e c h n i q u e s f o r
sequence analysis
Presentation and analysis of vertical sequences of
rock is not limited to M a r k o v analysis. Several
o t h e r , often simpler, techniques have been employ
ed with considerable success. P e r h a p s t h e most com
m o n are those that consider vertical changes in grain
size or bed thickness. T h e former have c o m m o n l y
been employed in t h e study of conglomerates (Figs
2.24c, 2.51 and 2.52) (Bluck, 1967; Steel etal., 1977;
H e w a r d , 1978; Surlyk, 1978; Allen, 1981). T h e aim
has largely been the detection of sequences showing
a unidirectional variation of m a x i m u m clast size, i.e.
coarsening up ( C U ) or fining up ( F U ) sequences.
T h e detection of such sequences has often been by
simple visual inspection of t h e d a t a but they are also
susceptible to techniques such as moving m e a n s .
Vertical changes in layer thickness have also b e e n
3.1
INTRODUCTION
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64
J. MCMANUS
3.2 S A M P L E P R E P A R A T I O N
T h e selection of materials to be processed is m a d e in
t h e field and usually collections comprising many
samples arrive in the laboratory at any o n e time.
T h e initial p r o c e d u r e in preparing for analysis is t h e
systematic checking of t h e materials to e n s u r e that
identification n u m b e r s and labels are all p r e s e n t and
legible. This is most readily achieved by laying out
cores, sample bags, bottles or blocks of material
sequentially. A n y internal n u m b e r i n g , unless en
graved o n indestructible material, may rapidly be
c o m e obliterated, and relabelling with external labels
is essential. G a p s in numerical sequences may b e
identified and samples lacking clear labels may at
this stage be r e t u r n e d to their correct sequential
position. If identification of misplaced samples can
not be completed with certainty at this stage t h e
samples have little value for subsequent analysis
and should be discarded. B e t t e r to have n o d a t a
t h a n unreliable data.
F u r t h e r p r e p a r a t i o n of all sediments relates t o t h e
form of size d e t e r m i n a t i o n to be carried out. Lithi
fied materials may require little m o r e than decision
o n t h e orientations of thin sections n e e d e d for later
examination u n d e r the optical microscope, but
special slide p r e p a r a t i o n and cementing media may
be required, particularly if soluble minerals are
thought t o be present (see C h a p t e r 4 ) .
3.3 D I R E C T M E A S U R E M E N T O F
GRAIN SIZE
T h e analysis of particle sizes of coarse unconsolid
ated sediments may be achieved through direct
m e a s u r e m e n t of individual pebbles. T h e lengths of
representative diameters or axes are d e t e r m i n e d
with t h e aid of vernier calipers (Briggs, 1977). F o r
every p e b b l e several possible diameters may be
recognized along t h e t h r e e principal axes of the
p e b b l e . A nominal d i a m e t e r may also be derived
from the volume of t h e p e b b l e .
T h e particle is placed o n a flat surface and t h e
length of t h e intermediate axis, / , is d e t e r m i n e d as
t h e shortest visible diameter. T h e length of the
largest axis, L , at right angles to / is next m e a s u r e d ,
and rotation of t h e particle by 90 about that axis
reveals the shortest axis, S which may then be
directly m e a s u r e d . It should be noted that L is not
t h e greatest possible dimension of the pebble but is
quite strictly defined in geometric terms. T h u s t h r e e
mutually perpendicular axes may be used to charac
terize t h e pebble (Fig. 3.1). Addition of the three
lengths, / , L and 5 , and division by three yields a
m e a n d i a m e t e r D for t h e particle. A second mean
M
http://jurassic.ru/
F
11111
65
volume = ^ r D .
6
v
3.4
SIEVING
I
Fig. 3.1. The principal axes measured in characterizing
pebble size.
2000
10
-0.75
12
-0.49
14
-0.27
16
-0.00
18
0.23
22
0.52
25
0.74
30
1.00
36
1.24
44
1.50
52
1.76
60
1.99
72
2.24
85
2.49
100
2.72
120
3.01
150
3.26
170
3.49
200
3.71
240
3.91
BS sie\ie. analysis
PG
VCS
3
oo
1
1000
CS
CS
E
3
00
i
2
500
Ta> Estuary sec iments programrr e
MS
MS
E
3
on
1
4
250
FS
FS
Pan
(loss)
E
3
on
1
8
125
VFS
http://jurassic.ru/
||^
| y ^ ^^^^^^^^^^^^^^^^^
Original weight
Sieving loss . . .
VFS
E
3
on
1
16
62
St/Cl
Total
(I
VCS
PG
St/Cl
Cumulative
(%)
.2?
Weight %/
Wentworth
classification
-1.04
Weight/
Wehtworth
classification
Weight
retained (g)
Approx.
value (urn)
Approx.
value (mm)
<t>
values
J . MCMANUS
Sieve
number
66
68
J . MCMANUS
Maximum
weight
(kg)
Sieve
diameter
(mm)
20
14
10
6.3
5
3.35
2.0
1.18
0.600
0.425
0.300
0.212
0.150
0.063
2.0
1.5
1.0
0.75
0.5
0.3
0.200
0.100
0.075
0.075
0.050
0.050
0.040
0.025
300
300
300
300
300
200
200
200
200
200
200
200
200
200
sv
/ = 1.32
sv
69
3.5.1 Pipette m e t h o d
3.5 S I Z E A N A L Y S I S B Y
SEDIMENTATION METHODS
Grain size analysis of fine sediments d e p e n d s not on
direct m e a s u r e m e n t of the particles themselves but
rather upon indirect c o m p u t a t i o n s of diameters
based on observation of t h e grain behaviour in fluids
or t h e response of t h e fluids to displacement by the
grains. T h e principal m e t h o d s based on the speed
with which particles settle through fluids yield set
tling velocities from which equivalent grain dia
m e t e r s are c o m p u t e d . Characterization of particles
in t e r m s of their dynamic behaviour is thought by
many to be m o r e environmentally significant than
direct m e a s u r e m e n t of particles with calipers or
sieves. In consequence t h e use of sedimentation
columns o r tubes to d e t e r m i n e the fall velocities of
sediment particles has b e c o m e very popular. T h e
t e c h n i q u e is relatively quick for coarse sediments
and may also be relevant for silt sized particles,
although time for completion of analyses increases
greatly within the silt size range.
C o m p u t a t i o n of t h e diameters of grains from a
knowledge of their settling velocities is d e p e n d e n t
u p o n the exploitation of Stokes' Law of settling.
W h e n a particle in static water settles at a constant
velocity t h e gravitational force exerted on t h e par
ticle is balanced by fluid resistances r e p r e s e n t e d by
viscosity and particle drag coefficient. T h e balance is
normally r e p r e s e n t e d within t h e equation
2
d (p
p)g
1 8 M-
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70
J . MCMANUS
h e x a m e t a p h o s p h a t e and 7 g of sodium c a r b o n a t e in
distilled water to give one litre of solution. Although
many variations of concentration have been tried
that found most useful is 50 ml of the solution to
1000 ml of distilled water. Alternative dispersants
used in some laboratories are Calgon (2 g per 1000
ml water) and Teepol (4 drops per 1000 ml of
water).
A sample of 20 g of fine sediment is suspended in
a 1000 ml measuring cylinder charged with water
containing dispersant, and thoroughly mixed through
end over end rotation or by m e a n s of a manual stirer
which travels from t h e base to the t o p of the fluid
column. A s t h e suspension begins standing a timing
device is started.
A pipette is inserted gradually into the fluid so
that its inlet is 20 cm below the surface and a volume
of 20 ml is withdrawn 58 s from the start of settling.
T h e fluid is released into a n u m b e r e d 50 ml b e a k e r
and any particles retained within the pipette washed
into the b e a k e r using distilled water.
Successive 20 ml aliquots are extracted from the
column at time intervals which calculations have
shown reveal particles of known d i a m e t e r (Table 3.3
after K r u m b e i n & Pettijohn, 1961). T h e aliquots are
withdrawn from specified depths at the time inter
vals shown for a full analysis of the fine particle
content.
mm
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
9.0
9.5
10.0
10.5
11.0
0.063
0.0312
0.0156
0.0078
0.0039
0.00195
0.00098
0.00049
urn
63
31.2
silt
15.6
7.8
3.9
1.95
clay
0.98
0.49
Depth (cm)
20
20
10
10
10
10
10
10
10
10
10
10
10
5
5
min
1
2
4
8
16
32
32
65
1
1
3
7
15
31
1
3
5
10
21
42
42
25
s
58
56
56
52
42
71
http://jurassic.ru/
J . MCMANUS
= 0.977
13
3.6 C O U L T E R C O U N T E R
A second technique which provides t h e possibility of
analysing sand, silt and clay sized particles in t h e size
range 0.00050.85 m m d e p e n d s on the detection of
variation in electrical current as fluids containing t h e
particles are passed through a p e r t u r e s of various
d i a m e t e r s . T h e principle on which t h e Coulter
c o u n t e r o p e r a t e s is that t h e particles are s u s p e n d e d
in an electrolyte which is drawn t h r o u g h t h e aper
t u r e . In t h e absence of particles an electrical current
across t h e a p e r t u r e r e m a i n s constant, but w h e n
particles of low electrical conductivity, such as
q u a r t z , pass the a p e r t u r e they cause current fluctua
tions, d e p e n d i n g upon their volume. T h e stream of
particles generates a series of pulses of c u r r e n t , u p
to 5,000 s ~ , which may be automatically recorded
as n u m b e r s and particle volumes.
1
2V0.003114 V p + fe(ps 4
p)
71
E
i
125
Ba)
C
>D
CD
500
>
CD
3.7 G R A I N S I Z E A N A L Y S I S O F
LITHIFIED SEDIMENTS
Ancient sedimentary deposits which cannot be read
ily disaggregated present major difficulties to the
potential size-analyst. Any grain size estimation
GO
1000
500
250
125
63
Thin section derived diameters (|xm)
73
3.8 G R A I N S I Z E A N A L Y S I S
3.8.1 Scales of size
Since sediment particles range in size from several
m e t r e s to less t h a n o n e m i c r o m e t e r , a scale using
uniform divisions by size places too much emphasis
on coarse sediment and too little on fine particles. In
c o n s e q u e n c e , a geometric scaling was introduced to
place equal emphasis on small differences in fine
particles and larger differences in coarse particles.
A l t h o u g h there is fairly general a g r e e m e n t on the
terms to be applied to sediment particles of various
sizes the definitions used for the bounding sizes is
not uniform. Most w o r k e r s take values based o n t h e
U d d e n - W e n t w o r t h scale (Table 3.4), which is a ratio
scale in which the grade boundaries differ by a factor
of 2. O n e grade coarser is twice the size of its
predecessor a n d o n e grade finer is half t h e size. T h e
g r a d e boundaries are established at 4, 2, 1, 0.5 and
0.25 m m etc. E v e n with a g r e e m e n t on the form of
t h e scale and g r a d e b o u n d a r i e s in t h e coarser ranges
different a u t h o r s still place t h e siltclay b o u n d a r y
variously at 2 urn (Briggs, 1977; Friedman & Sanders,
1978), which is a size commonly used by soil scien
tists, o r at 4 |xra, as in t h e original U d d e n - W e n t w o r t h
system ( T a n n e r , 1969; Pettijohn, 1975) as is m o r e
n o r m a l amongst geological sedimentologists.
In o r d e r to plot the results of grain size analysis
using the ratio scale it is necessary to use logarithmic
scale graph paper for size so that visual equality is
given t o the scale divisions. This led Krumbein
(1934) to introduce the phi transformation, which
recognized t h e logarithmic equality of scale divi
sions. H e expressed grain size such that
<h = - i
E
CO
r> 250
ed
/ = {0.111608 V p
rs
72
o g 2
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lillll
74
J . MCMANUS
Friedman & S a n d e r s
(1978)
phi
mm
-11
2048
-10
1024
-9
512
-8
256
-7
128
-6
64
-5
32
-4
16
Histogram
-3
Cobbles
Pebbles
Granules
V. coarse
Coarse
Medium
Fine
V. fine
Clay
-3
-2
-1
30
Frequency
percentage 2 0 h
by weight
20
10h
10
Unique
frequency
curve
phi 0
V. large
Large
Medium
30 h
100
Boulder
2001300 500
1000
2000
5000
3000
1000
Small
Large
Small
Cobbles
V. c o a r s e
9
10
Coarse
Medium
phi
- 4 - 3 - 2 - 1
1
10
20 30
50
100
Pebbles
Fine
- 4 - 3 - 2 - 1
V.fine
V. coarse
m i c r o n s Coarse
TJ 1
500
c
Medium
C
D
250
C
O Z
Fine
125
3
V.fine
62
4
V. coarse
31
5
Coarse
16
6
Medium
7
8
Fine
8
4
V.fine
9
2
Clay
Sand
Silt
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rfffiifffffii
99
Probability
scale of
percentage
finer than
a given size
70
50
30
10
1
-2-1 0 1 2
3
Grain size (phi)
Curve of
normal
distribution
76
J . MCMANUS
Cum
%
by
100
90
weight 80
70
CD
< in
60
50
40
30
20
10
0
/
J
-4-3-2-1
I
0
I
1
I I
2 3
L
4
Cum %
by
weight
99
98
95
90
80
S
70
j o 60
S 8 50
- co 40
30
20
10
5
2
1
/
/
/
/
J
I I L
J
I I I
-4-3-2-1
0 1 2
3 4
Grain diameter (phi)
16
Fig. 3.8. Cumulative frequency distribution curves plotted or arithmetic and probability scales.
3(
40
(b) S P R E A D A B O U T T H E A V E R A G E
S O R T I N G (a)
(a) M E A S U R E S O F C O M M O N S I Z E A N D
A V E R A G E SIZE
Mode. O n a size frequency histogram t h e size class
in which the greatest percentage of grains is r e p r e
sented provides t h e m o d a l class. O n the size fre
quency distribution plot the highest point on the
curve provides t h e m o d a l value. T h e m o d a l size is,
t h e r e f o r e , the c o m m o n e s t grain size in a distribution.
T h e frequency curves of many sediments exhibit
several p e a k s , the polymodal distributions indica
ting the presence of m o r e than o n e p o p u l a t i o n of
grains. S o m e w o r k e r s use modal values abstracted
directly from the size frequency distribution by
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84
16
01
~A
3.3
or
6.6
'
t s
50
25
84
1(
77
(c) P R E F E R E N T I A L S P R E A D
S K E W N E S S (a)
In a n o r m a l distribution with a bell-shaped fre
quency curve the median and m e a n values coincide.
A n y tendency for a distribution to lean to o n e side,
i.e. to deviate from normality, leads to differences
b e t w e e n t h e m e d i a n and m e a n values. T h e s e differ
ences are used t o characterize t h e asymmetry or
skewness of t h e curve. T h e skewness has a positive
or negative value w h e n m o r e fine or m o r e coarse
materials are p r e s e n t than in a normal distribution,
seen as tails to t h e right or left respectively on
frequency distribution plots. A g a i n , although skew
ness may be c o m p u t e d for t h e central s e g m e n t of the
distribution, for most p u r p o s e s b r o a d e r spreads are
used. Effectively skewness is d e t e r m i n e d from t h e
value of t h e m e a n less t h e m e d i a n , all divided by t h e
range used in defining t h e m e a n . M a n y possible
combinations of c o m p u t a t i o n are available. E x
pressed simply:
a<j> = ^ ( M < b -
Md$).
=
1
95
78
J . MCMANUS
T h e principles of m o m e n t statistics a r e lucidly
reviewed in F r i e d m a n & J o h n s o n (1982). Effectively
each grain in t h e population is t a k e n into account in
computing t h e characteristic p a r a m e t e r s of t h e sedi
m e n t . W h e r e a s in mechanics t h e m o m e n t is calcu
lated as t h e product of a force and t h e distance of its
application from a fulcrum, in statistics t h e m o m e n t
is c o m p u t e d from t h e p r o d u c t of t h e weight percen
tage in a given size class a n d t h e n u m b e r of class
grades from t h e origin of t h e curve. T h e first m o
m e n t , t h e m o m e n t p e r unit frequency, is t h e m e a n ,
x, of t h e distribution:
Phi
Dispersion
Mean
Md = P, M
Md = <j)
50
P75 + ^25
Azcj) =
PlS
QDa =
.
Ska ;
So = (Pis/Pis)*
Sk
Otj)
Mz =
Skewness
P25
<l>84 - <t>16
a, =
+ P -
2Md
Kqa
P75 ~ P25
2(Pc)o P10)
Md
M(() - Md$
a<t> o<()
SK,
995
P s
Kurtosis
V5
ocj)
x =
100
2.44(<t> -ij> )
75
25
50
6.6
2(4>95 - <t>s)
Sorting (o )
t
<0.35
035-0.50
0.50-0.70
0.70-1.00
1.00-2.00
2.00-4.00
>4.00
+0.3 to +1.0
+0.1 to +0.3
+0.1 to - 0 . 1
-0.1 to-0.3
-0.3 to-1.0
Kurtosis ( K )
G
Very platykurtic
Platykurtic
Mesokurtic
Leptokurtic
Very leptokurtic
Extremely leptokurtic
<0.67
0.67-0.90
0.90-1.11
1.11-1.50
1.50-3.00
>3.00
w h e r e x is t h e m e a n , / t h e frequency in weight p e r
cent a n d
is t h e mid-point of each class interval.
O n c e t h e position of t h e m e a n is defined t h e
spread of t h e distribution about it is calculated by
summing t h e m o m e n t s of each class interval about
the m e a n . In each of t h e subsequent m o m e n t calcu
lations t h e difference (m^ - x) is raised t o higher
powers.
T h e second m o m e n t has a value which is t h e
square of t h e standard deviation of t h e distribution:
,
Lf(m^
=
xf
Too
T h e third m o m e n t m e a s u r e s t h e symmetry of t h e
distribution about t h e m e a n a n d yields a value which
is t h e cube of t h e skewness:
,
Lf(m^
xf
100
Skewness is a positively or negatively signed
dimensionless n u m b e r ; it h a s neither metric n o r phi
value and lies within t h e range 1 to + 1 (Table 3.5).
(d) C O N C E N T R A T I O N O R P E A K E D N E S S O F
THE DISTRIBUTION KURTOSIS
N o t widely used, although frequently calculated, t h e
kurtosis is related b o t h t o t h e dispersion a n d t h e
normality of t h e distribution. Very flat curves of
poorly sorted sediments or those with bimodal fre
quency curves a r e platykurtic, whereas very strongly
p e a k e d curves, in which t h e r e is exceptionally good
sorting of t h e central part of t h e distribution, a r e
leptokurtic. T h e m e a s u r e of kurtosis, which is a
ratio of t h e spreads of t h e tails a n d centre of t h e
distribution (and is therefore also dimensionless) is
given by t h e expression:
4>95 ~ 4>5
2.44(<J, " 4>2 )'
75
3.8.4 Moment m e t h o d s
T h e second major a p p r o a c h t o analysing grain size
distributions, m o m e n t statistics, differs in concept
b u t yields measures analogous t o those of graphical
m e t h o d s . Neither technique is 'better' t h a n t h e
other. G r a p h i c techniques a r e especially appropri
ate for analysis of o p e n e n d e d distributions w h e r e a s
the m o m e n t m e t h o d s should n o t b e applied unless
all grain sizes present lie within t h e defined grain
size limits.
_ E/(m,|, 100
xf
A l t h o u g h t h e p a r a m e t e r s obtained a r e analogous to
those of graphical statistics their derivation e m
ploys t h e entire grain population a n d so they a r e
m o r e representative t h a n t h e graphically derived
values. O n c e again it should b e stressed that, b e
cause all grains a r e used, this form of analysis should
n o t be used unless t h e size distribution is fully known.
Distribution of t h e ' p a n residue' fraction from siev
ing a m o n g a specified n u m b e r of p h i classes 'to
permit application of m o m e n t m e t h o d s ' is n o t good
practise a n d m a y lead t o misleading, if n o t meaning. less, results being obtained. If a total of less than 1%
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80
J . MCMANUS
3.9
ENVIRONMENTAL
INTERPRETATION FROM
GRAIN SIZE DATA
3-5
3-0
/ Quiet water i
I/ slow deposition ]
\
2-5
c
o
to 2-0
>
+0-8
+0-6
+0-4
+ 0-2
0 4
-0-2-
CD
o
Z 1-5
Q1-0 -\Rivers
\
0-5
0
I
^
v Waves
\
j
Skewness
R i
6-0
Quiet water
slow deposition
I
I
^<s
--'
' Waves
v e r S l
N
J_J
I L
0-4h iVy
01
2 3 4 5 6 7 8
Median diameter (phi)
Fig. 3 . 9 . Bivariate plots which Stewart (1958) believed were of environmental significance.
10 000
Bedload.
Graded
\.
suspension
\
_
Fluvial
1000
Uniform
\
suspension
J
Pelagic / C \
suspension VL_y
i
1
-4!
-81
- 8 4 0
-4
Beach
/W ^ Turbidity
currents
/
i
10
100
M median (u,m)
I
1000 10 000
Skewness
Fig. 3.10. Skewness - kurtosis plots of sediments from the
Lake Ontario low energy ABCD and active environments
EFGH.
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illllllllllllllilllll
81
82
J. MCMANUS
CD
99-9
99
Suspension-,
>>
D -
90
50
Saltation-
10 Saltation'
E
o
0-1
0
-Rolling + sliding
J
I
I
1 2
3
4
Grain diameter (phi)
83
0-1
1
Median diameter (mm)
^
'.'
glacial
eolian
0
0
quiet water
flowing water
wave dominant
'
I
i
2-36
4-8
9-6
19-1
Test sieve aperture (mm)
38-1
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ill
84
J . MCMANUS
'
1 0 0 %
C L A Y
20
30
40
Porosity (%)
85
50
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Microscopical techniques: I.
Slices, slides, stains and peels
ROCK SAMPLE
Sawing
JOHN MILLER
Recording
(photograph or Xerox)
4.1
INTRODUCTION
87
X-ray
6 0 0 F
* J
Oiling
Smoothing
(
carborundum)
\
Etch
J }
Polish
Stain
Peel
-J
Low-medium power
binocular microscopy
Projected
microscopy
Covered
Normal thickness
30 vm
Ultra-thin
10 ixm
Uncovered
/ \
Etch^Stain
CL
Low-medium power
binocular microscopy
4.2 P R O C E S S I N G S A M P L E S
4.3
SLICES
J
Reflected-light
microscopy
Ultra-violet
Fluorescence
Fig. 4.1. Flow diagram showing various methods of sample preparation and possible techniques for microscopical study.
86
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111
88
J . MILLER
CARBONATE ROCKS
B e c a u s e of t h e inherent translucency of their ce
menting mineral crystals, many carbonates display
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89
Fig. 4.2. Cut and smoothed face of Waulsortian facies limestone, Dinantian, Ireland, showing 'sheet spars' with fibrous
ca cite and i n t e r f e r e d carbonate mud. Approximately x2. (a) Smoothed face photographed after coating with mineral
oil (b) Face after etching in dilute hydrochloric acid. Note the fine detail now revealed in the carbonate mud and the
differentiation of coarser geopetal floors in the spar-filled cavities. Photographs courtesy of A Lees
4.4 T H I N S E C T I O N P R E P A R A T I O N
4.4.1 Requirements f o r t h i n s e c t i o n s
OTHER ROCKS
With translucent or transparent rocks, the depth of
field of low power z o o m binocular microscopes can
be used advantageously for three-dimensional study
of included bioclasts and replacement fabrics in
88
J . MILLER
CARBONATE ROCKS
Because of the inherent translucency of their ce
menting mineral crystals, many carbonates display
89
Fig. 4.2. Cut and smoothed face of Waulsortian facies limestone, Dinantian, Ireland, showing 'sheet spars' with fibrous
calcite and interlayered carbonate mud. Approximately x2. (a) Smoothed face photographed after coating with mineral
oil. (b) Face after etching in dilute hydrochloric acid. Note the fine detail now revealed in the carbonate mud, and the
differentiation of coarser geopetal floors in the spar-filled cavities. Photographs courtesy of A. Lees.
OTHER ROCKS
With translucent or transparent rocks, the depth of
field of low p o w e r zoom binocular microscopes can
be used advantageously for three-dimensional study
of included bioclasts and replacement fabrics in
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iiiiiiiimmiHiiiiiiiimi
4.4 T H I N S E C T I O N P R E P A R A T I O N
4.4.1 Requirements f o r thin sections
A n acceptable rock thin section is of 30 pm nominal
thickness, b o n d e d t o a glass slide. Such s t a n d a r d
thin sections (STs) can be produced by hand or with
machine aid: they will usually be used for rapid bulk
sample examination or in teaching collections where
robustness outweighs their limited resolution. H o w
ever, much m o r e information can be obtained from
90
J . MILLER
matic and semi-automatic m e a n s . T h e extra e x p e n s e
of making these sections is offset by their versatility:
an uncovered D P T can be used for several different
analytical p u r p o s e s , and offers much m o r e p e t r o
graphic information. Machine-based systems give a
considerable increase in t h r o u g h p u t c o m p a r e d with
hand p r e p a r a t i o n . A flow-chart for t h e process (Fig.
4.3) shows stages at which section-making can be
simplified for less exacting r e q u i r e m e n t s , or where
special techniques can be followed for difficult rock
types.
MOST ROCKS
EVAPORITES, MUDROCKS
AND COALS
POORLY-CONSOLIDATED
AND FRIABLE ROCKS
Slice or grind
flat face IN DRY
1
Cut first face
on diamond saw
I
I
\
Lap first face with
abrasive and water
600 F
carborundum
1 (i.m
diamond
Mounting zero bond with epoxy
DPT
600F
1 u.m
diamond
- Cure
Add coverslip
t
ST
Rotating rods
with handles
Uncovered
Sealed by
O rings
DPT
Finishing lap
polish 1 u.m or
0.25 ixm diamond
GLASS SLIDE
Finishing lap
600-800F
ST
(a)
ST
/ V Vacuum gauge
Vacuum
Trim
DPT
-Handle
Trim
I
I
see Section 8.5.5). If the sediments are wet, a watermiscible acrylic or polyester resin can be used.
Otherwise, the specimen can be dehydrated by
passage through successively m o r e concentrated
ethanol/water mixtures, through absolute alcohol
into a c e t o n e , before placing in resin. If oil is pre
sent, r e m o v e as described in Section 8.5.1. Organic
matter can be removed with chlorox or hydrogen
peroxide. Poorly consolidated sediments and p o r o u s
sandstones may require impregnation with resin
u n d e r vacuum. Impregnation u n d e r pressure has
been advocated, but comparative tests have shown
that it may d a m a g e pores in sandstones, particularly
those lined with delicate clay minerals. V a c u u m
(strictly, low pressure: 1015 m m Hg) impregnation
has been found consistent and satisfactory for most
sediment types. Cold setting resins such as ' E p o - t e k '
are convenient for impregnation as they have a low
initial viscosity and thus p e n e t r a t e very well. It is
also possible to dilute s o m e Araldite resins with
t o l u e n e for pre-casting soak. D e p e n d i n g o n the
n a t u r e of t h e s a m p l e , a degree of experimentation
with resins of different types may be necessary before
Fig. 4.3. Flow chart showing sequence of operations in production of standard thin sections (ST) and double- polished thin
sections (DPT) for different types of rock samples.
91
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Iii
fffffffffffffffffff|f
92
J . MILLER
Lead weight
Pressure block
with handle
Sponge rubber
Fig. 4.5. Equipment used in semi-automatic preparation of thin sections, (a) Bench-mounted diamond-impregnated saw
with diamond-impregnated buffing wheel (to right) for rapid sample trimming. Note safety guards, (b) Precision flat
lapping machine (Logitech Ltd), showing vacuum chuck positioned on lap. (c) Close up view of sole face of vacuum chuck
for precision flat lapping machine. Note the slots for slide mounting, and the diamond impregnated rim which helps to
condition the lap. (d) Zero-bonding jig for applying controlled pressure to rock slice and section glass while resin cures
under gentle heat from hot-plate below.
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iiiiimiiiimiiiiiiiwiiii
93
GLASS SLIDE P R E P A R A T I O N
F o r t h e precision machine finishing process, the
glass slides must be of a precise and standard thick
ness. Commercial microscope slides rarely m e e t this
r e q u i r e m e n t and so are first ground on t h e flat
lapping machine as described above for rock slices.
F o r STs, polishing with 1 um d i a m o n d paste is usual.
With D P T p r e p a r a t i o n s , the 600F ground glass sur
face is used without final polish, as a slightly rough
zone is required as a 'key' to ensure adhesion at the
glass/resin interface.
94
J . MILLER
- 2
PRE-SECTION GUTTING
B o n d e d sections are next cut with a d i a m o n d blade
to form a parallel second face, leaving a slice 300
400 um thick on t h e slide. This initial thickness
allows the final 30 um section to be entirely in the
u n d a m a g e d layer. Cutting can be d o n e automati
cally on a d i a m o n d - i m p r e g n a t e d saw with a vacuum
chuck, holding u p to six slides simultaneously. Pre
cision is not i m p o r t a n t h e r e , as there is a machine
finishing stage to follow.
FINISHING
A t this stage, ST preparations are r e t u r n e d t o t h e
precision lapping machine for lapping to a final 30
um thickness with 600F or 800F C a r b o r u n d u m .
Thickness is automatically d e t e r m i n e d by pre-setting
t h e vacuum slide-holding chuck (Fig. 4.5c); slides
have reached t h e set thickness when they begin to
'float' on t h e lap, a process aided by t h e d i a m o n d i m p r e g n a t e d surround o n t h e lower face of t h e
chuck. Slide thickness can b e checked with a microm
eter or, less reliably, o n a microscope, looking for
the required interference colours, e.g. quartz greys.
This optical m e t h o d is of little use for limestones.
95
Fig. 4.7. (a) Polishing lap for final finishing of thin sections, showing a vacuum chuck and a weighted chuck in position,
(b) Sole face of vacuum chucks showing how various sizes and types of thin sections can be polished simultaneously.
COVERING
For research purposes it is best to leave thin sections
uncovered, as they may then be subjected to a
variety of t r e a t m e n t s including staining, etching,
cathodoluminescence and microprobe work. Coverslips a r e , of course, required for thin sections des
tined for teaching collections. D P T preparations
need n o oil for microscopic examination, but un
covered S T surfaces, being finished only t o 600F or
800F C a r b o r u n d u m , require oil or glycerine before
microscopic study.
All sections should be cleaned of abrasive residue
before examination. This may be d o n e by wiping
D P T s with a soft, d a m p tissue, or by brief immer
sion in an ultrasonic b a t h . ST preparations may be
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LABELLING
Standard thin sections required for teaching collec
tions o r archive purposes can now be given selfadhesive labels on which can be written all the
details of the sample. H o w e v e r , p a p e r labels should
not be used for those sections destined for use in
cathodoluminescence a n d scanning electron micro
scopes or m i c r o p r o b e , as they tend to char in the
b e a m and may interfere with conductive coatings.
4.4.3 Variations in p r o c e s s f o r
'difficult' rock t y p e s
Certain rocks, such as shales, evaporites, coals, soft
chalks and poorly-consolidated sediments require
special t r e a t m e n t at various stages of t h e sectionmaking p r o c e d u r e . Initial impregnation and em
bedding, if required, will have been completed as
96
J . MILLER
ETCHING LIMESTONES
II
4.5.2 Staining
While the mineralogical composition of rocks can be
d e t e r m i n e d by optical study of thin sections, this can
be a tedious, time consuming and error p r o n e pro
cess. F o r e x a m p l e , distinction between calcite and
dolomite is difficult because they have similar optical
properties. For similar reasons, small untwinned
feldspar grains and q u a r t z grains cannot easily be
distinguished. Chemical staining involves a reaction
which produces a coloured precipitate on a specific
mineral surface and therefore m a k e s that mineral
m o r e easily recognized. Usually the surface requires
s o m e p r e p a r a t i o n , often etching, t o receive and
retain t h e precipitate.
Sling support
FELDSPARS
H o u g h t o n (1980) gave a m e t h o d for staining plagioclase and alkali feldspars which is much m o r e reli
able than previous recipes.
R e a g e n t s : (a) Potassium rhodizonate (0.01 g
K-rhodizonate in 30 ml distilled water, filtered b e
fore use). M a x i m u m useful life o n e hour.
1 V
Wax coating
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Plastic box -
4.5 E T C H I N G A N D S T A I N I N G
4.5.1 Etching
97
98
J . MILLER
ARAGONITE
T h e most sensitive stain for aragonite was developed
by Fiegl (1937). Despite its sensitivity, it is not
always reliable.
R e a g e n t s : (a) 1 g commercial grade A g S 0 is a d d e d
to a boiling solution of 11.8 g M n S O . 7 H 0 in 100
ml distilled water.
(b) Cool and filter t h e suspension; add 2 d r o p s 1 0 %
sodium hydroxide solution.
(c) Stand for 2 h o u r s and then filter into a dark
storage bottle.
P r o c e d u r e : I m m e r s e t h e p l a q u e t t e or thin section in
t h e Fiegl's solution for a b o u t 10 min at 20C. Some
times a hot solution works better.
A r a g o n i t e is stained black while calcite remains
unstained.
2
MG-CALCITE
C h o q u e t t e & Trusell (1978) devised a m e t h o d of
making an alkaline Titan yellow stain p e r m a n e n t ,
enhancing the value of this technique. T h e stain can
detect t h e presence of Mg-calcite containing more
than about 3 % M g C 0 .
R e a g e n t s : (a) Stain: 1.0 g Titan yellow p o w d e r , 8.0 g
N a O H and 4.0 g d i N a E D T A dissolved in 1 litre
distilled water at r o o m t e m p e r a t u r e . Store in d a r k
bottle; shelf life at least two years,
(b) Fixer: 200 g N a O H pellets dissolved slowly in 1.0
litre distilled water. Caution! heat and fumes and
evolved, so best carried o u t in fume c u p b o a r d . Solu
tion is corrosive t o flesh. Store in polythene bottles
as 5 M caustic soda etches glass. Shelf life indefinite.
P r o c e d u r e (Caution! use surgical gloves as solutions
are corrosive): (a) Thin sections must be epoxy
m o u n t e d : Lakeside and C a n a d a Balsam are soluble
in t h e stain solution.
3
DOLOMITE
D o l o m i t e is often distinguished from calcite by its
failure to stain with solutions which react with cal
cite (see below). It can also be recognized after
etching, especially on a universal stage: dolomite
remains at 30 u m , giving fourth- and
fifth-order
pinks and greens, while calcite is reduced to 10 um
or s o , giving second- and third-order r e d s , blues and
yellows (Dickson, 1966, p . 491). Titan yellow in
alcohol and alkaline Alizarin r e d S a r e two reliable
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CALCITE
F r i e d m a n (1959) gave a n u m b e r of stains for calcite.
O n e of t h e simplest and most reliable is Alizarin red
S. Many c a r b o n a t e workers routinely acid etch o n e half of a thin section and stain it in acidified Alizarin
red S solution before covering. While this helps to
distinguish between red-stained calcite and unstain
ed dolomite and q u a r t z , it gives very little o t h e r
information about diagenesis and mineralogy. It
also m a k e s microphotography of that slide difficult.
A far m o r e valuable s c h e m e was given by Dickson
(1965, 1966) which in o n e operation differentiates
b e t w e e n ferroan phases in calcites and dolomites,
and is capable of revealing subtle growth zones in
c e m e n t crystals.
Dickson's m e t h o d reagents: (a) Etching sol
ution 15 ml of 3 6 % HC1 dissolved in 500 ml dis
tilled water, then topped up to 1000 ml with distilled
water.
(b) Staining solution part 1:0.2 g Alizarin red S
dissolved in 100 ml 1.5% HC1 solution.
(c) Staining solution part 2 : 2 g potassium ferricyanide crystals dissolved in 100 ml 1.5% HC1 solu
tion. This solution must be freshly m a d e for each
staining session.
(d) Mix staining solutions parts 1 and 2 in the ratio 3
of d y e t o 2 ferricyanide. T h e c o m b i n e d solution lasts
for only o n e staining session.
100
J . MILLER
Dickson's m e t h o d p r o c e d u r e (Caution!
use
r u b b e r gloves): (a) I m m e r s e thin section (grease
free surface) or faced sample in etching solution,
face u p p e r m o s t , for 1015 s at 20C (times are only
a p p r o x i m a t e , and may vary widely with grain size,
etc.). Cold solutions give very p o o r results. Experi
m e n t a t i o n is necessary to achieve the o p t i m u m etch.
W e a k etching gives a thin, patchy stain. Overetching, particularly with Alizarin red S, produces a
very dense stain which tends to spread a precipitate
even over dolomite and quartz if they are present.
(b) I m m e r s e specimen in t h e combined solution for
3045 s (again experimentation is r e q u i r e d ) . F o r
thin sections, best results are obtained if the stain is
w a r m e d . A s H C N fumes can be evolved from t h e
mixed stain, the safest way of doing this is t o im
m e r s e t h e slide in a dish of hot water before placing
in t h e bath of stain which is at r o o m t e m p e r a t u r e .
Avoid skin contact with the stain: ferricyanide
is
poisonous. Dickson suggested a further stage, briefly
dipping t h e stained slide or surface into Alizarin red
solution alone, but this is not often n e e d e d and
indeed may detract from t h e first stain.
(c) Wash the specimens gently in two changes of
distilled water (not tap water, which contains F e and
C a ) for only a few seconds at a time the stains a r e
relatively soluble.
(d) D r y t h e specimen surface quickly in a stream of
w a r m air (from a hair drier or equivalent). H a n d l e
carefully; the stain is a thin surface film and is easily
damaged.
This m e t h o d produces the following colour differ
entiation in c a r b o n a t e minerals:
Calcite
Varying through very pale pink
to red.
F e r r o a n calcite
Varying through m a u v e , purple
to royal blue with increasing F e
content.
Dolomite
N o colour.
Ferroan dolomite Pale t o d e e p turquoise with in
creasing Fe content.
Dickson (1966) pointed out s o m e useful features of
this stain coupling. Alizarin red S can differentiate
slightly different types of calcite: for e x a m p l e , dif
ferent kinds of bioclasts stain with differing intensi
ties depending on their crystallite size and structure.
T h e optic orientation of sparry c e m e n t crystals can
be discerned, as sections n o r m a l to t h e c-axis a r e
stained very pale pink, whereas sections parallel to
that axis stain d e e p pink. This is due to different
rates of etching. T h e potassium ferricyanide com
CLAY MINERALS
Stains for particular clay minerals usually require
p o w d e r e d and acid-extracted samples (Allman &
L a w r e n c e , 1972, p p . 1 0 9 - 1 1 1 ) and a r e therefore
beyond t h e scope of this chapter. It is often useful,
however, to be able to visualize the distribution of
clays in a sandstone or argillaceous c a r b o n a t e , since
clays are often related to otherwise obscure fabric in
these rocks. T h e Zyglo ultra-violet sensitive dye
described in Section 4.3.2 is useful h e r e . A simpler,
but not always predictable, technique is to soak
grease-free surfaces in a q u e o u s solutions of 0.5 g
malachite green, congo red or methylene blue in 250
ml water. T h e surface is lifted out of the solution
occasionally and gently washed until the stain is
found to be satisfactorily d e v e l o p e d : T h e dye colour
chosen should be c o m p l e m e n t a r y to the rock colour
so as to provide t h e greatest degree of contrast. A n
alcoholic solution of dye (equal parts ethanol or
m e t h a n o l and water) of methylene blue works well
on limestones, including chalks, with t h e alcohol
acting as a wetting agent and aiding p e n e t r a t i o n .
4.6
PEELS
P O L Y S A C C H A R I D E STAIN FOR
BIOTURBATION
Burrowing in sandstones and siltstones may often be
cryptic, and sometimes difficult to distinguish from
water escape structures. Risk & Szczuczko (1977)
developed a reliable m e t h o d for enhancing t h e mor
phology of burrowing in siliciclastics. It is based on
t h e tendency of many burrowing organisms to secrete
polysaccharide mucus as a burrow lining. T h e pre
sence of this c a r b o h y d r a t e can be detected by a
periodic acid Schiff ( P A S ) reaction. T h e m e t h o d
is not suitable for use with carbonates because of the
HC1 in t h e Schiff reagent.
P r o c e d u r e : (a) Cut a face or slice using water only as
a lubricant; avoid all grease and oil; d o not touch the
cut face with uncovered hands. Massive, unjointed
Peels are mostly used for limestones and calcitec e m e n t e d clastic rocks, although cherts and siliceous
elastics can be successfully treated. Best results are
obtained with n o n - p o r o u s samples; surface cavities
cause the film to bulge into t h e void, causing blisters
and a risk of tearing the completed peel. Porosity
can be reduced by v a c u u m impregnation with resin
before facing t h e samples (the resin used must not
b e soluble in acetone w h e n c u r e d ) . Larger holes
should be filled with d e c o r a t o r ' s filler paste (such as
Polyfilla), which is allowed to h a r d e n before t h e face
is rubbed down.
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101
102
J . MILLER
4.6.3 Procedure
PREPARING THE CUT FACE
Sawn faces should be lapped to at least 600F Car
b o r u n d u m stage. F o r greater detail, further smooth
ing by polishing with 1 um Aloxite or d i a m o n d
abrasives is r e c o m m e n d e d . Etching such a polished
surface gives a relief which is m o r e subtly fabricselective t h a n etches controlled by an imperfect
surface.
P R E P A R A T I O N OF FILM
Direction of application
Acetone pool
103
Etched surface
Plasticine or
modelling clay
Fig. 4 . 9 . Side view of sample prepared for acetate replica
process, showing how the curved acetate film is applied at
the edge of the slightly tilted sample before being unrolled
across its face, pushing the acetone before it.
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imiHimimiHiimiiHMtHHiim
4.7 E X A M I N A T I O N O F M I C R O S C O P
ICAL PREPARATIONS
Having gone to s o m e trouble to obtain high quality
sample p r e p a r a t i o n s , it is i m p o r t a n t to realize their
potential by using a p p r o p r i a t e techniques when
studying t h e m . Many workers begin immediately
with detailed study u n d e r m e d i u m to high power on
a petrographic microscope which has a very small
field of view. T h e r e is much to be gained from
104
J.MILLER
4.7.1 Photographic m a p
A suggested first step in t h e use of any p r e p a r a t i o n ,
be it peel or thin section, is to m a k e o n e or m o r e
p h o t o g r a p h s of t h e entire preparation (Fig. 4.10).
This ' m a p ' has m a n y advantages: it preserves a
record of the sample in its initial state before treat
m e n t ; it gives an overall view of the section o r peel
105
Fig. 4.10. Negative print of thin section, showing good contrast and detail obtained by projecting a thin section directly on
to bromide paper. Waulsortian facies, Dinantian, Crow Hill, near Clitheroe, Lancashire, England. Lime muds are pale
grey, fibrous calcite spars mid-grey and clear blocky calcite late cavity fill cements are black. Cavities are partially or
completely filled with peloidal geopetal sediment. Bioclasts include abundant sponge spicules, fenestellid bryozoan
fragments, gastropods and echinoderms. Scale is 5 mm.
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106
J . MILLER
4.7.3 Petrological m i c r o s c o p e
In o r d e r to optimize viewing conditions, t h e micro
scope should be correctly adjusted and all optical
surfaces clean. In particular, care should be t a k e n to
set t h e condenser correctly this is probably t h e
single greatest cause of p o o r results in microscopy.
C u r r y , Grayson & H o s e y (1982) gave details of how
to adjust substage condensers for s t a n d a r d and
K o h l e r illumination.
T h e next important factor is adjusting t h e contrast
to suit each specimen. Thin sections of c a r b o n a t e
rocks in particular require a high contrast, and this
may be obtained by stopping down t h e substage iris
s o m e w h a t . C o m p l e t e stopping-down, h o w e v e r , p r o
duces spurious interference effects at grain edges
and reduces resolution. N e u t r a l density filters should
then b e interposed to r e d u c e light intensity. R e
ducing t h e illuminator lamp intensity m a y n o t be
desirable as this alters t h e colour t e m p e r a t u r e of t h e
incident light.
Highly recrystallized and dolomitized c a r b o n a t e s
present particular difficulties. D e l g a d o (1977) n o t e d
that details such such as bioclasts and voids visible in
hand specimens or peels of such rocks vanished
u n d e r t h e petrological microscope. H e discovered
that diffusing the transmitted light resulted in a
dramatic increase in t h e resolution of such cryptic
features. T h e best diffuser was p r o d u c e d by coating
t h e undersurface of a thin section by b u r n i n g mag
nesium ribbon s o m e 0.20.25 m below t h e slide. A t
this distance, a 0.07 m length of Mg ribbon p r o d u c e s
a coating of about 20 urn thickness. T h e coated glass
surface is protected by a n o t h e r glass slide before
mounting on t h e microscope stage. (Caution!
use
goggles the bright flame of burning magnesium
can
cause retinal damage!) E x p e r i m e n t s n e e d to b e d o n e
with and without t h e condenser in place, d e p e n d i n g
on t h e specimen. Best results are o b t a i n e d with
magnifications of x l O or less.
In all cases, it is advantageous to take time to
4.8 M A N U F A C T U R E R S A N D
SUPPLIERS
4.7.4 P h o t o m i c r o g r a p h y
Most research petrological microscopes have p h o t o micrographic a t t a c h m e n t s , while simpler micro
scopes can be used with 35 m m S L R cameras fitted
with a p p r o p r i a t e a d a p t o r rings. Curry et al. (1982)
give useful hints a b o u t using these systems. In
genera], t h e most a p p r o p r i a t e films a r e fine grained,
high contrast types. This usually m e a n s they have
slow speed and concomitantly long exposure times,
so it is necessary to ensure that t h e microscope is
free from vibration, best d o n e by working on a stone
or concrete optical bench. T h e p h o t o m i c r o s c o p e
should be rigidly s u p p o r t e d .
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llilii
107
provenance
FIELD/SUBSURFACE
TECHNIQUES
mineralogy
DEPOSITIONAL
FABRICS
109
modal composition
grain m o r p h o l o g y
grain size
GILL HARWOOD
grain orientation
SEDIMENTARY
PETROGRAPHY
-mechanical compaction
5.1
INTRODUCTION
-solution compaction
DIAGENETIC
FABRICS
-cementation
-dissolution
-replacement
S O U R C E ROCK P O T E N T I A L
MIGRATION CONDUIT POTENTIAL
RESERVOIR P O T E N T I A L
Fig. 5 . 1 . Relationship of sedimentary petrography and petrographic fabrics to other branches of sedimentology.
108
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llllllllllllllllllllHMIIIIIIIIIIIIIIIIIIIIllllllf
110
G. HARWOOD
cement
5.2.2 Modal c o m p o s i t i o n
grains
porosity
Fig. 5.2. Fabrics of sedimentary rocks: (a) Grain-supported sediment; finer matrix has accumulated between a framework
of grains.
(b) Grain-supported sediment; pore spaces between grains are partially occluded by cement, although there is some
remaining porosity.
(c) Matrix-supported sediment; grains appear to 'float' in finer-grained matrix.
(d) In three-dimensional samples, this specimen can be seen to be grain-supported, with matrix between skeletal fragments.
In the two dimensions of a thin section, however, it appears to be matrix-supported.
5.2 D E P O S I T I O N A L F A B R I C S
5.2.1 Grain identification
Mineral identification in thin sections can be back
ed u p by X R D analysis of p o w d e r e d rock samples
( C h a p t e r 7 ) . T h e r e are many excellent texts on
mineral identification, all with much m o r e detail
than can be included h e r e . T h e properties of s o m e
c o m m o n e r minerals in sedimentary rocks are given
in Table 5 . 1 ; examples of these minerals in thin
sections are shown in m o d e r n coloured guides to
sedimentary constituents (Scholle, 1978, 1979;
A d a m s et al., 1984) plus the older s t a n d a r d descrip
tive texts (Carozzi, 1960; K r u m b e i n & Pettijohn,
1961; Milner, 1962a, b ; Pettijohn, 1975).
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111
TECHNIQUES
Table 5 . 1 .
S U M M A R Y
AND TUCKER
OF C O M M O N
MINERALS IN SEDIMENTARY
COMPILED
FROM KERR
(1959)
Table 5 . 1 .
(Continued)
( 1 9 8 1 )
GROUP/
CRYSTAL
MINERAL
SYSTEM
Quartz
TRIGONAL
COLOUR
RELIEF
CLEAVAGE
BIREFRINGENCE
OTHER
C E M E N T
N O N E
COLOURLESS
L O W
+ V E
N O N E
COLOURLESS
L O W
GREY
+ V E
AND
OCCURRENCE
OVERGROWTH
CEMENT
C O M M O N
Cherts
F O R M
FEATURES
GREY
A S
DETRITAL G R A I N S , C E M E N T S A N D AS D I A G E N E T I C
(REPLACIVE)
CHALCEDONY
AND
QUARTZ
A C I C U L A R CHERT ( C H A L C E D O N Y ) , M E G A Q U A R T Z
AND
MEGAQUARTZ
M I C R O Q U A R T Z ; ALL F O R M S D I A G E N E T I C U N L E S S A S
OCCLUDE
DETRITAL
VOIDS
GRAIN
FELDSPARS
MICROCLINE
TRICLINIC
COLOURLESS
PRESENT
L O W
VE
GREY
CROSSHATCH
ORTHOCLASE
MONOCLINIC
COLOURLESS
PRESENT
L O W
VE
GREY
SIMPLE
PLAGIOCLASE
TRICLINIC
COLOURLESS
PRESENT
L O W
VE
GREY
MULTIPLE
MONOCLINIC
COLOURLESS
PROMINENT
MODERATE
TWINS
M A Y
TWINS
TWINS
FORM
P R E S E N T AS DETRITAL M I N E R A L S B U T
COMMONLY
OVERGROWTH
H A V E C L O U D Y A P P E A R A N C E A S ALTER TO C L A Y
CEMENTS
MINERALS
MICAS
MUSCOVITE
+ V E
BRIGHT
COLOURS
PARALLEL
PLANAR
BIOTITE
MONOCLINIC
PROMINENT
BROWN-GREEN
MODERATE
+ V E
BRIGHT
PLANAR
CLAY
C O M M O N
DETRITAL
MINERAL
C O M M O N
DETRITAL
MINERAL
EXTINCTION
COLOURS,
PARALLEL
M A S K E D B Y COLOUR
EXTINCTION,
MINERALS
PLEOCHROIC
CHLORITE
MONOCLINIC
GREEN/BLUE
KAOLINITE
TRICLINIC
GREEN
PLANAR
MODERATE
COLOURLESS
PLANAR
L O W
+ V E
L O W
+ V E
VE
+ V E
GREY
P R E S E N T AS DETRITAL M I N E R A L S ,
GREY
C O M M O N
FINE
ILLITE
MONOCLINIC
COLOURLESS
PLANAR
SMECTITE
MONOCLINIC
COLOURLESS
PLANAR
L O W
GLAUCONITE
MONOCLINIC
GREEN
PLANAR
MODERATE,
AS
AS
ALTERATION P R O D U C T S OF SILICATES A N D
GRAINED
GREY
BURIAL
CEMENTS
AS C E M E N T S
GREY^
GREY, MASKED
MASKED BY
ZEOLITES
MOST
L O W ,
COLOURLESS
MOST
COLOUR
VE
BY
C O M M O N L Y
COLOUR
C O M M O N L Y
REPLACES
CHARACTERISTIC OF LOW S E D I M E N T A T I O N
RATES,
M A Y INFILL F O R A M TESTS, E T C .
PELLETS
GREY
C O M M O N
WHERE
AS C E M E N T S
SEDIMENTS
VOLCANICS
CARBONATES
ARAGONITE
ORTHORHOMBIC
COLOURLESS
RECTILINEAR
MODERATEHIGH
H I G H
COLOURS
CALCITE
TRIGONAL
COLOURLESS
R H O M B I C
L O W H I G H
VERY
H I G H COLOURS
DOLOMITE
TRIGONAL
COLOURLESS
R H O M B I C
L O W H I G H
V E R Y H I G H COLOURS
SIDERITE/
TRIGONAL
COLOURLESS/
R H O M B I C
L O W - H I G H
VERY
ANKERITE
PALE
C O M M O N L Y
|
DISTINGUISHED
>
BY
M A N Y
ACICULAR.
CEMENT
MORPHOLOGIES
STAINING
H I G H COLOURS J
P R E S E N T AS DETRITAL G R A I N S , C E M E N T S
AND
R E P L A C E M E N T FABRICS I N CARBONATES.
C O M M O N
REPLACEMENT MINERAL IN
IRONSTONES
BROWN
EVAPORITES
G Y P S U M
MONOCLINIC
COLOURLESS
PLANAR
L O W
GREY
ANHYDRITE
ORTHORHOMBIC
COLOURLESS
RECTILINEAR
MODERATE
BRIGHT
C O M M O N
COLOURS
BURIAL
CELESTITE
ORTHORHOMBIC
COLOURLESS
PLANAR
LOWMODERATE
GREY
BURIAL
HALITE
CUBIC
COLOURLESS
RECTILINEAR
L O W
ISOTROPIC
O N L Y PRESENT IF SECTION
C O M M O N
P R E P A R E D I N OIL
BARYTE
ORTHORHOMBIC
PLANAR
COLOURLESS
LOWMODERATE
C O M M O N L Y
EVAPORITE
CEMENT
CEMENT
C O M M O N L Y
C R Y S T A L L I N E D U E TO R E P L A C E M E N T
PARTIALLY REPLACIVE
BURIAL
CEMENT
M A Y
GREY
B E ASSOCIATED WITH
SULPHIDE
M I N E R A L I Z A T I O N ; DIFFICULT TO
F R O M CELESTITE U N D E R
IRON
OF
SEQUENCES
DISTINGUISH
MICROSCOPE
MINERALS
PYRITE
CUBIC
O P A Q U E
MAGNETITE
CUBIC
O P A Q U E
HAEMATITE
CUBIC
O P A Q U E ,
CHAMOSITE/
MONOCLINIC
GREEN
DISTINGUISHED
BROWN
TINGE
MODERATE
GREY,
BY
NON-CRYSTALLINE
BROWNS
BITUMENS
NON-CRYSTALLINE
O P A Q U E
("YELLOW
-{
[
BERTHIERINE
COLLOPHANE
IN
REFLECTED LIGHT
MODERATE
GREY-BLACK
C O M M O N
AUTHIGENIC
MINERALS
RED-GREY
O C C U R S I N O O I D S I N I R O N S T O N E S A N D AS
MASKED
P A R T I A L P O R E FILLS
COLOUR
R E P L A C I V E TEXTURES, C O M M O N L Y
ISOTROPIC
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FLUORESCENCE
IN
I N CARBONATES
FLUID
INCLUSIONS
114
G. HARWOOD
Terrigenous
10%
Allochemical
Orthochemical
Symbol from
Fig. 5.3
T
Terrigenous rocks
IA Impure allochemical
rocks
IO Impure orthochemical
rocks
A Allochemical rocks
O
Orthochemical rocks
Approx, % of
strat. record
6 5 - 75
8 - 15
10- 15
2- 5
2- 8
115
Table 5.3. Summary of the components of sedimentary rocks and their symbols, for use with triangular compositional
diagrams similar to those of Fig. 5.5 (modified from Folk, 1974b)
Symbol
Origin
Components
Igneous quartz
Qi
Q
Quartz (Q)
Metamorphic quartz
Plagioclase
P
K
R
Rv
Rmet
Rpu
it
Pel
s
O
G
M
M
F
r n s
d e p
ic
^
ap
Cvh
ert
J
]
Orthoclase/microcline
J
Sedimentary rock fragment
Volcanic rock fragment
Metamorphic rock fragment
Plutonic rock fragment
Feldspar (F)
Terrigenous
components
Rock fragments
(or lithic clasts)
(LorRF)
Detrital
Skeletal fragments
Pellets/peloids
Ooids
Unidentifiable grains
Some carbonate muds
Carbonates
Allochemical
Chemical/diagenetic
Orthochemical
in situ
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1111
r
i
)
116
G. HARWOOD
117
Table 5 . 4 . Data sheet for use when point counting thin sections (or grain mounts). Modified from Galehouse (1971a)
Thin section/sample number
Rock name
Stage type
Counter type
Initial slide position
Horizontal interval
Vertical interval
Mineral
Number
Date
Operator initials
Percentage
:
.
Counter reading
Start
Name
Finish
Number
of
Points
Comments
1
2
3
4
5 '
6
7
8
9
10
11
Opaque
Total
Accessory minerals:
(present but not at point count sites)
GRAIN MORPHOLOGY
Fig. 5 . 4 . Percentage estimation comparison charts (from Folk et al., 1970). This chart combines the visual comparator of
Terry & Chilingar (1955) with computer-generated visual comparators.
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118
G. HARWOOD
PRINCIPLES OF SEDIMENTARY PETROGRAPHY
119
Quartz
Q
F
Feldspar
RF
Rock (or lithic)
fragments
Terrigenous sediments
(b)
Brachiopods and
bryozoans
Carbonate mud
Crinoids
Carbonate sediments
(0
(d)
Fig. 5.7. Visual comparators for random sections through log normally distributed sets of spherical grains. Actual sorting
in (a) is 0.35 <t>, in (b), 0.50 <t>, in (c), 1.00 (j> and in (d) is 2.00 <t>. Apparent sorting is 0.69,0.77,1.16 and 2.08 (j) respectively
(from Harrell, 1984).
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environmental conditions, possibly mixing of sedim e n t from two different e n v i r o n m e n t s , storm mixing
of material in a high energy environment or multiple
sources of sediment supply. T h e s e conditions a r e
n o t always a p p a r e n t from field/core studies and
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G. HARWOOD
121
Fig. 5.8. Bimodal distribution in modern ooid sands. Radial ooids from Great Salt Lake are mostly 600 urn in diameter, but
larger grains average over 1,000 urn. Recent, Utah, USA.
Fig. 5.9. Grain orientation in a carbonate turbidite. Elongate grains have preferential near-horizontal orientation with
some imbrication. Miocene, Site 626, ODP Leg 101, Straits of Florida. Sample courtesy of ODP.
illustrate the uses of t h e additional information o b
tainable from thin section petrography. In inter
p r e t a t i o n , it should b e r e m e m b e r e d t h a t t h e r e is
very little size reduction of quartz sand grains during
t r a n s p o r t , b u t that selective sorting may m e a n that
t h e small grains are carried farther, or are w i n n o w e d
and deposited by w e a k e r currents (Folk, 1974b).
GRAIN ORIENTATION
M e a s u r e m e n t of grain orientation (e.g. Fig. 5.9)
necessitates t h e use of oriented field samples plus
m e a s u r e m e n t s from t h r e e perpendicular thin sec
tions. T h e orientation of t h e long axis of t h e grains
can be m e a s u r e d directly from the microscope or
s h a d o w g r a p h , or it can be m e a s u r e d by a p h o t o
metric m e t h o d which integrates t h e extinction be
haviour of all the grains in t h e field of view (Sippel,
1971). Orientations d e t e r m i n e d can be plotted on
rose diagrams, balloon diagrams or, b e t t e r , stereonets as for field palaeocurrent analysis ( C h a p t e r 2).
Compaction after sedimentation may have consider
ably reduced any a n g l e o f cross lamination m e a s u r e d
from grain orientation;'the significance of this can be
estimated from compaction features visible in t h e
Q u a r t z grains may b e single crystals (monocrystalline) and show straight extinction or undulose
extinction (best m e a s u r e d on a universal stage).
T h e y may also be composite (or polycrystalline)
with straight o r u n d u l o s e extinction within individ
ual subcrystals and m a y , or may n o t , show elonga
tion within t h e subcrystals. Q u a r t z grains may also
contain trails of inclusions, commonly fluid or gas
filled. Subparallel trails of very small inclusions, or
B o e h m lamellae, are t h e products of intense strain,
and indicate strain to have occurred within the
quartz lattice, either in situ or before incorporation
in t h e present sediment. T h e two. may be distin
guished by measuring t h e strain directions in several
quartz grains; a r a n d o m strain direction indicates
strain prior to deposition, whereas a constant strain
direction indicates stress was applied to the sedi
m e n t . Q u a r t z grains may also contain solid inclu
sions, t h e mineralogy of which may give evidence of
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122
G. HARWOOD
5.3 D I A G E N E T I C F A B R I C S
Sedimentary rocks exhibit a vast r a n g e of diagenetic
fabrics from compaction to c e m e n t a t i o n , dissolution
to complete replacement. T h e s e diagenetic fabrics
can be important indicators both of the depositional
environment of t h e sediment and of t h e chemistry of
a variety of fluids which have been flushed through
t h e sediment during burial. Mineralogical changes
can also b e u s e d t o indicate t e m p e r a t u r e and d e p t h
of burial; this is of particular importance when
correlated with organic t e m p e r a t u r e / d e p t h indi
cators in studies of petroleum generation and migra
tion. T h e sequence of diagenetic events within a
sediment governs its potential as a hydrocarbon
reservoir, as a host for mineralization, as a conduit
for mineralizing fluids/hydrocarbons, or as a source
for hydrocarbons. Research o n diagenetic fabrics
supplements information from field/core based work
and from studies of depositional fabrics.
Fig. 5.10. Average modal compositions of groups of sandstones from different tectonic environments. This technique is
only valid where many different sandstone modal compositions are available and cannot be used for single sandstone
samples (modified from Folk, 1974b). Component details are documented in Table 5.5.
Quartz
Explanation
Association
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123
POROSITY NOMENCLATURE
Porosity n o m e n c l a t u r e is based on two classic
p a p e r s : C h o q u e t t e & Pray (1970) a n d Schmidt,
M c D o n a l d & Piatt (1977). Porosity within a sedi
m e n t may be primary, a result of depositional voids
between or within grains, or secondary, the result of
dissolution, shrinkage or fracturing within the sub
surface ( C h o q u e t t e & Pray, 1970). Primary porosity
is commonly intergranular (or interparticle) (Fig.
5.16a), although r a r e intragranular porosity may be
p r e s e n t within rock fragments, skeletal material and
o t h e r detrital grains (Fig. 5.16b); intracrystalline
primary porosity can be significant within clays and
clay coatings and s o m e dolostones. Secondary p o r o
sities can be d u e to t h e dissolution of detrital grains
(Fig. 5.16c, d ) , of cements a n d authigenic minerals
(Fig. 5.16e) plus shrinkage of certain sediments
(particularly glauconitic sediments), a n d fracturing
after c e m e n t a t i o n . B o t h primary and secondary
porosity types may be mutually interconnected (Fig.
5.16a), therefore resulting in high permeabilities, or
isolated (Fig. 5.16b), with consequent low p e r m e
abilities. T h e effective porosity of a sediment is
d e p e n d e n t on t h e degree of interconnection of t h e
p o r e spaces, which a r e t h u s utilized during fluid
migration t h r o u g h t h e sediment.
Submicroscopic porosity (in places mistakenly term
ed 'chalky' porosity) is present in chalks, mudrocks
and some altered detrital grains. Efficient impregna
tion with coloured resin within these sediments will
d e m o n s t r a t e t h e presence of submicroscopic poro
sity u n d e r a good p e t r o g r a p h i c microscope; further
124
G. HARWOOD
totally
recrystallized
metamorphic
stressed
igneous
volcanic
reworked
sedimentary
recrystallized
metamorphic
(gneiss)
igneous
hydrothermal
125
stressed
metamorphic
(schist)
stressed
metamorphic
(gneiss)
increasing recrystallization
authigenic
increasing d e f o r m a t i o n
straight extinction
*~
composite
Fig. 5.12. Provenance of quartz grains: (a) Single, subrounded, monocrystalline quartz grain, showing straight extinction,
from an igneous or vein quartz source. Crossed polars. Permian, Yellow Sands, Co. Durham, UK.
(b) Single, rounded, monocrystalline quartz grain, with undulose extinction, from an igneous, or stressed igneous, source.
Crossed polars. Permian, Yellow Sands, Co. Durham, UK.
(c) Single, rounded, composite quartz grain, showing numerous subcrystals from a metamorphic source. Crossed polars.
Permian, Yellow Sands, Co. Durham, UK.
(d) Authigenic, euhedral quartz grain in carbonate grainstone. Inclusions of carbonate are present in the outermost
portions of the quartz crystal. Jurassic, Gilmer Formation, east Texas, USA.
* * solid inclusions
"
:
f l u i d inclusions
quartz o v e r g r o w t h
Boehm lamellae
Fig. 5.11. Summary diagram of quartz grain fabrics for use as provenance indicators (modified from Folk, 1974b).
5.3.2 Compaction fa b r i c s
C O M P A C T I O N BY M E C H A N I C A L
PROCESSES
COMPACTION
FABRICS
DIAGENETIC
FABRICS
mechanical
(or brittle)
solution (or c h e m i c a l )
compaction
compaction
. cementation
CHEMICAL .
ALTERATIONFABRICS
dissolution
mineral r e p l a c e m e n t
(authigenic mineral formation)
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126
G. HARWOOD
sediment
deposition
I
penecontemporaneous _
processes
\ ^
near-surface
burial
(eogenetic)
depth
processes
uplift o r
unconformity-related
(telogenetic) p r o c e s s e s
Diagenetic environment
Penecontemporaneous
(syndepositional)
Eogenetic
(near-surface)
Mesogenetic
(burial)
burial
(mesogenetic)
processes
Telogenetic
(uplift or unconformity
related)
time
127
Description
Diagenetic processes which occur within the
depositional environment
Diagenetic processes which occur within the zone
of action of surface-related processes and
surface-promoted fluid migration
Diagenetic processes that take place during burial,
away from the zone of major influences of
surface-related processes
Diagenetic processes which are related to uplift
and commonly result from surface-related fluid
migration
mixing of
meteoric and m a r i n e
phreatic z o n e s
Fig. 5.15. Theoretical cross-section showing near-surface diagenetic environments.
C O M P A C T I O N BY C H E M I C A L P R O C E S S E S
I: S O L U T I O N C O M P A C T I O N B E T W E E N
INDIVIDUAL GRAINS
Compaction by chemical processes, or pressure
solution, takes place in two ways: (i) in an unce
m e n t e d sediment, by dissolution at isolated stressed
grain to grain contacts and (ii) within a cemented
sediment, by dissolution being concentrated along a
particular surface, usually irregular, t e r m e d a stylolite. Pressure solution has been defined as t h e pre
ferential dissolution of mineral material at points of
stress (Wanless, 1979).
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llllllllll
Fig. 5.16. Porosity types: (a) Intergranular porosity in aeolian sandstone; sandstone has been impregnated with coloured
epoxy to demonstrate porosity. Cretaceous, Loch Aline Sandstone, Argyll, UK.
(b) Intragranular porosity within foraminifer test in poorly cemented carbonate sands; sample has been impregnated with
coloured epoxy to demonstrate porosity. Holocene, Shark Bay, western Australia.
(c) Secondary porosity (arrowed) resulting from feldspar dissolution; clays indicate original shape of grain. If the clays were
removed by flushing, an oversized pore would result. Sandstone was cemented prior to feldspar dissolution or pore space
would not have been preserved. Cretaceous, Woodbine Formation, subsurface Arkansas, USA. Photomicrograph courtesy
o f D r W . Ward, UNO.
(d) Secondary, intragranular, porosity (arrowed), resulting from partial dissolution of aragonitic ooid coatings.
Surrounding cement, which maintains sediment fabric, is low Mg calcite. Pleistocene, Shark Bay, western Australia.
(e) 'Expansion' porosity, later occluded by calcite, in fitted-texture grainstone. Fractures surrounded individual grains after
fitted-texture had been developed. Jurassic, Smackover Formation, east Texas, USA.
Fig. 5.17. Shelter porosity and brittle fracture: (a) Shelter porosity created by large platey benthic foraminifer bridging pore
space. Grains (ooids, superficial ooids and peloids) are packed on top of foraminifer, whereas shelter porosity (here later
occluded by calcite cement) is maintained below. Eocene carbonates, east India.
(b) Brittle fracture of foraminifer, a result of increase in overburden pressure before cementation. Brittle fracture has
destroyed shelter porosity. Fractures have since been healed by calcite cement. Eocene carbonates, east India.
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aiiiiiiiiiiiiiiiiiiiiiiiiii
Fig. 5.18. Brittle fracture: (a) Brittle fracture of large foraminifer and thin-walled brachiopod (arrowed) in carbonate
wackestone. Permian, Cadeby Formation, Yorkshire, UK.
(b) Brittle fracture and deformation of detrital mica flake in sandstone; acicular carbonate cement has later grown around
mica. Lower Carboniferous, Lower Crag Point Sandstone, Northumberland, UK.
(c) Brittle fracture in plant material; section through conifer wood from peat showing collapse of earlier, central cells.
Reflected light, oil immersion. Palaeocene, North Dakota, USA (from Ting, 1977).
(d) Brittle fracture after formation of secondary porosity. Flushing by fluids during diagenesis has caused ooids to dissolve,
leaving framework of dolomitized circumgranular cements which have since fractured (arrowed). Jurassic, subsurface
Smackover Formation, east Texas, USA.
(e) Brittle fracture of clay coatings. Clay coatings originally formed around altering feldspar grain, which has since
completely dissolved (cf. Fig. 5.16c) leading to collapse of clay coatings. Surrounding pore space maintained by earlier
cementation of quartz sand grains. Cretaceous, Tuscaloosa Formation, subsurface Arkansas, USA. Photomicrograph
courtesy of Dr W. Ward, UNO.
131
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illilll
132
G. HARWOOD
800 /j,m
133
C O M P A C T I O N BY C H E M I C A L P R O C E S S E S
I I : S O L U T I O N C O M P A C T I O N IN
CEMENTED SEDIMENTS
Stylolites and solution seams are present within
many sediment types ( H e a l d , 1955,1959; T h o m p s o n ,
1959; Weller, 1959; T r u r n i t , 1968; B r o w n , 1969;
B a t h u r s t , 1975; L o g a n & S e m e n i u k , 1976; M i m r a n ,
1977; Wanless, 1979; Gillett, 1983 and o t h e r s ) . Both
stylolites and solution seams transect t h e c e m e n t e d
sediment and develop perpendicular to the axis of
m a x i m u m stress, which may b e either o v e r b u r d e n
pressure or tectonic stress. Because stylolites and
solution seams are zones of preferential solution
within a sediment, small fragments of less soluble
minerals tend to accumulate along the solution seam.
T h u s , in i m m a t u r e sandstones and carbonates, clay
minerals may b e c o m e concentrated along a seam.
B o t h Weyl (1959) and Oldershaw & Scoffin (1967)
K-feldspar
calcitized
zeolitized
dissolved
kaolinized
albitized
Plagioclase
calcitized
dissolved
albitized
zeolitized
Carbonate rock
fragments
dissolved
dolomitized
recrystallized
Volcanic rock
fragments
calcitized
dissolved
chloritized
zeolitized
Micaceous metamorphic
rock fragments
mashed
dissolved
Chert rock
fragments
dissolved
calcitized
Claystone/shale/
siltstone rock
fragments
mashed
Muscovite
kaolinized
dissolved
Biotite
dissolved
argillized
Unstable heavy
minerals
dissolved
calcitized
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ill
134
G. HARWOOD
135
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llllll
137
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fMWtiHHHHIItHlimttlllllttlimHHWMtlHttHtiiHHIl
It,
''Wllllllllllilll
138
G. HARWOOD
Interweaving
ESTIMATION OF AMOUNTS OF
COMPACTION
A l t h o u g h t h e r e a r e m a n y qualitative studies d e m o n
strating t h e wide distribution of mechanical and
chemical compaction fabrics, published quantitative
results are considerably rarer. M e a s u r e m e n t of sty
lolite amplitudes (Fig. 5.22b, c) or of solution seam
thickness provides only a m i n i m u m estimate of t h e
a m o u n t of sediment r e m o v e d (Stockdale, 1926;
M o s s o p , 1972) and becomes m o r e difficult with low
amplitude stylolites and solution seams (Fig. 5.22f).
V o l u m e reductions in c a r b o n a t e s of approximately
4 0 % were detailed by D u n n i n g t o n (1967) and Park
& Schot (1968, p . 72); similar calculations a r e lack
ing for o t h e r sediments. P e r h a p s a future valid
contribution to this field could be m a d e by a com
bination of experimental simulation of mechanical
and chemical compaction in conjunction with the
use of c o m p u t e r imagery in volume reconstruction;
at present we only k n o w compaction is extremely
effective at reducing b o t h absolute volume and
porosity in m a n y sediments.
-III boundary
NON-SEAM SOLUTION
Pervasive solution-dolomitization
Clayey limestones
5.3.3 Cementation
Scattered
micro stylolites
Uniform
stress and
responsiveness
S w a r m s or
seams in
responsive
zone
Limestone ^ C l a y e y &o/r
HSdolomitc
g C l a y &o/r
dolomite
Non-uniform
responsiveness
g j S e a m rjTJResistant unit
^ R e s i s t a n t grains
Fig. 5.23. Basic styles of solution compaction in carbonates (from Wanless, 1979). These styles can also be used to describe
solution compaction in siliciclastic sediments.
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139
C E M E N T T Y P E S I: G R A I N O V E R G R O W T H
CEMENTS
G r a i n overgrowth c e m e n t s (or conformable ce
ments) commonly develop o n q u a r t z and feldspar
detrital grains and o n s o m e skeletal c a r b o n a t e frag
m e n t s (Fig. 5.26). Q u a r t z overgrowth cements can
b e clearly recognized using a petrological micro
scope if clay- o r hematite-rich coatings (commonly
inaccurately t e r m e d 'dust' rims) a r e t r a p p e d be
tween overgrowth c e m e n t and grain (Fig. 5.26a, b ) .
M o r e rarely, two coatings may b e c o m e t r a p p e d ,
indicating two stages of d e v e l o p m e n t of t h e over
growth c e m e n t . W h e r e n o such coatings are present,
quartz overgrowth cements are much m o r e difficult
to recognize. Such c e m e n t s a r e , however, typically
inclusion-free (or, at least, inclusion-poor) and t h u s ,
with c a r e , may b e distinguished from t h e p a r e n t
grain. F u r t h e r , if sufficient intergranular p o r e space
is present within t h e sediment, t h e overgrowth ce
m e n t s will develop planar euhedral crystallographic
faces (Fig. 5.26c, d ) , although it should b e r e m e m
bered that continued e n l a r g e m e n t of the overgrowth
cements will lead to c o m p r o m i s e b o u n d a r i e s b e
tween the cements. Such compromise boundaries
may be difficult to distinguish from compacted
fabrics: cathodoluminescence can, in some cases,
140
G. HARWOOD
Cement
terminology
Less correct
terminology
needle
(or fine acicular)
whisker
needle fibre
pendant or
microstalactitic
fibrous
'micritic' or
microcrystalline
circumgranular
isopachous
acicular
equant
blocky
circumgranular
equant
cement
pelodial
columnar
Fig. 5.24. Disconformable crystal cements: (a) Multiple nucleation sites, resulting in circumgranular, acicular, aragonite
cements growing on skeletal fragments in modern, shallow-water, carbonate sands. Crossed polars. Recent, US Virgin
Islands.
(b) Few nucleation sites, resulting in poikilotopic calcite cement enclosing quartz grains; two calcite cement crystals only
are present, their boundary is arrowed. Crossed polars. Permian, Yellow Sands, Co. Durham, UK.
Description
thin (do /xm) cements of single
or en echelon crystals; form in
or near soil zone
overg rowth
sparry
poikilotopic
baroque
(or saddle)
grain
porosity
Fig. 5.25. Summary diagram of descriptive terms used for cement morphologies. For scale, grains shown have an average
diameter of 500 urn.
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Fig. 5.27. Grain overgrowth cements II: (a) Echinoderm overgrowth cements in crinoidal grainstone. Original grains (G)
appear greyer than overgrowth cements as they include traces of the original internal pores plus some microdolomite
crystals. Overgrowth cements occlude intergranular porosity and form compromise boundaries. Mississippian, Burlington
Formation, Illinois, USA. Sample courtesy of W.B. Meyers, SUNY.
(b) Crossed polars photomicrograph of (a), demonstrating optical continuity of overgrowth cements and occlusion of
intergranular porosity.
(c) Echinoid overgrowth cement on echinoderm spine from winnowed carbonate tubidite. Overgrowth cement grew in
deep water (>1000 m) sediment. Miocene, Site 626, ODP Leg 101, Straits of Florida. Sample courtesy of ODP.
(d) Radiating overgrowth cements (arrowed) on planktonic foraminifer. Cements grow in optical continuity with radial
calcite of foraminifer test in deep water (>1000 m) sediment. Miocene, Site 626, ODP Leg 101, Straits of Florida. Sample
courtesy of ODP.
Fig. 5.26. Grain overgrowth cements I: (a) Thin quartz overgrowth cements (arrowed) adjacent to open pore (P).
Overgrowth cements grew on rounded and subrounded grains, Permian, Penrith Sandstone, Cumbria, UK.
(b) Crossed polars photomicrograph of (a), showing composite nature of detrital quartz grain plus optical continuity of
overgrowth cements with their substrate. Haematite-rich coatings (arrowed) define detrital grain surfaces.
(c) Planar, euhedral faces of quartz overgrowth cements, which have grown into pore.spaces (P). Cement thickness varies
around pore space and is partially a function of crystal orientation and subsequent growth direction. Haematite-rich
coatings on detrital grain surfaces are clearly visible. Permian, Penrith Sandstone, Cumbria, UK.
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(d) Crossed polars photomicrograph of (c). Note optical continuity of overgrowth cement on strained, detrital quartz grain
(Q). Altered feldspar grain (F) has no overgrowth cement.
itiiimmmmmi
144
G. HARWOOD
2 km burial
Secondary
porosity
K Al S i 0 + AI Si 0 (OH)
Feldspar
Kaolinite
3
K AI Si O (OH) + S i 0 + H 0
lllite
Quartz Water
3
10
Fig. 5.28. Chemical reactions between feldspar and kaolinite are triggered by continued burial to produce illite, quartz
overgrowth cements plus secondary porosity (from Bj0rlykke, 1983).
warn
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145
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148
G. HARWOOD
Fig. 5.31. Carbonate cements II: (a) Columnar, isopachous, circumgranular cements on ooids and ooid-coated echinoderm
fragments. Remaining porosity is occluded by equant low Mg calcite cements. Lower Carboniferous, Brofiscin Oolite
Formation, Glamorgan, UK. Photomicrograph courtesy of K. Hird and M.E. Tucker, University of Durham, UK.
(b) Acicular, aragonite, 'ray' cements which grew within a reef cavity, later filled by internal sediment (IS). 'Ray' fans
exhibit sweeping extinction. Crossed polars. Recent, Jamaica. Photomicrograph taken courtesy of C.H. Moore, LSU.
(c) Radiaxial acicular calcite cements, showing characteristic curved cleavages of crystals; crystals are now low Mg calcite but
149
analysis (M.C. Akhurst, personal communication) indicates they were originally high Mg calcite. Growth direction was from
right to left; Mississippian, Carbonate mound core, Co. Galway, Ireland.
(d) Compromise boundaries (arrowed) formed by columnar cements competing for growth in intergranular pore spaces in
ooid grainstone (see also Harwood & Moore, 1984). Jurassic, subsurface Smackover Formation, east Texas, USA.
(e) Equant low Mg calcite cements in exposed ooid grainstone. Holocene, Joulters Cay, Bahamas.
(f) Baroque (or saddle) dolomite cement (D) in ooid grainstone. Dolomite is inclusion-rich and shows undulose extinction.
Calcite spar cement (C) occludes remaining pore space. Crossed polars. Jurassic, subsurface Gilmer Formation, east Texas,
USA.
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151
In o t h e r sandstones, q u a r t z overgrowth c e m e n t s d o
n o t form until after considerable solution c o m p a c
tion; h e r e t h e solution compaction can b e t h e major
source of silica, although reactions b e t w e e n clay
minerals in i m m a t u r e sandstones may also contri
b u t e silica (Fig. 5.28) (Bj0rlykke, 1983).
C E M E N T TYPES II: D I S C O N F O R M A B L E
CRYSTAL CEMENTS
Disconformable crystal c e m e n t s nucleate as separ
ate crystals o n sediment grains and, as such, are
distinct from overgrowth c e m e n t s . T h e size and
n u m b e r of these crystals a r e largely d e p e n d e n t o n
Fig. 5.33. Cements in carbonate sediments: (a) Anhydrite cement (A) occluding porosity in dolomitized ooid grainstone.
Dolomitized circumgranular cements (arrowed) coat ooids which have been partially dolomitized before dissolution of
remaining calcite. Opaque coating in ooid centres is bitumen, from hydrocarbon migration after anhydrite cementation
(see also Harwood & Moore, 1984). Jurassic, subsurface Smackover Formation, east Texas, USA.
(b) Multiphase carbonate cements. Dolomitized algal laminae (D) adjacent to void. Void fill was in several stages; first,
zoned dolomite cement (Z), second, rare marcasite (M), third, complexly zoned large calcite spar (C|) and last, voidoccluding calcite spar (C ). Photomicrograph taken under cathodoluminescence. Permian, subsurface Cadeby Formation,
Selby Coalfield, Yorkshire, UK.
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152
G. H A R W O O D
PRINCIPLES OF S E D I M E N T A R Y P E T R O G R A P H Y
153
c
HI
BURIAL CEMENTS
C a r b o n a t e burial c e m e n t s are commonly coarsely
crystalline, and include b a r o q u e d o l o m i t e and cal
cite spar (Fig. 5.31f), in places z o n e d . Burial c e m e n t s
in o t h e r sediments are c o m p o s e d of a complex range
of mineralogies, n o t all of which are readily distin
guishable with a petrological microscope ( T a b l e 5.1).
S o m e are finely crystalline (clay minerals, h e m a t i t e ,
limonite), o t h e r s are coarsely crystalline (similar to
c a r b o n a t e burial cements) and c o m m o n l y poikilo
topic, w h e r e a s yet o t h e r s are both coarsely crystal
line a n d , to s o m e extent, a p p e a r to replace t h e host
sediment ( a n h y d r i t e , halite, p h o s p h a t e s , glauconite)
(Fig. 5.33a). Q u a r t z overgrowth c e m e n t s a r e a fur
ther c o m m o n burial c e m e n t , although their p r e s e n c e
alone is not an indication of d e e p burial. In silici
clastic sediments careful attention to p e t r o g r a p h i c
detail, particularly t h e compaction history, is neces
sary t o d e t e r m i n e w h e t h e r a c e m e n t formed during
d e e p burial ( > 2 , 0 0 0 m ) or at an earlier stage in t h e
diagenetic history.
A t w h a t e v e r stage in the diagenetic history of t h e
sediment they form, c e m e n t s are a record of t h e
fluctuating
p o r e w a t e r history of a s e d i m e n t .
N u m e r o u s , clearly identifiable stages of c e m e n t a t i o n
in a sediment are evidence of changes in p o r e w a t e r
chemistry and saturation states, even if all the p r e
cipitated phases are of a single mineralogy (e.g. Fig.
5.33b). M o r e i m p o r t a n t , p e r h a p s , is t h e evidence
given by the termination of precipitation of a c e m e n t
p h a s e , indicating a decrease in saturation, or supersaturation, of that phase within the p o r e fluid and, in
places, dissolution of pre-existing c e m e n t phases
w h e n u n d e r s a t u r a t e d p o r e fluids are introduced into
a sediment. Analysis of t h e chemistry and isotopic
compositions of t h e various c e m e n t phases can give
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G. HARWOOD
Fig. 5.35. Corrosion and dissolution of grains: (a) Corrosion of detrital quartz grain margins (arrowed) by migrating pore
fluids prior to precipitation of poikilotopic calcite cement (C). Adjacent grain margins (G) show no corrosion but planar
margins from euhedral overgrowth cements. Permian, Penrith Sandstone, Cumbria, UK.
(b) Corrosion of precursor dolomite. Dolomitization of former carbonate grains with micrite envelopes has resulted in
coarsely crystalline dolostone with remnants of micrite envelopes preserved. Subsequent corrosion of dolomite crystals has
led to truncation of micrite relics (arrowed) with later porosity occlusion by calcite. This apparent replacement of dolomite
by calcite is termed calcitization or, less correctly, dedolomitization. Section stained with Alizarin red S. Permian, Cadeby
Formation, Yorkshire, UK.
(c) Corrosion along cleavages in dolomite, probably an effect of recent weathering. Dolomite within 5 mm of pore
space has been corroded along cleavage planes with subsequent precipitation of iron oxides, defining amount of
dissolution. Further away from pore space (bottom right corner of photomicrograph) dolomite remains uncorroded.
Permian, Cadeby Formation, Yorkshire, UK.
(d) Corrosion and secondary porosity formation along cleavage planes in feldspar. Impregnation has shown intragranular
porosity (arrowed) within feldspar grains Carboniferous, Upper Crag Point Sandstone, Northumberland, UK.
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156
G. HARWOOD
157
5.3.4 Dissolution fa b r i c s
Dissolution in t h e subsurface generates secondary
porosity ( C h o q u e t t e & Pray, 1970) (Section 5.3.1).
This m a y n o t necessarily b e large-scale dissolution
(e.g. Fig. 5.16d), b u t may result only in slight corro
sion of t h e detrital grains or pre-existing cements in
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CORROSION FABRICS
Initial dissolution leads to t h e corrosion of grain
margins and c e m e n t t e r m i n a t i o n s . This is c o m m o n
158
G. HARWOOD
ALTERATION FABRICS
D u r i n g t h e t e m p e r a t u r e a n d pressure increases
through burial and during migration of p o r e waters,
m a n y previously-stable minerals, or minerals which
w e r e deposited a n d b u r i e d t o o rapidly t o b e c o m e in
equilibrium with surface t e m p e r a t u r e s and pres
sures, are "brought into a regime w h e r e they are
unstable in the prevailing conditions. T h e s e minerals
break down to form m o r e stable products, generally
in t h e site of t h e original mineral (e.g. Fig. 5.16c);
c o m m o n examples are heavy minerals w h e r e , in U S
Gulf Coast sandstones, t h e degree of alteration has
b e e n related t o burial depths (Fig. 5.38) (data of
159
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CD
D.
F
Fig. 5.37. Triangular diagram showing the present
composition of five sandstones, after dissolution and
alteration, and their reconstructed composition, assuming
15% of the grains which occupied oversized pores were
rock fragments and 85% were feldspar (from McBride,
1985).
E .
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Q.
CD
Q
12 H
1.4 H
16 H
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160
G. HARWOOD
TIMING OF DISSOLUTION, A L T E R A T I O N
AND REPLACEMENT
T h e timing of dissolution, alteration and replace
m e n t can be established relative to o t h e r diagenetic
events. For e x a m p l e , L o u c k s , D o d g e & Galloway
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161
Bitlillill
(c) Partial fabric retention during doldmitization; dolomitized ooid grainstone retains fabric of original isopachous
circumgranular cements and form of ooids. although textures within the ooids are obliterated with formation of partial
oomoldic porosity. Intergranular porosity has been partially occluded by bitumen. Jurassic, subsurface Smackover
Formation, east Texas, USA.
(d) Fabric destruction during dolomitization; dolomitization has produced coarse sub- to euhedral dolomite crystals with
vestige of original fabric and considerable variation in dolomite crystal size. Crystal size also varies according to position
within sediment (Harwood, 1986). Permian, Cadeby Formation, Nottinghamshire, UK.
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165
Fig. 5.41. Timing of replacement: (a) Dolomite rhombs in crinoid grainstone; dolomite has grown replacively after
formation of crinoid overgrowth cements in crinoid grainstone of low porosity and permeability. Voids (arrowed) are the
result of plucking during section-making and thus show false porosity. Section stained with alizarin red S. Mississippian,
Burlington Formation, Illinois, USA. Sample courtesy of W.B. Meyers, SUNY.
(b) Dolomite rhombs in ooid grainstone; dolomite has formed after cementation of ooid grainstone and after partial
dissolution and compaction of ooid (arrowed) (from Harwood & Moore, 1984). Jurassic, subsurface Smackover
Formation, east Texas, USA.
(c) Dolomite and euhedral authigenic quartz growth after compaction and cementation. Ooid grainstone with
interpenetrating grain to grain contacts and later intergranular calcite cements (see also Fig. 5.40a, b) with later replacive
dolomite rhombs (D) and authigenic quartz crystals (Q). The relative timing of dolomite and quartz growth is not
determinable as the two are not found intergrown. Jurassic, subsurface Smackover Formation, Arkansas, USA.
(c) Replacement of certain parts of detrital sedimentary grains; calcite of intergranular cement has replaced components of
the derived sediment grains, leaving quartzose portions unreplaced. Permian, Yellow Sands, Co. Durham, UK.
(e) Crossed polars view of Fig. 5.40(d), showing that calcite within detrital grains is in optical continuity with poikilotopic
intergranular calcite. Former mineralogy of replaced components cannot be determined.
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Quartz
Fig. 5.42. Diagenetic potential of sedimentary rocks: (a) Triangular diagram of siliciclastic end members, demonstrating
mechanical and chemical resistance to diagenetic alteration (modified form Bj0rlykke, 1983). Width of arrow increases
with increased diagenetic potential.
(b) Similar diagram for carbonate mineralogical end members, showing high diagenetic potential of aragonite and high Mg
calcite dominated sediments. Carbonate minerals have similar rigidities, but the aragonite-low Mg calcite transformation is
by dissolution-reprecipitation (albeit on a fine scale in some cases) whereas that of high Mg calcite to low Mg calcite appears
to involve no structural recrystallization, but simply magnesium 'stripping'. It should be remembered that many Palaeozoic
carbonates were dominated by high Mg calcite or low Mg calcite, with little or no aragonite. Width of arrow increases with
increased diagenetic potential.
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5.4
CONCLUSIONS
168
G. HARWOOD
Petrographer
Date
Description Form
Specimen
Terrigenous s e d i m e n t s
Hand s p e c i m e n
Colour: Fresh
Weathered
Structures:
Grain size:
Max
Min
Models)
mm
Roundness
Sphericity
Allochemical
Orthochemical
Sorting:
Other features:
Framework
Cement
Diagenetic events
Thin s e c t i o n
Detrital composition
Quartz
K feldspar
Plagioclase
Rock fragments
Muscovite
Biotite
Heavy minerals
Opaque minerals
Carbonates
Matrix
Others
Diagenetic components
Cement
Other authigenic
minerals
Max
Min
Models)
Roundness.
Sphericity .
Sorting
monocrystalline < ^ ,
polycrystalline < ^
Matrix components:
Porosity:
Type
Primary
Secondary
Fig. 5.43. Data sheets for systematically recording petrographic observations; sheet A is for terrigenous sediments and
sheet B for carbonates. Sheets can be combined if all observational criteria are not itemized.
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170
G. HARWOOD
Sedimentary Petrography
Diagenetic components
Petrographer ...
Date ...
Description Form
Cement type
Porosity
%
Specimen ...
Primary
Secondary
Carbonate/evaporite sediments
Hand s p e c i m e n
Colour: Fresh
Weathered ..
Induration:
Grain size:
Type
Other authigenic
minerals
Structures:
x
Max.
Min.
Mode(s)
Sorting:
Other features
Components on triangular diagrams
1. Origin of components
Thin s e c t i o n
2. Fabric of components.
Detrital
Detrital grains
Skeletal types
Size
((im)
Roundness
Fragmentation
Allochemical
Orthochemical
Framework
grains
Cement
(I = impure)
Intraclasts
Ooids
Pellets
Peloids
Quartz grains
Feldspar grains
Other detrital
minerals
Matrix
Evaporites
Gypsum
Anhydrite
Halite
Others
A Matrix
3. Three
appropriate
components
Diagenetic events
...
Size
Comments
,
(b)
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T
172
G. HARWOOD
Location/well
Elevation/depth
Grain supported
Matrix supported
Carbonate minerals
Calcite
Fe-calcite
Dolomite
Fe-dolomite
Diagram/photomicrograph
Terrigenous minerals
Quartz
K feldspar
Plagioclase
Mica
Rock name
Sedimentary structures
'
Skeletal components
Chert
Others
Matrix
Cement
Porosity
Comments
(c)
Fig. 5.44. Abridged data sheet of a type used by many petroleum company research laboratories.
nill
173
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CATHODOLUMINESCENCE MICROSCOPY
Cathodoluminescence microscopy
JOHN MILLER
- 8
6.1
INTRODUCTION
6.2 P H Y S I C A L E X P L A N A T I O N O F
LUMINESCENCE
6.2.1 Excitation f a c t o r s
A n explanation of luminescence was not forth
coming until the d e v e l o p m e n t of q u a n t u m theory.
Q u a n t u m approaches to luminescence a r e outlined
by Nickel (1978), Marfunin (1979) and W a l k e r
1
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174
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176
J . MILLER
CATHODOLUMINESCENCE MICROSCOPY
3 +
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177
3 +
6.3
EQUIPMENT
Pump valve
High
voltage
cable
Deflection
magnet
assembly
25 mm
1"
Stage motion
knobs
Microscope p - ,
objective | i |
Specimen
Optic axis
-J
- Focus
coil
Cathode
Fig. 6 . 1 . Schematic drawings of the Nuclide ELM-2A Luminoscope specimen chamber in top view and cross-section.
Courtesy of D. Marshall, Nuclide Corporation.
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6.3.1 Operation
Figure 6.1 shows a schematic cross-section of a
typical C L a p p a r a t u s . T h e electron b e a m is gener
ated by applying a potential u p to 30 k V between a
small tungsten steel c a t h o d e disc and an annular
a n o d e which lie within an evacuated glass t u b e . A t
low pressures, a plasma is established with a dis
charge of positive ions travelling towards the cathode.
A n electron b e a m (together with s o m e negative
ions) is emitted in the opposite direction, attracted
towards t h e collimating a n o d e and passing t h r o u g h
its central hole. In t h e Nuclide Luminoscope (Fig.
178
J . MILLER
CATHODOLUMINESCENCE MICROSCOPY
6.3.2 Microscopes f o r
cathodoluminescence
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179
6.4 S A M P L E P R E P A R A T I O N
C L observations are usually m a d e on uncovered thin
sections. T h e y must be b o n d e d with thermo-stable
epoxy resin (see C h a p t e r 4). Bonding agents such as
Lakeside 70 a n d C a n a d a Balsam "are unsuitable
m o u n t a n t s for C L work as they a r e volatile, causing
blistering and rapid charring under the electron beam.
S o m e epoxy resins also show luminescence (usually
yellow) which can interfere with observations.
Polished surfaces give t h e best optical resolution,
and t h e double polished thin sections described in
C h a p t e r 4 are ideal. If great detail is not required,
surfaces can be quite crudely p r e p a r e d . Etching of
180
J . MILLER
CATHODOLUMINESCENCE MICROSCOPY
offers n o i m p e d i m e n t to t h e electron b e a m .
D e p e n d i n g on the size of t h e specimen c h a m b e r ,
rock slices can also be examined u n d e r C L . T h e
standard Nuclide Luminoscope c h a m b e r in parti
cular is large enough to take slices over 5 m m in
thickness, and t h e r e is a special d e e p version which
can take sawn core samples for rapid examination,
possibly on site. Best results are obtained from
s m o o t h e d surfaces, but even b r o k e n faces can give
useful information. P u m p - d o w n times a r e corres
pondingly increased for these larger and m o r e por
ous samples, which should be well dried before
evacuation.
Single crystals and loose sediment can also be
viewed with little p r e p a r a t i o n . A rapid a n d simple
technique for checking t h e mineralogy of placer
sands is simply to sprinkle s o m e sand on t o t h e speci
m e n tray glass or on a standard slide and evacuate
it in t h e c h a m b e r ( R y a n & Szabo, 1981). If t h e r e is
a tendency for grains to b e c o m e charged and leap
about disconcertingly in t h e b e a m , a dried a q u e o u s
grain suspension usually has sufficient adhesion.
6.5 I N T E R P R E T A T I O N A N D
DESCRIPTION OF CL RESULTS
C L colour and brightness are d e p e n d e n t o n several
factors, including b e a m voltage, current, surface
current density (a function of beam focus), n a t u r e of
sample surface, time for which sample has previous
ly b e e n irradiated, degree of heating (thermal quen
ching or emission of thermoluminescence) and t h e
geochemical composition of t h e sample itself. Mar
shall (1978) has suggested a standard for reporting
C L results so that comparisons b e t w e e n t h e results
of different w o r k e r s m a y be m o r e valid. With t h e
cold c a t h o d e e q u i p m e n t , so many variable factors
are involved that t h e r e is s o m e d o u b t w h e t h e r a true
standard can be established (Fairchild, 1983). H o w
ever, it certainly facilitates communication and com
parison if t h e observation conditions are r e p o r t e d as
Marshall suggested. Experience has also shown that
t h e same samples can have different a p p e a r a n c e s
u n d e r C L in machines from different manufacturers.
Details such as fine zonation in calcite c e m e n t s may
be visible in o n e case but not in a n o t h e r . T h e
reasons for this are not fully u n d e r s t o o d ; t h e metal
used for the c a t h o d e disc may be a factor, and t h e
angle at which the beam impinges on the specimen
surface may b e a n o t h e r . Cold c a t h o d e systems may
g e n e r a t e s o m e C L as a result of ion b o m b a r d m e n t ,
and t h e n a t u r e of t h e ion content of t h e plasma is
likely to be m a c h i n e - d e p e n d e n t . T h e r e f o r e , t h e type
of e q u i p m e n t should be specified as well as t h e
observation conditions.
P r o b l e m s in communication of results arise from
t h e difficulty of describing C L colours and intensi
ties. A u t h o r s refer t o 'bright' o r 'dull' luminescence,
but such t e r m s are relative to their sample suites and
a r e also highly subjective. T h e descriptions d e p e n d
o n t h e sensitivity of t h e observer's eye to specific
wavelengths, instrumental variation (such as cham
b e r p r e s s u r e , voltage, b e a m focus and b e a m current)
and t h e wavelength-dependent transmission proper
ties of t h e optical system, including t h e gradual build
u p of b r o w n pyrlysis deposits o n t h e viewing window.
F u r t h e r m o r e , h u m a n eyes a r e u n e v e n in their per
ception of t h e visible spectrum, with p e a k s and
troughs in sensitivity across t h e frequency r a n g e .
A significant p r o p o r t i o n of t h e population (mainly
males) is also affected with 'colour-blindness' of o n e
kind or a n o t h e r , often to a subtle d e g r e e which may
n o t b e a p p a r e n t in n o r m a l life. R e p o r t i n g of colour
perception is also subject to variations in linguistic
understanding of words for describing colours. T h e s e
a r e learned at an early age and reflect t h e bias and
b a c k g r o u n d of o u r p a r e n t s . U p o n asking a n u m b e r
of p e o p l e to describe t h e C L colour of a given
sample, I have received responses including 'bright
r e d ' , 'dull o r a n g e ' , 'purple-brown' and 'crimson'; a
red-green colour-blind person perceived 'grey'. T o
help overcome this potentially serious p r o b l e m , o b
servations should b e m a d e u n d e r internally consis
tent operating conditions and descriptions of C L
characteristics chosen to b e as u n a m b i g u o u s as pos
sible. Careful p h o t o g r a p h i c recording is most impor
tant t o support subjective descriptions, but this has
p r o b l e m s in itself (see below).
W h a t steps can be t a k e n to minimize subjectivity
in recording and reporting C L results? Several
petrographic uses of C L involve comparisons of C L
intensities and colours between samples or within
different areas of a single sample. Pierson (1981)
suggested t h a t a s a m p l e with t h e brightest observed
luminescence be k e p t in t h e c h a m b e r and used as a
reference against which t h e intensity of o t h e r sample
areas could be less arbitrarily j u d g e d . H e also advo
cated t h e use of a colour chart (fig, 21-1 in Pauling,
1970) for determining C L colour. This colour chart
is quite i n a d e q u a t e for registering t h e subtle range
of C L colours, and s t a n d a r d rock colour charts d o
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mmmm
181
182
J . MILLER
6.6 A P P L I C A T I O N S
Cathodoluminescence has several general applica
tions in sedimentology:
(1) Rapid visualization of mineral distribution,
w h e r e minerals have closely similar optical p r o p e r
ties or are very fine-grained. F o r e x a m p l e , yelloworange C L of calcite generally distinguishes it from
t h e d a r k e r red-crimson of d o l o m i t e , and feldspars
are very bright blues, reds or greens c o m p a r e d with
subdued violets and browns for q u a r t z grains. C o m
plex intergrowths of minerals such as halite and
sylvite (blue-grey and silver-grey C L respectively)
CATHODOLUMINESCENCE MICROSCOPY
can be easily visualized. It is essential to be very
cautious and check mineral identifications with other
techniques, as C L has complex origins and emission
colours are rarely diagnostic.
(2) Fabric and textural characteristics are often
m o r e easily visible, especially in recrystallized car
b o n a t e rocks (Fig. 6.3). Fossils in n e o m o r p h o s e d
limestones or c a r b o n a t e - c e m e n t e d sandstones re
a p p e a r and can give otherwise unavailable strati
graphic and environmental information (Figs 6.4c, d,
6.5a, b ) . Point counts carried o u t o n such rocks
u n d e r C L may differ significantly from those per
formed u n d e r transmitted light, particularly in t h e
greater proportion of bioclasts detected. C L m a k e s
it much easier to d e t e r m i n e if sparry fabrics are of
n e o m o r p h i c or cement origin by displaying growth
zones in crystal aggregates (Dickson, 1983). Sparry
crystal aggregates might display t h e outline of pri
mary void systems u n d e r C L (Fig. 6.3a, b ) , p r o
viding m o r e information on porosity evolution than
available with transmitted light alone.
(3) Small-scale features, which a r e difficult or
impossible to see in transmitted light microscopy,
may be well-displayed with C L . Fine veins, grain
fractures (caused by extension or c o m p a c t i o n ) , and
authigenic mineral overgrowths readily b e c o m e ap
p a r e n t (Fig. 6.5c, d ) .
(4) P r o v e n a n c e studies a r e m o r e exact, since
m a n y grain suites carry characteristic luminescence
'fingerprints' which can be related to their source
rocks (Fig: 6.5f). T h e origin of quartz grains can be
d e t e r m i n e d to s o m e d e g r e e , and mixing of quartz
grains, feldspars and heavy minerals from different
sources m o r e easily detected, e.g. Stow & Miller
(1984), Richter & Zinkernagel (1975). This aspect
of C L p e t r o g r a p h y has received little a t t e n t i o n , but
it could be extremely valuable in p e t r o l e u m explora
tion, giving an extra feature for use in correlation of
borehole core sequences and interpretation of their
depositional e n v i r o n m e n t s .
(5) Diagenetic and geochemical studies a r e en
hanced by t h e very fine C L resolution of growth
histories in crystals (Fig. 6.4). T a k e n t o g e t h e r with
o t h e r evidence, these geochemical variations may
indicate variations in g r o u n d w a t e r chemistry and
burial d e p t h s , greatly increasing t h e resolution of
diagenetic histories (e.g. G r o v e r & R e a d , 1983).
(6) Mechanically
induced
post-depositional
changes in sediments such as compaction, stylolitization and structural deformation can m o r e easily b e
detected and evaluated with the aid of C L .
Fig. 6.3. Drawings made from photographs of CL in limestones from the Dinantian (Lower Carboniferous) of Ireland.
(a) Coarse sparry calcite mass seen in transmitted light, (b) Same view but with cathodoluminescence, showing a void
developed in micrite (coarse stipple), with a cement sequence of radial fibrous spar (light stipple), non-luminescent ferroan
calcite (black) and brightly luminescent outer zone (white). The void fill is completed by dolomite (hashures). (c) Mediumgrained blocky spar mosaic seen under transmitted light is revealed under cathodoluminescence (d) as a neomorphosed,
brightly luminescent biomicrite with gastropods, bivalves and foraminifera which are weakly luminescent.
6.7 E X A M P L E S O F C L U S E IN
SEDIMENTOLOGY
Exhaustive discussions of t h e C L properties of
minerals are beyond the scope of this chapter, and
t h e r e a d e r is referred t o t h e reviews of Nickel (1978),
A m i e u x (1982) and W a l k e r (1985). S o m e of t h e
most i m p o r t a n t petrographic uses of C L a r e outlined
below for t h e m o r e c o m m o n sedimentary rock types.
6.7.1 Carbonate r o c k s
PRINCIPLES
C a r b o n a t e minerals give bright and stable lumine
scence at low accelerating voltages, so limestones
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ill
183
2 +
2 +
2 +
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J . MILLER
CATHODOLUMINESCENCE MICROSCOPY
Fig. 6.4. Paired photomicrographs of limestone thin sections, with transmitted light view to the left and
cathodoluminescence view to the right. All from the Dinantian (Lower Carboniferous) of South Wales, (a), (b) Pwll-yCwm Oolite. Calcite cement fill of bivalve mould, showing details of crystal growth by fine luminescent and nonluminescent growth bands, (c), (d) Blaen Onneu Oolite. Syntaxial calcite overgrowth on an echinoid spine, showing
preferential nucleation on the crystallographically suitable substrate. CL reveals detail of the internal structure of the
recrystallized spine. Changes in CL intensity in the overgrowth cement are due to varying concentrations of F e quencher,
(e), (f) Gilwern Oolite. Details of the internal structure of ooids is better revealed by CL. Thin, non-luminescent calcite
cement fringes occur on the ooids, followed by brightly-luminescent microspar associated with calcrete formed during
subaerial exposure. Photographs by courtesy of Dr M. Raven.
185
Fig. 6.5. Paired photomicrographs of sandstones from North Sea cores, transmitted light view to the left and CL view to
the right, (a), (b) Medium-grained sandstone with a carbonate cement is seen under CL to have a fairly high fossil content,
mainly echinoderms: crinoid fragments and an echinoid spine (top left) provide substrates for large, zoned overgrowths
which have occluded the primary porosity, (c), (d) Coarse sandstone with non-luminescent authigenic quartz overgrowths
on violet-luminescing quartz grains. A subsequent zoned calcite cement is being dissolved by kaolinite (white on picture,
royal blue CL). (e), (f) Violet luminescing (V) and brown (B) quartz grains showing a mixture of metamorphic and igneous
sources. A sparry calcite cement (S) is suffering dissolution by brightly-luminescing kaolinite (K).
2 +
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J . MILLER
186
CATHODOLUMINESCENCE MICROSCOPY
2 +
2 +
2 +
2 +
2 +
2 +
2 +
2 +
2 +
2 +
2 +
2 +
CEMENT STRATIGRAPHY
O n e of the c o m m o n e s t applications of C L in car
b o n a t e rocks is in revealing successive stages o r
zones of void-filling cements with far greater pre
cision than that possible with optical microscopy.
C e m e n t stratigraphy (Fig. 6.4) involves t h e applica
tion of stratigraphic principles at an inter-granular
and void level, correlating stages of cementation
within a given basin of s e d i m e n t a t i o n .
Meyers (1974, 1978) p i o n e e r e d c e m e n t strati
graphy, demonstrating that 'zones' of c a r b o n a t e
c e m e n t s , as revealed by their C L and o t h e r p e t r o
graphic characteristics, could b e correlated both
vertically and regionally in the Mississippian of the
S a c r a m e n t o M o u n t a i n s , New Mexico. G r o v e r &
R e a d (1983) performed a similar study in t h e O r d o vician of Virginia, and related the sequence to dia
genetic changes resulting from changes in formation
water composition during shallow a n d d e e p burial.
W a l k d e n & Berry (1984) correlated C L zones in
overgrowth cements from the U p p e r Dinantian of
n o r t h e r n Britain, and ascribed t h e m to cyclic re
plenishment of vadose and shallow meteoric water
tables in calcretized m a r i n e limestones.
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187
6.7.2 Sandstones
QUARTZ
T h e causes of C L in quartz a r e not yet fully deter
mined (Walker, 1985). A l p h a quartz shows visible
C L with t w o b r o a d emission b a n d s in t h e blue and
r e d ( Z i n k e r n a g e l , 1978). Various authors have attri
buted these emissions to Ti and M n respectively b u t ,
as W a l k e r (1985) pointed out, t h e spectral b a n d s are
present in highly p u r e synthetic silica, and it seems
certain that emission is intrinsic rather t h a n d u e to
impurities. C L from natural q u a r t z is characteristi
cally thermally unstable. H e a t i n g collapses the blue
spectral p e a k , causing t h e violet luminescence t o
shift t o w a r d s red. T h i s p r e s e n t s a major p r o b l e m for
observation of quartz grains u n d e r an electron b e a m :
its heating effect can quickly cause t h e fed coloura
tion to b e assumed. H i g h accelerating voltages and
current densities speed t h e change, which is per
m a n e n t . It may b e very difficult t o obtain accurate
colour p h o t o g r a p h s of q u a r t z luminescence because
t h e shift to red may occur during t h e time of
exposure.
Z i n k e r n a g e l showed t h a t natural q u a r t z grains
have a luminescence which apparently reflects their
source (or, m o r e correctly, their thermal history).
Broadly, violet C L is typical of igneous sources, but
brown grains originate in certain types of m e t a m o r
phic rocks (Fig. 6.5f). This scheme of provenance
using C L was further elaborated by M a t t e r & R a m seyer (1985). Q u a r t z overgrowths and other forms
of authigenic quartz a r e commonly non-luminescent
u n d e r n o r m a l C L conditions (Fig. 6.5d), while zoned
C L is typical of grains derived from hydrothermal veinquartz. C L is thus a very sensitive m e t h o d of deter
mining presence and timing of p o r e occlusion by
quartz authigenesis, particularly where t h e r e are n o
obvious dust-rims on grain cores.
Owing to the t h e r m a l instability described above,
with violet grains easily becoming brown while in
188
J . MILLER
HODOLUMINESCENCE MICROSCOPY
FELDSPARS
T h e causes of C L in this mineral g r o u p are relatively
well-known from investigations on lunar rocks
( G e a k e et al., 1977) and-carbonatites ( M a r i a n o , Ito
& Ring, 1973). Feldspars have low C L thresholds
and are thus obvious even at low accelerating volt
ages. Typical C L colours are brilliant blue (possibly
Ti
activation), red to infra-red ( F e
substitution
for A l ) and green ( M n substitution probably for
C a ) . Feldspar C L is polarized and s o m e intensity
variation is seen u p o n rotation of a polaroid sheet
interposed b e t w e e n t h e viewing window and t h e
microscope eyepiece. This property often helps to
distinguish feldspars from o t h e r minerals of similar
C L colour. In general, authigenic feldspars a r e nonluminescent or very dully luminescent (Kastner,
1971), serving to differentiate detrital cores from
their overgrowths.
2 +
3 +
3 +
2 +
2 +
In t e r m s of p r o v e n a n c e , t h e r e is n o evidence to
suggest that feldspar C L is related to specific igneous
or m e t a m o r p h i c origins. H o w e v e r , t h e presence of
feldspar 'suites' containing consistent p r o p o r t i o n s of
t h e rarer red and/or green emitter grains amongst
t h e c o m m o n blue emitters can be used t o trace
particular sources of clastic feldspar supply (e.g.
Stow & Miller, 1984).
Because even the smallest feldspar grains
luminesce brightly, a far m o r e accurate estimate of
t h e percentage of feldspar in a clastic sediment is
6.8 P H O T O G R A P H I C
OF CL
RECORDING
HEAVY MINERALS
M a n y accessory minerals of clastic rocks contain at
least traces of r a r e earth or transition metal impuri
ties and are therefore liable to luminesce. Nickel
(1978) listed the k n o w n C L characteristics of such
minerals. A p a t i t e s give particularly bright C L , with
e u r o p i u m a c o m m o n activator ( M a r i a n o & Ring,
1975). A p a t i t e emissions r a n g e from bluish-violet,
lilac, pink and o r a n g e to yellow. P o r t n o v & G o r o b e t s
(1969) have p r o p o s e d that certain of these colours
a r e related to particular igneous or m e t a m o r p h i c
origins. If this can b e confirmed, it would b e an
invaluable adjunct to p r o v e n a n c e studies. A g a i n ,
t h e small size of many heavy mineral grains m e a n s
that they are often overlooked and easily u n d e r
estimated in transmitted light p e t r o g r a p h y of clastic
rocks. Invariably, use of C L produces an often sur
prising re-evaluation of the i m p o r t a n c e of accessory
grains.
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189
190
J . MILLER
6.8
CONCLUSIONS
6.9 M A N U F A C T U R E R S OF
CL EQUIPMENT
Nuclide C o r p o r a t i o n , A G U Division, 916 M a i n
Street, P O B o x 315, A c t o n , M A 01720, U S A .
T E C H N O S Y N Ltd, Coldhams Road, Cambridge
CB1 3EW, England.
7
7.1
INTRODUCTION
Water cooled
7.2 T H E O R Y O F X - R A Y
DIFFRACTION
F o r a comprehensive t r e a t m e n t of theory, the r e a d e r
is referred to t h e classic text of Klug & A l e x a n d e r
(1974). Only a simplified t r e a t m e n t for the under
standing and evaluation of basic analytical proce
d u r e s is given h e r e . A very useful introduction can
be obtained from t h e Philips organization in the U K
called ' A n introduction to X-ray p o w d e r diffractom e t r y ' by R. Jenkins and J . L . de Vries. T h e address
is Pye U n i c a m L t d , Y o r k Street, C a m b r i d g e C B 1
2 P X , tel. C a m b r i d g e (0223) 358866.
5-35 mA
12 V
Fig. 7 . 1 . A section of a Rontgen X-ray tube (based on
Phillips & Phillips, 1980).
191
http://jurassic.ru/
192
a
Koci
5000
K a ,
Continuous
spectrum
Characteristic line
spectrum from
copper
-2500
0.5
1.0
1.5
2.0
Wavelength \(A)
2.5
Tadiation
193
Cr
Fe
Co
Cu
Mo
2.291
1.937
1.791
1.542
0.710
2.085
1.757
1.621
1.392
0.632
V
Mn
Fe
Ni
Zr
2.269
1.897
1.744
1.488
0.688
16
16
18
21
108
0.5
5000
1.0
1.5
2.0
Wavelength \(A)
Ka2
o 2500
K a b s o r p t i o n e d g e (1.49A)
Ka-]
Q. C
Transmission
Transmission
M shell
X-ray
-A,
0.5
Absorption
1.0
2.0
1.0
1.5 _ 2.0
Wavelength (A)
2.5
W a v e l e n g t h (A)
Electrons
Fig. 7.3. The generation of X-rays of the line spectrum of copper due to the transfer of electrons into the K shell and the
generation of the continuous spectrum due to complete or partial electron collisions (from Phillips & Phillips, 1980).
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194
X-ray source
Monochromator
crystal
Specimen
w h e r e n is an interger, X is the wavelength of the Xrays, d is the lattice spacing in angstroms and 0 is the
angle of diffraction (Fig. 7.9). T h e diffracted b e a m
is passed through a receiving slit and collimator a n d ,
then a scatter slit is introduced to reduce any scat
tered X-rays o t h e r than the diffracted b e a m s from
finally entering t h e detector. In the case of a m o n o
c h r o m a t o r being used (Fig. 7.7), the b e a m passes
straight from t h e receiving slit to the crystal m o n o
c h r o m a t o r and then t o the detector. T h e signal
produced by the X-ray p h o t o n s on the detector is
first amplified, and then passed on to the electronic
recording e q u i p m e n t .
Scatter slit
Receiving parallel
slit assembly
Counter tube
Scatter slit
Receiving parallel Uf.
slit assembly
1
I
Divergence
slit
Specimen
Receiving slit
Focusing circle-
7.3 X R D A N A L Y S I S O F S E D I M E N T S
X R D is particularly useful in the analysis of fine
grained material which is difficult to study by other
m e a n s , but t h e r e are a whole range of applications
to the various c o m p o n e n t s of sediments, as defined
by either size and/or mineralogy.
Fig. 7 . 8 . Schematic representation of
the geometry of a typical
diffractometer (from Philips UK
Goniometer Manual).
http://jurassic.ru/
Mllilll
195
2d
d sin 8 + d sin 6 =
sin 9 = A.
For diffraction to occur A must equal a whole number of
wavelengths: 2d sin 9 = rik (Bragg's Law).
196
<O
C
O
Ci\
C
M
oO
<D
05
ro
iii i.. .
40
i
oo
C
O
<
00
c\i
C
D
IS)
JL
Background X-rays
45
o
oo
^r oo
50
<
C
D
<>
t C
N
J
35
30
25
20
26
Fig. 7.10. A strip chart of diffractometer trace of the X-ray diffraction pattern of the mineral calcite. The 29 angle increases
from right to left on the horizontal scale and the intensity of the diffracted peak above background is given by the vertical
scale. The X-ray tube target was copper.
Wth
i monochromator
Cu radiation 40 kV/25 mA
1 divergence slit
0.2 mm receiving slit
4 scatter slit
j
Scanning speed 126 m i n
Full scale 2.000 cps
Pulse height analyser
Proportional counter
- 1
U
High background due to FeKa fluorescence
Wtihout monochromator
Cu radiation 40 kV/25 mA
1 divergence slit
0.2 mm receiving slit
1 scatter slit
Fig. 7.12. A comparison of diffractometers with and without a curved crystal monochromator on the mineral haematite
using copper radiation (from Philips UK Information Sheet).
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197
198
X-RAY POWDER D I F F R A C T I O N
Table 7.2. (a) Conversion charts of 29 to angstroms (D-spacing) for copper Ka radiation (Computed by M.J. Smith,
University of Durham)
CuKaIpha
0
2
3
4
5
6
7
8
9
18
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
I ambda = 1 .5418A
4 4 . 172 4 2 . 0 6 8 4 0 . 156
2 9 . 450 2 8 . 500 2 7 . 609
2 2 . 089 21 . 551 21 . 038
17. 673 17. 327 16. 994
1 4 . 730 1 4 . 489 14. 255
12. 628 1 2 . 450 12. 277
11 . 051 1 0 . 915 10. 782
9. 826 9 . 718 9 . 612
8 . 845 8 . 758 8 . 672
8 . 0 4 3 7 . 971 7. 900
7 375 7 314 7 255
6 8 1 0 6 758 6 707
6 326 6 281 6 237
5 906 5 867 5 829
5 539 5 505 5 471
5 216 5 185 5 155
4 928 4 901 4 874
4 647 4 623
4 671
4 439 4 418 4 396
4 230 4 210 4 191
4 040 4 022 4 004
3 867 3 850 3 834
3 708 3 6 9 3 3 678
3 562 3 548 3 534
3 427 3 414 3 401
3 302 3 290 3 278
3 187 3 175 3 164
3 079 3 069 3 058
2 979 2 969 2 959
2 885 2 876 2 867
2 .797 2 . 7 8 8 2 780
2 . 7 1 4 2 . 7 0 6 2 698
2 .637 2 . 6 2 9 2 622
2 .564 2 .557 2 .550
2 . 4 9 5 2 . 4 8 8 2 .481
2 . 4 3 0 2 . 4 2 3 2 .417
2 . 3 6 8 2 . 3 6 2 2 .356
2 . 3 0 9 2 . 3 0 4 2 .298
2 . 2 5 4 2 . 2 4 9 2 .243
2 .201
2 . 1 9 6 2 .191
2 . 151 2 . 1 4 6 2 . 141
2 . 1 0 3 2 .099 2 . 0 9 4
2 . 0 5 8 2 . 0 5 3 2 .049
2 .014 2 .010 2 .006
1 .965
1 .973
1 .969
1 .926
1 .929
1 .933
1 .888
1 .892
1 .895
1 .852
1 .859
1 .855
1 .817
1 .824
1 .821
1 .791
1 .787 1 .784
2. 0
3 8 . 411
26. 773
20 549
16 674
14 029
12 109
10 6 5 3
9 509
8 588
7 830
7 196
6 657
6 194
5 791
5 438
5 126
4 848
4 599
4 375
4 171
3 986
3 818
3 663
3 520
3 389
3 267
3 153
3 048
2 950
2 858
2 771
2 691
2 614
2 .543
2 .475
2 .411
2 .350
2 .292
2 .238
2 . 186
2 .137
2 .090
2 .045
2 .002
1 .961
1 .922
1 .884
1 .848
1 .814
1 .781
3 6 . 810
2 5 . 986
20 082
16. 3 6 5
13 8 1 0
11 946
10 526
9 408
8 506
7 762
7 138
6 607
6 151
5 754
5 405
5 096
4 822
4 575
4 353
4 152
3 969
3 802
3 648
3 507
3 376
3 255
3 143
3 038
2 940
2 849
2 763
2 683
2 607
2 536
2 468
2 404
2 344
2 287
2 .233
2 .181
2 .132
2 .085
2 .040
1 .998
1 .957
1 .918
1 .881
1 .845
1 .811
1 .778
35 338
2 5 . 244
19 636
16 068
13 598
11 787
10 402
9 309
8 425
7 695
7 081
6 559
6 109
5 717
5 372
5 068
4 796
4 552
4 332
4 133
3 952
3 786
3 633
3 493
3 363
3 243
3 132
3 028
2 931
2 840
2 755
2 675
2 600
2 529
2 462
2 398
2 338
2 281
2 .227
2 176
2 . 127
2 .080
2 .036
1 .993
1 .953
1 .914
1 .877
1 .841
1 .807
1 .774
of
2THETA
979
543
209
781
392
632
282
213
346
628
025
511
067
680
340
039
770
529
311
114
3 934
3 770
3 619
3 480
3 351
3 232
3 121
3 018
2 921
2 831
2 747
2 667
2 592
2 522
2 455
2 392
2 332
2 276
2 222
2 171
2 .122
2 .076
2 032
1 .989
1 .949
1 910
1 .873
1 .838
1 .804
1 .771
32 721
23 879
18 801
15 504
13 192
11 481
10 164
9 118
8 268
7 563
6 970
6 463
6 026
5 644
5 309
5 011
4 745
4 506
4 291
4 095
3 917
3 754
3 604
3 466
3 339
3 220
3 110
3 008
2 912
2 823
2 739
2 659
2 585
2 515
2 449
2 386
2 327
2 270
2 217
2 166
2 117
2 071
2 027
1 985
1 945
1 907
1 870
1 834
1 .801
1 .768
33
24
19
15
13
11
10
9
8
7
7
6
6
5
5
5
4
4
4
4
to
8
31
23
18
15
12
11
10
9
8
7
6
6
5
5
5
4
4
4
4
4
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
553
251
409
237
999
334
048
025
192
500
916
417
985
609
277
983
720
484
270
077
900
739
590
453
326
209
100
998
903
814
730
652
578
508
442
380
321
265
212
161
113
067
023
981
941
903
866
831
797
765
CuKaIpha
51 . 9
, lambda = 1.5418A
.1
9
30
22
18
14
12
11
9
8
8
7
6
6
5
5
5
4
4
4
4
4
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
1
1
1
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
465
655
034
979
810
191
936
934
117
437
862
371
946
574
246
955
695
462
250
058
883
723
576
440
314
198
089
988
894
805
722
644
571
501
436
374
315
259
206
156
108
062
019
977
937
899
863
828
794
762
1 .759
1.728
1 .698
1 .670
1.642
1 .616
1 .590
1 .566
1 .542
1 .519
1 .497
1 .475
1 .455
1 .435
1 .415
1 .397
1 .379
1 .361
1 .344
1 .328
1 .312
1 .296
1 .281
1 .266
1 .252
1 .238
1 .225
1 .212
1 .199
1 . 187
1 .175
1 . 163
1 . 152
1 .141
1 .130
1 .120
1.110
1 . 100
1 . 090
1 .081
1 .072
1 .063
1 .054
1 .046
1 .037
1 .029
1 .021
1 .014
1 .006
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
.755
.725
.695
.667
.639
.613
.588
.563
.539
.517
.495
.473
.453
.433
.414
.395
.377
.359
.342
.326
.310
.294
.279
.265
.251
.237
.224
.211
.198
.186
.174
1 . 162
151
140
129
1.119
1 .109
1 .099
1 .089
1 .080
1 .071
1 .062
1 .053
1 .045
1 .037
1 .029
1 .021
1 .013
http://jurassic.ru/
i l l l
52.0
.2
1 .752
1 .722
1 .692
1 .664
1 .637
1 .610
1.585
1 .561
1.537
1 .514
1 .492
1 .471
1 .451
1 .431
1 .412
1 .393
1 .375
1 .358
1 .341
1 .324
1 .308
1 .293
1 .278
1 .263
1 .249
1 .236
1 .222
1 .209
1 .197
1 . 185
1 .173
1.161
1 . 150
1 . 139
1 . 128
1 .118
1 . 108
1 .098
1 .088
1 .079
1 .070
1 .061
1 .052
1 .044
1.036
1 .028
1.020
1-.012
of
2THETA
to
.6
1 .749
1 .719
1 .689
1 .661
1 .634
1 .608
1 .583
1 .558
1 .535
1 .512
1 .490
1 .469
1 .449
1 .429
1 .410
1 .391
1 .373
1 .356
1 .339
1 .323
1 .307
1 .291
1 .277
1 .262
1 .248
1 .234
1 .221
1 .208
1 .196
1 .183
1 .172
1 . 160
1 . 149
1 . 138
1 . 127
1.117
1 . 107
1 .097
1 .087
1 .078
1 .069
1 .060
1 .052
1 .043
1 .035
1 .027
1 .019
1 .012
1 .746
1 .716
1 .687
1 .658
1 .631
1 .605
1 .580
1 .556
1 .533
1 .510
1 .488
1 .467
1 .447
1 .427
1 .408
1 .389
1 .372
1 .354
1 .337
1 .321
1 .305
1 .290
1 .275
1 .261
1 .247
1 .233
1 .220
1 .207
1 .194
1 . 182
1 .170
1 .159
1 .148
137
126
116
106
1 .096
1 .086
1 .077
1 .068
1 .059
1 .051
1 .042
1 .034
1 .026
1 .018
1 .011
1 .743
1 .713
1 .684
1 .656
1 .629
1 .603
1 .578
1 .554
1 .530
1 .508
1 .486
1 .465
1 .445
1 .425
1 .406
1 .388
1 .370
1 .352
1 .336
1 .319
1 .304
1 .288
1 .274
1 .259
1 .245
1 .232
1 .218
1 .206
1 . 193
1 .181
1 .169
1 .158
1 . 147
1 . 136
1 .125
1.115
1 . 105
1 .095
1 .085
1 .076
1 .067
1 .058
1 .050
1 .041
1 .033
1 .025
1.018.
1 .010
1 .740
1 .710
1 .681
1 .653
1 .626
1 .600
1 .575
1 .551
1 .528
1 .506
1 .484
1 .463
1 .443
1 .423
1 .404
1 .386
1 .368
1 .351
1 .334
1 .318
1 .302
1 .287
1 .272
1 .258
1 .244
1 .230
1 .217
1 .284
1 .192
1 .180
1 .168
1 .157
145
135
124
114
1 .104
1 .094
1 .085
1 .075
1 .066
1 .058
1 .049
1 .041
1 .032
1 .025
1 .017
1 .009
100.0
.9
1 .737
1 .707
1 .678
1 .650
1 .623
1 .598
1 .573
1 .549
1 .526
1 .503
1 .482
1 .461
1 .441
1 .421
1 .402
1 .384
1 .366
1 .349
1 .332
1 .316
1 .301
1 .285
1 .271
1 .256
1 .242
1 .229
1.216
1 .203
1 . 191
1 .179
1 .167
1 . 155
1 .144
1 . 134
1 .123
1.113
1 .103
1 .093
1 .084
1 .074
1 .065
1 .057
1 .048
1 .040
1 .032
1 .024
1 .016
1 .009
1 .734
1 .704
1 .675
1 .647
1 .621
1 .595
1 .570
1 .546
1 .523
1 .501
1 .480
1 .459
1 .439
1 .419
1 .400
1 .382
1 .365
1 .347
1 .331
1 .315
1 .299
1 .284
1 .269
1 .255
1 .241
1 .228
1 .215
1 .202
1 . 189
1 .177
1 .166
1 .154
1 .143
1 . 132
1 . 122
1.112
1 . 102
1 .092
1 .083
1 .073
1 .065
1 . 056
1 .047
1 .039
1 .031
1 .023
1 .015
1 .008
1 .731
1 .701
1 .672
1 .645
1 .618
1 .593
1 .568
1 .544
1 .521
1 .499
1 .478
1 .457
1 .437
1 .417
1 .399
1 .380
1 .363
1 .346
1 .329
1 .313
1 .298
1 .282
1 .268
1 .254
1 .240
1 .226
1 .213
1 .201
1 . 188
1 . 176
1 .165
1 .153
1 .142
1 . 131
1 .121
1.111
1 . 101
1 .091
1 .082
1 .073
1 .064
1 .055
1 .046
1 .038
1 .030
1 .022
1 .015
1 .007
199
200
X-RAY POWDER D I F F R A C T I O N
2.0
5
4
42 741
30 172
23 317
19 002
16 035
13 871
12 222
10 924
9 876
9 012
8 288
7 672
7 142
6 681
6 276
5 918
5 599
5 313
5 055
4 821
4 608
4 414
4 236
4 071
3 920
3 779
3 649
3 527
3 414
3 308
3 208
3 115
3 027
2 944
2 866
2 792
2 722
2 655
2 592
2 532
2 475
2 421
2 369
2 319
2 272
2 227
2 .184
2 .142
2 .102
2 064
41
29
22
18
15
13
12
10
9
8
8
7
7
6
6
5
5
5
5
4
4
4
4
4
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
032
311
799
656
789
686
078
809
782
934
222
615
093
638
238
884
569
286
030
799
588
395
219
056
905
766
636
516
403
298
199
106
018
936
858
785
715
649
586
526
470
416
364
315
268
222
179
138
098
060
of
6
39
28
22
18
15
13
11
10
9
8
8
7
7
6
6
5
5
5
5
4
4
4
4
4
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
454
497
304
324
550
506
938
697
690
857
157
560
044
595
201
851
539
259
006
777
568
377
202
040
891
753
624
504
392
287
189
097
010
928
851
778
708
642
580
521
464
410
359
310
263
218
175
134
094
057
2THETA
7
37
27
21
18
15
13
11
10
9
8
8
7
6
6
6
5
5
5
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
993
727
830
002
318
331
801
587
600
782
093
505
997
554
164
818
509
232
982
755
548
359
185
025
877
739
612
493
381
277
180
088
002
920
843
770
701
636
574
515
459
405
354
305
258
214
171
130
091
053
to
8
36
26
21
17
15
13
11
10
9
8
8
7
6
6
6
5
5
5
4
4
4
4
4
4
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
636
997
375
692
093
160
667
479
511
708
030
451
950
512
127
786
480
206
958
734
529
341
168
009
862
726
599
481
371
267
170
079
993
912
836
763
695
630
568
509
453
400
349
300
254
209
167
126
087
049
CoKalpha
51.9
35
26
20
17
14
12
11
10
9
8
7
7
6
6
6
5
5
5
4
4
4
4
4
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
373
305
939
393
874
994
536
374
424
635
968
397
903
472
091
754
452
180
935
712
509
323
152
994
848
713
587
470
360
257
161
070
985
904
828
756
688
623
562
503
448
395
344
296
249
205
163
122
083
046
http://jurassic.ru/
i
, Iambda = 1.7902A
2 042
2 006
1 972
1 939
1 907
1 876
1 846
1 818
1 790
1 764
1 738
1 713
1 689
1 666
1 643
1 622
1 601
1 580
1 561
1 541
1 523
1 505
1 487
1 470
1 454
1 438
1 422
1 407
1 393
1 378
1 364
1 351
1 338
1 325
1 312
1 300
1 289
1 277
1 266
1 255
1 244
1 234
1 224
1 214
1 204
1 .195
1 .186
1 177
1.168
2 038
003
1 968
1 935
1 903
1 873
1 843
1 815
1 788
1 761
1 735
1 711
1 687
1 664
1 641
1 620
1 599
1 578
1 559
1 540
1 521
1 503
1 486
1 469
1 452
1 436
1 421
1 406
1 391
1 377
1 363
1 350
1 336
1 324
1 311
1 299
1 287
1 276
1 265
1 254
1 243
1. 233
1 223
1 213
1 204
.1 . 1 9 4
t .185
1 .'176
CM
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
, lambda = 1.7902A
.2
2.035
1 .999
1 .965
1 .932
1 .900
1 .870
1 .840
1 .812
1 .785
1 .758
1 .733
1 .708
1 .684
1 .661
1 .639
1 .617
1 .597
1 .576
1 .557
1 .538
1 .519
1 .501
1 .484
1 .467
1 .451
1 .435
1 .419
1 .404
1 .390
1 .375
1 .362
1 .348
1 .335
1 .322
1 .310
1 .298
1 .286
1 .275
1 .264
1 .253
1 .242
1 .232
1 .222
1.212
1 .203
1 . 193
1,184
1 .175
52.0
of
2THETA
.4
.5
.6
.7
2 031
1 .996
1 962
1 929
1 897
1 867
1 838
1 809
1 782
1 756
1 730
1 706
1 682
1 659
1 637
1 615
1 595
1 574
1 555
1 536
1 517
1 500
1 482
1 465
1 449
1 433
1 418
1 403
1 388
1 374
1 360
1 347
1 334
1 321
1 309
1 297
1 285
1 274
1 263
1 252
1 241
1 231
1 221
1 211
1 202
1 192
1 183
1 175
2 027
1 .992
1 .958
1 .926
1 894
1 864
1 835
1 .807
1 .779
1 753
1 728
1 703
1 680
1 657
1 635
1 613
1 592
1 572
1 553
1 534
1 516
1 498
1 480
1 464
1 447
1 432
1 416
1 401
1 387
1 373
1 359
1 346
1 333
1 320
1 308
1 296
1 284
1 273
1 261
1 251
1 240
1 230
1 220
1 210
1 201
1 191
1 182
1 174
2 .024
1 .989
1 .955
1 .922
1 .891
1 .861
1 .832
1 .804
1 .777
1 .751
1 .725
1 .701
1 .677
1 .655
1 .633
1 611
1 590
1 570
1 551
1 532
1 514
1 496
1 479
1 462
1 446
1 430
1 415
1 400
1 385
1 371
1 358
1 344
1 331
1 319
1 306
1 294
1 283
1 271
1 260
1 250
1 239
1 229
1 219
1 209
1 200
1 191
1 182
1 173
2 .020
1 .985
1 .952
1 .919
1 .888
1 .858
1 .829
1 .801
1 .774
1 .748
1 .723
1 699
1 675
1 .652
1 630
1 609
1 588
1 568
1 549
1 530
1 512
1 494
1 477
1 460
1 444
1 428
1 413
1 398
1 384
1 370
1 356
1 343
1 330
1 317
1 305
1 293
1 282
1 270
1 259
1 249
1 238
1 228
1 218
1 208
1 199
1 190
1 181
1 172
2 .017
1 .982
1 .948
1 .916
1 .885
1 .855
1 .826
1 .798
1 .771
1 .746
1 .720
1 .696
1 .673
1 .650
1 .628
1 .607
1 .586
1 .566
1 .547
1 528
1 510
1 493
1 475
1 459
1 443
1 427
1 412
1 397
1 382
1 368
1 355
1 342
1 329
1 316
1 304
1 292
1 280
1 269
1 258
1 247
1 237
1 227
1 217
1 207
1 198
1 189
1 180
1 171
to
.8
100.
.9
2 .013 2 .010
1 .978 1 .975
1 .945 1 .942
1 .913 1 .910
1 .882 1 .879
1 .852 1 .849
1 . 8 2 3 1 .821
1 .796 1 .793
1 .769 1 .766
1 .743 1 .740
1 .718 1 .716
1 . 6 9 4 1 .691
1 .671
1 .668
1 .648 1 .646
1 .626 1 .624
1 .605 1 .603
1 .584 1 .582
1 .564 1 .563
1 .545 1 .543
1 .527 1 .525
1 508 1 507
1 491
1 489
1 474 1 472
1 457 1 456
1 441
1 439
1 425 1 424
1 410
1 409
1 395 1 394
1
381 1 380
1 367 1 366
1 354
1 352
1 340 1 339
1 327 1 326
1 315 1 314
1 303 1 302
1 291
1 290
1 279 1 278
1 268
1 267
1 257 1 256
1 246
1 245
1 236 1 235
1
226 1 225
1 216 1 215
1 206
1 .205
1 . 197 1 .196
1 188 1 .187
1 .179 1 .178
1 .170 1 .169
201
202
X-RAY POWDER D I F F R A C T I O N
203
57. 073
3 9 . 781
3 0 . 533
24. 775
20 845
17 9 9 3
15 828
14 129
12 761
11 635
10 692
9 891
9 203
8 605
8 088
7 616
7 283
6 833
6 500
6 198
5 923
5 672
5 442
5 230
5 035
4 854
4 686
4 529
4 383
4 246
4 118
3 998
3 885
3 778
3 677
3 582
3 492
3 406
3 .325
3 .248
3 .175
3 .105
3 .038
2 .974
2 .914
2 .855
2 .800
2 .746
2 .695
2 .646
5 4 . 695
3 8 . 611
2 9 . 839
2 4 . 316
20 520
17 750
15 640
13 979
12 638
11 5 3 3
10 606
9 818
9 139
8 549
8 031
7 573
7 164
6 798
6 468
6 169
5 897
5 649
5 420
5 210
5 016
4 836
4 669
4 514
4 369
4 233
4 106
3 986
3 874
3 768
3 667
3 573
3 483
3 398
3 317
3 241
3 168
3 098
3 .032
2 .968
2 .908
2 .850
2 .794
2 .741
2 .690
2 .641
5 2 . 508
3 7 . 508
2 9 . 176
23 874
20 205
17 514
1 5 . 456
13 8 3 3
12 518
11 433
10 522
9 745
9 077
8 494
7 983
7 530
7 126
6 764
6 437
6 141
5 871
5 625
5 399
5 190
4 998
4 819
4 653
4 499
4 355
4 220
4 093
3 975
3 863
3 757
3 658
3 564
3 474
3 390
3 309
3 233
3 160
3 091
3 025
2 962
2 902
2 .844
2 .789
2 .736
2 .685
2 .637
5 0 489
36 467
28 542
23 448
19 899
17 284
15 277
13 689
12 401
11 335
10 438
9 674
9 015
8 440
7 935
7 487
7 088
6 730
6 406
6 113
5 846
5 601
5 377
5 170
4 979
4 802
4 637
4 484
4 341
4 207
4 081
3 963
3 852
3 747
3 648
3 554
3 466
3 382
3 302
3 226
3 153
3 084
3 019
2 956
2 896
2 .838
2 .784
2 .731
2 .680
2 .632
2THETA
7
48
35
27
23
19
17
15
13
12
11
10
9
8
8
7
7
7
6
6
6
5
5
5
5
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
619
482
935
037
602
059
102
548
285
238
357
604
954
387
888
445
050
696
376
085
820
578
356
150
961
785
622
469
327
194
069
952
841
737
638
545
457
373
294
218
146
078
012
958
890
833
778
726
675
627
51 . 9
to
883
548
354
641
314
841
930
418
172
143
276
535
894
334
841
484
813
662
345
058
795
555
334
131
943
768
606
455
313
181
057
940
830
727
629
536
448
365
286
211
139
071
086
944
884
827
773
721
670
622
45
33
26
22
19
16
14
13
12
11
10
9
8
8
7
7
6
6
6
6
5
5
5
5
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
, lambda = 2.2909A
8
46
34
27
22
19
16
14
13
12
11
10
9
8
8
7
7
7
6
6
6
5
5
5
5
4
4
4
4
4
4
4
3
3
3
3
3
3
3
3
3
3
3
3
2
2
2
2
2
2
2
CrKalpha
52
53
54
55
56
57
58
59
68
61
62
63
64
65
66
67
68
69
78
71
72
73
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
98
91
92
93
94
95
96
97
98
99
100
267
663
796
257
035
628
763
275
860
050
197
466
834
282
795
363
977
629
315
030
770
532
313
111
925
751
590
440
300
168
045
929
820
717
619
527
440
357
278
204
132
064
000
938
878
822
767
715
666
618
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1
613
567
523
481
440
401
363
326
291
257
224
192
162
132
103
075
048
022
997
973
949
926
903
882
1 861
1 840
820
1 801
1 782
1 764
1 746
1 729
712
1 695
1 680
664
1 649
1 634
1 620
1 606
1 592
579
1 566
1 554
541
1 529
1 518
1 506
1.494
11
1
1
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
608
563
519
477
436
397
359
323
287
254
221
189
159
129
108
073
046
020
995
970
1 946
923
1 901
1 879
1 858
838
1 818
1 799
1 780
1 762
1 744
1 727
710
694
1 678
1 663
1 647
633
1 618
1 605
1 591
1 578
1 565
1 552
548
528
51 /
505 .
1
1
1
52.0
2THETA
.3
.4
.5
.6
.7
604
558
514
472
432
393
355
319
284
250
218
186
156
126
098
070
043
017
992
968
944
921
1 899
1 877
1 856
1 836
1 816
1 797
1 778
1 760
1 742
725
1 709
1 692
676
1 661
646
1 631
1 617
603
1 598
1 577
564
1 551
1 539
527
1. 515
584 .
2 .599
2 .554
2 518
2 .468
2 428
2 389
2 352
2 315
2 281
2 247
2 214
2 183
2 153
2 123
2 895
2 067
2 840
2 015
1 990
1 965
1 942
1 919
1 897
1 875
1 854
1 834
1 814
1 795
1 776
1 758
1 741
1 724
1 707
1 691
1 675
1 659
1 644
1 630
1 616
1 602
1 588
1 575
1 562
1 550
1 538
1 526
1 514
1 503
2 .594
2 .549
2 .506
2 .464
2 .424
2 .385
2 348
2 .312
2 277
2 244
2 .211
2 180
2 150
2 120
2 092
2 064
2 038
2 012
1 987
1 963
1 939
1 917
1 895
1 873
1 852
1 832
1 812
1 793
1 775
1 757
1 739
1 722
1 705
1 689
1 673
1 658
1 643
1 628
1 614
1 608
1 587
1 574
1 561
1 .549
1 .537
1 .525
1 .513
1 .582
2 .598
2 .545
2 .502
.460
2 .420
.381
2 .344
2 .308
2 .274
2 .240
2 .208
2 .177
2 .147
2 .117
2 .089
2 062
2 835
2 010
1 985
961
1 937
1 914
1 892
1 871
1 850
830
810
791
773
1 755
1 737
720
1 704
687
1 672
656
642
627
613
599
586
573
560
1 547
.
1 .535
1 524
.
1 .512
501
2.585
2.540
2.497
2.456
2.416
2.378
2.341
2.305
2.270
2.237
2.205
2 . 174
2 . 144
2.115
2.086
2.059
2.033
2.007
1 .982
1 .958
1 .935
1 .912
1 .890
1 .869
1 .848
1 .828
1 .808
1 .789
1 .771
1 .753
1 .736
1 .719
1 .702
1 .686
1 .670
1 .655
1 .640
1 .626
1 .611
1 .598
1 .584
1 .571
1 .559
1 .546
1 .534
1 .522
1 .511
1 .500
2.581
2.536
2.493
2.452
2.412
2.374
2.337
2.301
2.267
2.234
2.202
2 . 171
2.141
2.112
2.084
2.056
2.030
2.005
1 .980
1 .956
1 .933
1 .910
1 .888
1 .867
1 .846
1 .826
1 .807
1 .788
1 .769
1 .751
1 .734
1 .717
1 .700
1 .684
1 .669
1 .653
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
1
1
1
1 1 1
1 1
1
1 1
1
1
1
1 11 1
1
1 1
CM
6 5 . 6 3 3 6 2 . 508 5 9 . 667
4 3 . 7 5 8 4 2 . 347 41 . 0 2 4
3 2 . 821 3 2 . 021 31 . 259
2 6 . 2 6 0 2 5 . 746 2 5 . 251
21 . 887 21 . 528 21 . 181
1 8 . 7 6 3 18. 499 18. 242
1 6 . 421 16. 218 16. 021
1 4 . 599 14. 439 14. 2 8 3
1 3 . 143 1 3 . 0 1 3 12. 8 8 6
11 . 951 11 . 844 11 . 738
1 0 . 9 5 8 18. 868 10 7 7 9
1 0 . 119 10. 042 9 966
9 . 399 9 . 333 9 267
8 . 776 8 . 718 8 661
8 230 8 180 8 129
7 750 7 705 7 660
7 322 7 282 7 242
6 9 4 0 6 904 6 868
6 596 6 564 6 532
6 286 6 256 6 227
6 8 8 3 5 976 5 950
5 7.45 5 721 5 697
5 589 5 487 5 464
5 292 5 271 5 251
5 892 5 073 5 054
4 987 4 889 4 871
4 735 4 718 4 702
4 575 4 559 4 544
4 426 4 411 4 397
4 286 4 273 4 259
4 156 4 143 4 131
4 8 3 3 4 021 4 009
3 918 3 907 3 896
3 809 3 799 3 788
3 .707 3 .697 3 687
3 . 6 1 0 3 .601 3 591
3 . 5 1 8 3 .509 3 501
3 . 4 2 3 3 415
3 .431
3 . 3 4 9 3 .341 3 . 3 3 3
3 .263 3 .256
3 .271
3 . 1 9 6 3 . 189 3 . 1 8 2
3 . 1 2 5 3 .118 3 . 1 1 2
3 . 0 5 8 3 .051 3 . 0 4 5
2 . 9 9 3 2 .987 2 .981
2 .932 2 .926 2 .928
2 . 8 7 3 2 .867 2 .861
2 . 8 1 6 2 .811 2 . 8 0 5
2 . 7 6 2 2 .757 2 . 7 5 2
2 . 7 1 0 2 .705 2 . 7 0 0
2 .656 2 .651
2 .661
of
CM
2
3
4
5
6
7
8
9
18
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
2 0
I ambda = 2 .2909A
111
1
1
1
111
111 .
11 .
1.
1
1
1
1
1
1
.8
2.576
2.532
2.489
2.448
2.408
2.370
2.333
2.298
2.264
2.230
2.199
2.168
2.138
2.109
2.081
2.054
2.027
2.002
1 .977
1 .953
1 .930
1 .908
1 .886
1 .865
1 .844
1 .824
1 .805
1 .786
1 .767
1 .749
1 .732
1 .715
1 .699
1 .683
1 .667
1 .652
1 .637
. 6.2643 91 . 6 2 3
1 .609
. 5.9661 01 . 5 9 5
. 5 8 3 1 .582
1 .569
. 5.5577 01 . 5 5 6
1 .544
. 5.3534 51 .532
.521 1 . 5 2 0
1 .509
. 4 9 9 1 .497
1
1
1
1
.510
1
to
1
.9
2.572
2.527
2.485
2.444
2.404
2.366
2.330
2.294
2.260
2.227
2.195
2 . 165
2 . 135
2.106
2.078
2.051
2.025
2.000
1 .975
1 .951
1 .928
1 .906
1 .884
1 .863
1 .842
1 .822
1 .803
1 .784
1 .766
1 .748
1 .730
1 .714
1 .697
1 .681
1 .666
1 .650
1 .636
1 .621
1 .607
1 .594
1 .580
1 .567
1 .555
1 .543
1 .531
1 .519
1.507
1 .496
http://jurassic.ru/
.III
lUUUliUlllllllliI.
illllll
204
(a)
Measure mid-point
at i height
.26
(b)
26
20,
(c)
http://jurassic.ru/
llliil
W,
T),7,p
K;
(1)
where
(2)
If all c o m p o n e n t s are t a k e n into account, e q u a t i o n
(2) b e c o m e s 1LW = u ^ E F L I i = 1 the sum of all
t h e weight fractions.
t
Rearranging: ^
e q u a t i o n (2)
w. =
HiIi
(3)
^ M I N ^ M I N M T H
(unknown component)
^QUARTZ
^QUARTZ ^QUARTZ Mm
(reference c o m p o n e n t ) .
206
Table 7.3. Dominant X-ray diffraction peaks of selected minerals likely to occur in sediments in order of decreasing
intensities (I/h) including 26 angles for Cu and Co Ka radiations. Minerals are listed in order of decreasing d (A) value of
the most intense line (from JCPDS, 1974).
RECTORITE
Regular interstratified
mica - montmorillonite
d(k)
Ilh
hkl
24.7
100
001
12.4
50
002
3.10
18
008
4.94
8
005
1.902
4
0013
Table 7.3.
(Continued)
CHLORITE
d(k)
Penninite
Hh
hkl
7.19
100
002
4.80
100
003
3.60
100
004
14.3
60
001
2.88
60
005
2.56
40
132
20
26 o
12.31
14.30
18.48
21.49
24.73
28.79
6.18
7.18
31.05
36.21
35.05
40.93
3.54
2
007
C u
26
C u
26
c
SMECTITE
d(k)
Saponite
Vh
hkl
3.58
4.15
15.7
100
001
7.13
8.28
4.58
100
020
28.79
33.56
2.56
100
200
17.95
20.88
1.53
100
060
47.82
56.15
3.63
60
004
25.16
29.30
KAOLINITE
d(k)
2.95
60
005
Hh
hkl
7.17
100
001
26
26
12.34
14.34
62.36
73.90
7.07
100
002
14.1
90
001
12.52
14.55
6.27
7.28
25.15
29.28
Hh
hkl
6.26
100
020
3.29
90
120
2.47
80
031
26
26
14.15
16.44
27.10
31.57
36.37
42.49
46.90
55.05
52.86
62.24
4.53
100
020
15.0
90
002
4.97
75
006
30.0
60
001
2.54
50
19.60
22.79
5.89
6.84
17.85
20.75
2.94
3.42
34.34
41.27
Hh
hkl
4.18
100
110
2.69
30
130
26
26
21.25
24.73
33.31
38.87
C o
20
26
SMECTITE
Montmorillonite
C u
C o
d(k)
Hh
hkl
26
26
VERMICULITE
C u
C o
d(A)
I'h
hkl
5.63
6.54
15.0
100
001
5.89
6.84
14.2
100
002
19.38
22.54
4.50
80
020
19.73
22.95
1.528
70
060
35.05
40.93
5.01
60
003
17.70
20.58
4.57
60
020
60.51
71.61
3.02
60
005
29.58
34.48
2.615
50
200
24.52
28.55
1.50
50
060
61.85
73.27
2.570
50
132
30.30
35.33
CHLORITE
d(k)
Thuringite
Hh
hkl
1.493
50
62.17
73.67
LEPIDOCROCITE
2e
Cu
26
C o
d(k)
2.525
45
202
CORRENSITE
Regular interstratified
chloritemontmorillonite
26
C u
26
C u
d(k)
Hh
hkl
26
26
ILLITE
Cu
Co
d (A)
Hh
hkl
6.22
7.23
14.0
100
002
6.31
7.33
10.0
100
002
60.60
71.72
7.08
60
004
12.50
14.53
4.48
90
020
19.42
22.59
3.53
60
008
25.23
29.38
3.33
90
006
34.29
40.03
29.0
30
001
3.05
3.54
2.61
60
200
34.91
40.76
4.72
30
006
18.80
21.86
1.53
60
060
35.55
41.53
Regular interstratified
montmorillonite - chlorite
d(k)
Hh
hkl
4.62
30
020
19.21
22.34
26
26
GOETHITE
C u
C o
d(k)
2.42
40
133
C o
29cu
26 o
8.84
10.27
d(A)
9.97
100
003
MUSCOVITE
Hh
hkl
26
C u
2e
GYPSUM
Co
d (A)
8.87
10.30
7.56
100
020
26
26
11.70
13.60
C u
3.331
100
009
26.76
31.18
26.77
31.18
4.99
55
006
17.77
20.67
34.36
40.11
1.999
45
0015
45.37
53.20
60.51
71.61
2.564
25
112
35.00
40.86
37.15
43.42
ARAGONITE
d(k)
Hh
hkl
4.49
20
100
19.77
23.00
26
26
QUARTZ
3.059
55
141
29.19
34.03
4.27
50
121
20.80
24.20
2.679
28
022
33.44
39.04
2.867
25
002
31.20
36.38
3.79
20
031
C u
C o
d(k)
:
Hh
hkl
19.82
23.05
207
Hh
hkl
20 -
20<
c
23.47
27.32
http://jurassic.ru/
111
3.396
100
111
26.24
30.56
3.343
100
101
; 26.67
31.06
1.489
90
060
1.977
65
221
45.90
53.84
4.26
35
100
20.85
24.26
3.579
80
002
24.88
28.97
3.541
60
004
2.452
25
111
36.65
42.82
3.273
52
021
27.25
31.74
1.817
17
112
50.21
. 59.03
1.620
70
133
56.83
67.08
4.726
30
003
18.78
21.84
1.937
70
200
2.192
20
140
41.18
48.20
2.700
46
012
33.18
38.72
1.541
15
211
60.03
71.02
4.366
60
110
20.34
23.66
2.845
30
005
31.44
36.68
1.732
40
151
1.721
20
221
53.22
62.68
2.372
38
112
37.93
44.34
2.458
12
110
36.56
42.71
1.589
60
134
58.04
68.57
2.576
30
131
34.83
40.67
1.524
40
231
60.77
71.94
1.509
50
060
61.44
72.77
2.490
16
040
36.07
42.14
2.481
33
200
36.21
42.30
2.282
12
102
39.49
46.19
208
Table 7.3.
(Continued)
A = area
d(A)
ALKALI FELDSPAR
Orthoclase
ilh
hkl
26
C u
26
C o
3.31
100
220
3.77
80
130
4.22
70
201
3.24
65
002
3.29
60
202
26.94
31.38
23.60
27.47
21.05
24.49
27.53
32.07
27.10
31.57
2.992
50
131
29.86
34.82
d(A)
PLAGIOCLASE FELDSPAR
Albite
Hh
hkl
20
26co
C u
d(A)
CALCITE
C u
C o
d(A)
DOLOMITE
Cu
C o
30.99
36.14
d(A)
Ilh
hkl
2.79
100
104
26
26
32.08
37.43
d(k)
llh
hkl
2.69
100
104
29cu
26
33.31
38.87
C o
3.780
25
111
23.54
27.40
2.285
18
113
39.43
46.12
2.192
30
CO
hkl
SIDERITE
29.43
34.31
2.886
100
104
///,
2G
26
27.92
32.53
3.035
100
104
Illi
hkl
26
26
3.196
100
002
41.18
48.20
1.734
80
018
52.79
62.16
6.39
20
001
13.86
16.10
2.095
18
202
43.18
50.59
1.786
30
009
51.14
60.16
3.684
20
130
24.16
28.12
1.913
17
108
47.53
55.80
1.804
20
018
50.60
59.50
4.03
16
201
22.06
25.67
3.663
16
130
201
24.30
28.29
2.495
14
110
48.55
57.03
36.00
42.05
2.015
15
202
1.389
15
030
44.99
52.75
3.59
60
012
0.931
70
3012
2.13
60
113
24.80
28.88
111.80
148.07
42.44
49.70
2.51
50
110
1.838
40
024
~J~
20 peak
207
(a)
1.875
17
116
C o
1.633
100
311
d(A)
PYRITE
Ilh
hkl
26
28
Dividing:
MIN
QUARTZ
C u
C o
56.34
66.48
'MIN
Hi
QUARTZ
QUARTZ
(4)
1.690
60
116
54.28
63.96
2.709
85
200
33.07
38.59
35.77
41.78
2.423
65
210
37.10
43.36
49.60
58.29
2.212
50
211
40.79
47.74
1.484
35
214
67.42
80.24
1.963
60
202
46.25
54.26
62.59
74.19
1.916
40 ,..
220
47.45
55.70
1.452
35
300
(b)
Fig. 7.14. Measurement of intensity of a diffraction peak
by integration of area, (a) Single peak, (b) Overlapping
peaks.
64.14
76.12
3.128
35
111
28.54
33.26
M I N
http://jurassic.ru/
11
T h e r e a r e m a n y m o r e published m e t h o d s of quan
titative analysis b u t all suffer from similar p r o b l e m s
which affect t h e m e a s u r e m e n t of intensities, in par
ticular: (i) t h e crystallinity of s o m e species can vary
widely, e.g. micas, kaolinites (Fig. 7.15); (ii) chemi
cal variations, e.g. solid solution series, which can
cause p e a k shifts as well as varying intensities; (iii)
t h e ordering of t h e c o m p o n e n t chemical elements
within t h e structure, e.g. d o l o m i t e ; (iv) large mass
absorption differences b e t w e e n standards and u n
k n o w n samplers.
peak
HEMATITE
209
m m i i f mill
7.4 C L A Y M I N E R A L A N A L Y S I S
X R D provides t h e most efficient m e t h o d for t h e
d e t e r m i n a t i o n of clay minerals in m u d r o c k s , sand
stones and limestones. A knowledge of t h e clay
mineralogy can b e most useful for p r o v e n a n c e
studies and it can also give information o n t h e burial
history for t h e formation. A l t h o u g h s o m e clay
minerals are evident in whole rock diffractograms,
the most satisfactory m e t h o d is to extract and separ
ately analyse t h e clay fraction (usually defined as
less than 2 microns, < 2 urn). It is particularly impor
tant t o d o this in t h e case of very fine grained and
poorly crystalline clays, which are unlikely to give
recognizable diffraction patterns in a whole rock
scan. Also chemical p r e - t r e a t m e n t s are sometimes
210
211
Distilled water
Rock samples
^Jransd^ucer^,
(a)
Power supply
Distilled water
Sample
(b)
12
Degrees 26
(a)
(b)
Fig. 7.15. X-ray diffraction scans of the (001) lattice spacing of: (a) a well crystalline kaolinite from Cornwall; (b) a poorly
crystalline kaolinite from a fireclay from N England, using Cu Ka radiation and similar analytical conditions.
necessary to r e m o v e large a m o u n t s of certain nonclay and cementing materials and in so doing con
centrate t h e clay mineral fraction in t h e samples.
If high levels of c a r b o n a t e material are expected
this can be r e m o v e d by acid attack. H o w e v e r , cer
tain clay minerals, in particular chlorites and s o m e
smectites, are susceptible t o attack from dilute
mineral acids, e.g. dilute hydrochloric acid. Instead,
weak organic acids a r e r e c o m m e n d e d , in particular
t h e m e t h o d described by H e i n , Scholl & G u t m a c h e r
(1976) in which t h e samples are heated in a buffered
solution of sodium acetate and glacial acetic acid
( M o r g a n ' s solution).
Similarly, if large quantities of organic m a t t e r a r e
expected, this may be r e m o v e d by p r e - t r e a t m e n t
with 3 5 % hydrogen peroxide ( H 0 ) after Jackson
(1958, 1979). L a r g e amounts, of iron c o m p o u n d s
2
2ga\d
7.4.1 Separation
C o m p l e t e disaggregation is desirable before size
separation is a t t e m p t e d , and this is best effected by
ultrasonic m e a n s ( G i p s o n , 1963), although, for
poorly lithified samples, vigorous shaking with dis
tilled water will sometimes suffice. T h e sediments
should be b r o k e n (e.g. by percussion) to particles of
approximately 10 m m d i a m e t e r or less, placed in a
b e a k e r , covered with distilled water and immersed
in an ultrasonic bath (Fig. 7.16a). Alternatively, an
ultrasonic p r o b e can b e inserted into t h e b e a k e r
(Fig. 7.16b).
d)
2
w h e r e g is t h e acceleration d u e to gravity, a is t h e
sphere radius, d is t h e density of the particles, d
that of t h e settling m e d i u m (usually water) and u, its
viscosity. This law is empirical only, and applies t o
spherical particles in a non-turbulent m e d i u m at a
constant t e m p e r a t u r e , w h e r e t h e suspension is suffi
ciently dilute to avoid particleparticle interaction.
Because of the platey n a t u r e of clay particles, they
must b e regarded as having an equivalent spherical
d i a m e t e r (esd) w h e n applying Stokes' Law. A cen
trifuge may be used as an alternative to a settling
column, the effect being to increase t h e value of g in
the e q u a t i o n . T h e usual size fraction separated for
routine clay analysis is < 2 u m , and T a b l e 7.4 gives
1
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11J11111I11111111
7.4.2 Preparation
After extraction by p i p e t t e , at t h e required depth
from t h e measuring cylinder, the less than 2 um
fraction is p r e p a r e d for X R D analysis as an oriented
and also as an u n o r i e n t e d m o u n t . T h e r e are various
schools of thought on making oriented samples;
212
Table 7.4. (a) Pippette withdrawal times calculated from Stokes' Law for spherical particles (SG = 2.65) in a settling
column of water at different temperatures (after Galehouse, 1971)
Oriented clay
Pippetted
suspension
Temperature
Diameter in
micrometres
finer than
Withdrawal
depth
(cm)
62.5
44.2
20
20
31.2
22.1
15.6
7.8
3.9
1.95
0.98
0.49
10
10
10
10
5
5
5
5
20 s
1 m 54 s
Restir
1 m 54 s
3 m 48 s
7 m 36s
30 m 26 s
60 m 51s
4h3m
16 h 14 m
64h 54 m
20 s
1 m49s
Restir
1 m 49 s
3 m 37 s
7 m 15 s
28 m 59 s
57 m 58 s
3h52m
15 h 28 m
61 h 50 m
20 s
lm51s
Restir
1 m 51 s
3 m 42 s
7 m 25 s
29 m 41 s
59 m 23 s
3h58m
15 h 50 m
63 h 20 m
20 s
1 m46s
Restir
1 m46s
3 m 32 s
7m5s
28 m 18 s
56 m 36 s
3h46m
15h6m
60 h 23 m
20 s
1 m44s
Restir
1 m44s
3 m 27 s
6 m 55 s
27 m 39 s
55 m 18 s
3h41 m
14 h 45 m
48 h 59 m
20 s
1 m41 s
Restir
1 m41 s
3 m 22 s
6 m 45 s
27m I s
54 m 2s
3h36m
14 h 25 m
57 h 38 m
(b) Time required at various centrifuge speeds and temperatures for sedimentation of particles using a standard 100 ml
tube, 100 mm suspension depth, 90 mm of fall and 1000 mm (1 cm ) of sediment (from Jackson, Whitting & Pennington,
1950)
3
Limiting particle
diameter
(um)
5
2
0.2
Ceramic tile
Elapsed time for withdrawal of sample in hours (h), minutes (m), and seconds (s)
22
23
24
20
21
25
Density of
particles
gem"
3
2.65
2.65
2.50
Centrifuge
speed
(rpm)
300
750
2400
20C
25C
3.3
3.3
35.4
2.9
2.9
31.4
Vacuum p u m p
213
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214
a.
< y
K Q
<
l l
-C
060 near 1.
<I
001's
<
060 near 1.
in
060 near 1.
hk bands p
<
060 near 1 .
Check hkls
against sta
pu
Check hkls
against sta nd;
LLI
tttt r r T T r ^ s v
26
CuKa
Fig. 7.18. Diffractometer traces of a typical clay sample and component clay minerals (after Gibbs, 1967).
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or slight
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215
2i
Table 7.6. X-ray identification of the principal clay minerals (<2 um) in an oriented mount of a separated clay fraction
from sedimentary material (from Carroll, 1970)
Mineral
Glycolation effect;
1 hr, 60C
Kaolinite
No change
Kaolinite, disordered
No change
Halloysite, 4 H 0
Halloysite, 2 H 0
2
No change
No change
Mica, 2M
No change
Mite, lMd
No change
Montmorillonite Group
Vermiculite
(001) expands to 17 A
with rational sequence
of higher orders
No change
Chlorite, Mg-form
Chlorite, Fe-form
Mixed-layer minerals
Attapulgite
(palygorskite)
Sepiolite
Amorphous clay,
allophane
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No change
No change
No change unless an
expandable
component is present
Expands if
montmorillonite is a
Heating effect,
1 hr
Becomes amorphous at
550-600C
Becomes amorphous at lower
temperatures than kaolinite
Dehydrates to 2 H O at 110C
Dehydrates at 125-150C;
becomes amorphous at
560-590C
(001) becomes more intense on
heating but structure is
maintained to 700C
(001) noticeably more intense on
heating as water layers are
removed; at higher
temperatures like mica
At 300C (001) becomes 9 A
z
Dehydrates in steps
(001) increases in intensity;
<800C shows weight loss but
no structural change
(001) scarcely increases;
structure collapses below
800C
Various, see descriptions of
individual minerals
Depends on minerals present in
inter-layered mineral
constituent
Dehydrates stepwise
No change
No change
Dehydrates and loses weight
No change
216
217
001
004
(a)
003
004
003
I/004
Mineral A
002
1.0 16.9A M
002
(Mixture of
'Iminerals
001
Q01
B+ C
(b)
005
004
003
, , 002
Regularly
|interstratified(
mineral
(B-C)
(c)
Fig. 7.19. Diagram showing the XRD
peaks of: (a) single clay mineral; (b)
mixture of clay minerals; (c) tegular
interstratified clay minerals (rational
sequence); and (d) randomly
interstratified clay minerals (irrational
sequences) (fromThorez, 1976).
"004"
"003"
"002
Randomly
interstratified
structure
B-C
001"
(d)
2eCuKa
T h e m e t h o d proposed by Weir et al. (1975) uses
t h e equation:
^KAOLINITE
25
,
'iLLiTE
.
1
,
'sMEcrrTE
,
'
^CHLORITE
20
= 100%.
T h e divisors have the function of correcting for t h e
relatively greater X-ray responses of kaolinite and
chlorite.
This m e t h o d has t h e serious disadvantage com
m o n to all normalizing techniques in that an e r r o r in
o n e c o m p o n e n t affects all t h e others, and also n o
account is t a k e n of t h e presence of X-ray a m o r p h o u s
material.
If o n e wants a truly quantitative t e c h n i q u e a m o r e
rigorous a p p r o a c h must be a d o p t e d . T h e introduc
tion of an internal s t a n d a r d is certainly necessary
and a material such as b o e h m i t e ( y - A I O O H ) which
Fig. 7.20. Calculated diffraction profiles assuming random interstratification of 10 and 16.9 A layers (illite and
montmorillonite, glycolated). Fraction of montmorillonite layers are 1.0,0.8,0.6,0.4,0.2 0 1 and 0 (from Reynolds &
Hower, 1970).
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218
2 +
2 +
2 +
219
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iitmwmiittiiiiiiimiiiiiini
220
X-RAY POWDER
TUCKER
2 +
than the C a
ion, this results in a decrease in t h e
rf
lattice spacing (Goldsmith & Graf, 1958a).
Several authors have p r o d u c e d a graph showing t h e
mole % M g C 0 against d
in angstrom units and
20 for C u Ka radiation and Fig. 7.22 from Gold
smith, Graf & H e a r d (1961) is the o n e most com
monly used. T h e precise position of the rf 4 p e a k is
obtained by using an internal standard such as halite,
quartz or fluorite which has a major peak close to
t h e main calcite p e a k (Table 7.3).
O n t h e basis of magnesium content, calcite occurs
in two forms: low Mg calcite ( L M C ) with 0 to 4 mole
% M g C 0 and high M g calcite ( H M C ) with m o r e
than 4 mole % , but with a range of 1 1 - 1 9 mole %
being most c o m m o n . In m o d e r n tropical c a r b o n a t e
sediments, H M C is mainly of biogenic origin, coming
from calcareous red algae, echinoderms, bryozoans
and some benthic foraminifera. H M C micritic and
bladed c e m e n t s are c o m m o n in reefs. L M C is also
mostly of biogenic origin, coming from planktonic
foraminifera, coccoliths and some molluscs. In addi
tion t o t h e 'vital' effect, t h e M g
content of bio
genic calcite is d e t e r m i n e d by water t e m p e r a t u r e :
lower M g occurs in skeletons precipitated in cooler
waters. With marine calcite c e m e n t s , t o o , those
precipitated in colder, commonly d e e p e r waters,
have lower M g . A l t h o u g h H M C grains and ce
m e n t s generally lose their M g
during diagenesis,
so that most ancient calcite is low in magnesium, a
m e m o r y of t h e original high M g is commonly retain
ed. In limestones, original L M C will typically have
01 m o l e % M g C 0 , w h e r e a s original H M C may
have a little m o r e (23 mole % ) .
104
10
2 +
Percentage of rock
Kaolinite
Illite
2 +
XRD traces
2 +
2 +
Upper
Brent
Sand
Middle
Brent
Sand
7.5.2 Mixtures of C a C 0
feet
Lower
Brent
Sand
Kaolinite
peak
7.16A
0 10 20
10 20
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minerals
M a n y m o d e r n c a r b o n a t e sediments consists of a
mixture of t h r e e C a C 0 minerals, aragonite, low
M g calcite and high M g calcite. A r a g o n i t e is a major
constituent, coming from t h e shells and skeletons of
green algae, corals and molluscs, and forming ooids
and m a n y marine c e m e n t s . X-ray diffraction is t h e
quickest m e t h o d for determining the mineralogical
composition of m o d e r n c a r b o n a t e s , although there
has been discussion over w h e t h e r peak height or
p e a k area analysis should b e used.
Careful grinding of the sample is important since
this process determines t h e particle size of the
p o w d e r and t h e structural d a m a g e to the minerals,
which respond differently to the grinding. T h e s e
differences can affect t h e X R D p e a k intensities
3
MlllllllllltlllttMllllllllf
CaC0
.0
3.04
3.02
3.00
2.98
2.96
2.94
2.90 2.88
10
DIFFRACTION
mole % M g C 0
20
30
221
40
50
29.4
29.6
29.8
30.0 *
30.2
s
\
\
\
\
\
\
\
CD
30.4 m
\
\
30.6
\
N 30.8
31.0
Fig. 7.22. Displacement of the d peak of calcite with
increasing M g C 0 to dolomite (based on Goldsmith et al.
1961).
i(H
222
r~
30
28
26
Fig. 7.23. X-ray diffractograms (A, and A aragonite; C,
calcite) showing the effect of extended grinding on the
peak intensity of a 5050 mixture of mollusc aragonite
and oyster calcite. Grinding times (circled numbers) are in
cumulative minutes (from Milliman, 1974).
2
hA-,
hA-, + hC-,
2 +
4 8
Mg52-
2 +
(b)
U wAi
(hA-wA) V
aA-, + aCi
V* {hA wA) + V (hC wC)
_
hA wA
hA wA + hC wC
2
2 +
W4
(Af o )
Af o, =
W4
lM
(c)
aA-,
aA-, + S a d
2 +
% m g calcite =
% t
~ where
laC-, = aC-, + a mg
aC, = 2 x ( a d / 2 )
W4
http://jurassic.ru/
n n
C l
{*?' x *
calcite
SaCi
2 +
224
100
1.4
1.3
80
2.9
1.2
<
60
1.1 h
o 2.89
to40
1.0
0.9
Order
ratio 0.8
l[221]
0.7
l[101]
A'
20
2.88
6
10
F e C 0 wt%
14
18
0.6
20
40
60
80
100
0.5
104
Percentage aragonite
0.4
0.3
0.2
0.1
50
51
52
Mole% C a C 0 in dolomite
3
Degree of ordering
2 +
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.llM i l l
53
Key
vein dolomites
pervasive dolomites
dolomicrites
226
227
Trends in dolomite
stoichiometry
Precipitational
conditions
Mg:Ca Salinity (%>)
Mole % C a C 0
48
50
52
54
Fig. 7.29. Diagram of dolomite stoichiometry data and inferred precipitational conditions. Group 1 is composed of ancient
sucrosic and sparry dolomites. Group 2 is composed of finely crystalline modern and ancient dolomites not associated with
evaporites and Group 3 are finely crystalline modern and ancient dolomites associated with evaporites (from Morrow,
1982).
U3
..
i ....i
i . i
i . i
.i
5 10 20 30
70 80 90 95 98
% Dolomite (probability scale)
Fig. 7.30. Calibration curve for determination of dolomite
in calcite, using dolomite/calcite ratio of area of [113]
peaks. Main line connects points obtained with standards
prepared using calcite ground for 30 minutes. Vertical bars
give range of one standard deviation. Dashed line
connecting squares is for standards prepared with calcite
ground for 15 minutes, i.e. relatively coarse crystalites.
Dashed line connecting triangles is for standards prepared
with chemical calcite, i.e. relatively fine crystallites (from
Lumsden, 1979);
W4
HHnmmTiHmtMitiMMifmHfl
1 1 3
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7.6 X R D O F S I L I C A
MINERALS
228
opal
8.1
INTRODUCTION
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JiliJiiJMiMiim
230
N.H. TREWIN
8.2 B A S I C F U N C T I O N A N D M O D E S
OF OPERATION OF THE SEM
T h e S E M (Fig. 8.1) comprises an electron gun which
produces a stream of electrons to which an acceler
ating voltage of 2 - 3 0 k V is applied. T h e b e a m
passes through a series of two o r m o r e electromag
netic lenses t o p r o d u c e a small (10 n m or less)
demagnified image of t h e electron source o n the
specimen. F o r most geological work a tungsten hair
pin filament is used as t h e electron source with a
vacuum of about 1 0
torr. Brighter images and
better definition can b e obtained with a L a B gun at
1 0 ~ torr and for ultrafine definition a field emission
source operating at I O t o r r can b e used, b u t this
requires special seals and p u m p i n g a r r a n g e m e n t s to
achieve t h e required v a c u u m .
- 5
- 9
Electron beam
b
a
=
Anode (earthed)
Spray aperture
Condenser lens 1
Condenser aperture
Condenser lens 2
Scan coils
Collector Photomultiplier
Scan
generator
Video
amplifier
Screen
231
Electron beam
Electron beam
Specimen
/
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232
N.H. TREWIN
(c) Differences
in electrical potential
on the
specimen surface. T h e trajectories of low energy
secondary electrons a r e affected by small variations
in surface charge on the specimen. A r e a s of t h e
specimen which are relatively negative a p p e a r bright
on the image and this results in t h e effect k n o w n as
charging which occurs if t h e point of b e a m impact is
not effectively e a r t h e d by either the natural conduc
tivity of t h e specimen o r its applied coating. C h a r g e
accumulations of only a few volts give rise to charging
features with low energy electrons, but with high
energy reflected electrons a charge build-up of
several kilovolts is required; thus B S E images are
charge free.
F o r t h e examination of most geological materials
t h e S E M is o p e r a t e d in the combined S E - B S E
m o d e . Increasing use is being m a d e of B S E imaging
of polished surfaces with t h e advent of efficient
back-scattered detectors. A l t h o u g h on many instru
m e n t s it is possible t o obtain a back-scattered image,
with t h e n o r m a l d e t e c t o r t h e quality is usually p o o r
since t h e detector is not designed for t h e collection
of reflected electrons.
8.2.3 C a t h o d o l u m i n e s c e n t m o d e o f
operation
T h e C L operation m o d e utilizes t h e visible light
emitted when electrons strike t h e specimen. M a t e r
ials vary greatly in their luminescent p r o p e r t i e s a n d
minor traces of impurities can affect t h e luminescent
properties. Emission is also altered by lattice strain
resulting from crystal defects a n d residual strain.
Collection of t h e emitted light is achieved by
focussing it with a lens into a light guide a n d o n t o a
photomultiplier. Picture contrast is d u e t o a variety
of factors. T o p o g r a p h y of t h e specimen is i m p o r t a n t
but t h e resulting features of greater interest are d u e
to chemical variations, crystal defects a n d crystal
orientation. F u r t h e r details on this t e c h n i q u e using
t h e S E M can b e found in Muir & G r a n t (1974),
G r a n t (1978), Krinsley & Tovey (1978) a n d Smart &
Tovey (1982). T h e multiple scintillator-photomultiplier type of B S E detector can b e a d a p t e d for catho
doluminescence work. In the Philips Multi-Function
D e t e c t o r , cathodoluminescence detector elements
can b e substituted for B S E detector elements (Pye
& W i n d s o r - M a r t i n , 1983). R u p p e r t et al. (1985)
illustrated contrasting B S E and C L images of a
s a n d s t o n e , and further examples are shown in Fig.
8.8. T h e r e a d e r is also referred to C h a p t e r 6 on
cathodoluminescence in this volume.
8.3 S E M A N C I L L A R Y E Q U I P M E N T
AND TECHNIQUES
8.3.1 Photographic equipment a n d
techniques
TECHNIQUES
T h e excellent resolution a n d great d e p t h of field of
t h e S E M have m a d e it very p o p u l a r for providing
illustrations for a wide variety of geological studies.
T h e quality of S E M p h o t o g r a p h s in geological jour
nals is highly variable, ranging from excellent to
examples displaying m a n y of t h e faults illustrated
and discussed in Section 8.6.2. In s o m e cases the
p a p e r quality of t h e journal is responsible for p o o r
reproduction.
F o r most sedimentological work simple views of
surfaces a r e all that is required a n d with most
machines a zoom facility enables t h e o p e r a t o r to
c o m p o s e t h e p h o t o g r a p h satisfactorily. If it is pro
p o s e d t o m a k e a multiple plate of p h o t o g r a p h s it is
helpful to t a k e t h e shots at t h e same magnification
or at multiples of a basic magnification. T h e incor
p o r a t i o n of a micron m a r k e r in the p h o t o g r a p h is
essential and easier to ' r e a d ' t h a n a p h o t o g r a p h
captioned as x 4350! E n s u r e that t h e micron m a r k e r
contrasts with its b a c k g r o u n d , o r e n h a n c e and label
t h e m a r k e r for publication p u r p o s e s .
EQUIPMENT
T h e choice of a c a m e r a for use with an S E M is
largely a m a t t e r of user preference. Many machines
233
MONTAGES
P h o t o g r a p h i c m o n t a g e s m a y h a v e t o b e constructed
to cover large areas at high magnification. T h e
construction of both controlled a n d uncontrolled
montages is discussed by Smart & Tovey (1982).
U n c o n t r o l l e d m o n t a g e s a r e m a d e merely by match
ing features in the overlap area of the p h o t o g r a p h s
(Fig. 8.5), b u t because the area scanned is generally
trapezoidal severe distortions in orientation develop
if large n u m b e r s of micrographs a r e joined. It is
preferable that p h o t o g r a p h s are t a k e n at magnifica
tions > 2 0 0 0 a n d that less t h a n c. 10 p h o t o g r a p h s a r e
joined together.
Controlled m o n t a g e s (Fig. 8.5) a r e p r e p a r e d by
photographing on a regular grid p a t t e r n and noting x
a n d y shift co-ordinates of t h e centre of each p h o t o
graph a n d then mounting t h e p h o t o g r a p h s on a
regular grid. Matching will n o t b e perfect but dis
tances and orientations will be better preserved. All
p h o t o g r a p h s must b e t a k e n with ample overlap (c.
2 5 % ) , without altering the magnification, and must
be enlarged by the same factor in processing.
Distortion effects in m o n t a g e construction are
greatest at low magnifications and high tilt angles of
t h e specimen. T h e m o u n t i n g a n d printing of p h o t o
graphs for m o n t a g e s requires skill. Contrast of ad
jacent p h o t o g r a p h s must b e reasonably close to
(a)
(b)
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11111
HtiMtiljjtih
lM
l' M
l JtiT^
234
N.H.
TREWIN
STEREOSCOPIC MICROGRAPHS
A n y specimen stage which enables t h e specimen to
be tilted permits t h e taking of stereoscopic pairs.
M e t h o d s that can b e employed are discussed by
T o v e y (1978) and Smart & Tovey (1982). T h e most
c o m m o n m e t h o d used is t h e 'tilted convergent'
m e t h o d whereby t h e specimen is tilted by a small
angle (25) about a m e a n tilt angle. This m e t h o d
ensures that t h e specimen is facing t h e detector in
both positions. T h e illumination is effectively from
t h e side in this m e t h o d and t h e p h o t o g r a p h s must b e
rotated by 90 for stereoscopic viewing.
Techniques vary d e p e n d i n g o n t h e t y p e of speci
m e n stage, but in general o n e must ensure that t h e
same a r e a is p h o t o g r a p h e d on each occasion. This
can b e achieved by sketching t h e first view o n a
t r a n s p a r e n t overlay on t h e screen. T h e magnifica
tion is t h e n reduced t o less t h a n x 200 while keeping
track of a convenient reference feature n e a r t h e
centre of t h e screen. T h e stage can t h e n be tilted by
t h e desired a m o u n t and t h e reference feature
brought back t o its previous position using t h e X , Y
controls. T h e magnification can t h e n be increased t o
t h e correct figure and t h e desired feature checked
with its outline previously d r a w n o n t h e screen over
lay. A n y refocussing should be d o n e with t h e Z
control to avoid image rotation and magnification
changes d u e t o alteration of working distance. T h e
second p h o t o g r a p h can t h e n be t a k e n .
D e t a i l e d discussion of stereographic techniques
can b e found in Clarke (1975) including m e t h o d s for
T H E S E M IN S E D I M E N T O L O G Y
235
Enlarged rough
specimen surface
8.3.5 Charge-Free A n t i c o n t a m i n a t i o n
System (CFAS)
T h e C F A S system can b e used in conjunction with a
back-scattered electron detector such as the Robin
son detector and o p e r a t e s by maintaining a small
residual gas pressure of b e t w e e n 0.01 and 0.5 torr in
Fig. 8 . 7 . General view of sandstone to illustrate the use of EDS analysis at five points. The sample was gold coated, hence
the gold peaks on the EDS traces. Analysis identifies at point (1) quartz overgrowths; (2) K-feldspar with overgrowth;
(3) ferroan calcite of diagenetic origin growing into pore space and overgrowing quartz; (4) kaolinite in pore space either
growing around the ferroan calcite or being forced apart by growth of the carbonate; (5) siderite rhomb on quartz grain
surface. Minor Si peaks associated with siderite and calcite analyses are probably due to secondary reflection.
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238
T H E S E M IN S E D I M E N T O L O G Y
N.H. T R E W I N
t h e specimen c h a m b e r . It is o p e r a t e d by having
s e p a r a t e diffusion p u m p s o n t h e c h a m b e r a n d
column, gas leakage through the 200 um final aper
ture is not significant. In fitting t h e C F A S system t h e
secondary electron detector H V supply is discon
nected, thus it is not possible to switch directly from
n o r m a l operation to C F A S o p e r a t i o n .
T h e advantage of t h e system is that specimens can
b e p u t in as received without t h e n e e d for any
special preparations and coatings. G a s ionization in
t h e c h a m b e r is always equal to charge accumulation
and t h u s charging is automatically eliminated.
Specimens which a r e d a m p or oily and which would
normally c o n t a m i n a t e t h e column can be e x a m i n e d .
This system is excellent for geological use on any
samples requiring rapid examination for mineralogi
cal composition, especially rapid search for small
heavy-element grains ( B . W . R o b i n s o n , 1980; Robin
son & Nickel, 1979). A n a d d e d advantage is t h a t
filament life is r e p o r t e d t o b e increased as c o m p a r e d
with conventional o p e r a t i o n , b u t m o r e frequent
cleaning of t h e column may b e found necessary.
239
8.4 S A M P L E C O L L E C T I O N
8.4.1 Surface material and o u t c r o p s
Field sampling of material for S E M studies r e q u i r e s
that s o m e elementary precautions are t a k e n and
sufficient observations m a d e at the sample site. Since
S E M studies will probably only constitute part of
any laboratory study, sufficient material m u s t b e
g a t h e r e d for all possible aspects, such as grain-size
analysis and thin section p r e p a r a t i o n .
Unconsolidated material in which t h e fabric is not
required t o b e preserved can b e collected as a bag
sample (dry) or bottle sample (wet). Samples con
taining live or d e a d organic material may n e e d to be
preserved in alcohol if t h e samples cannot be i m m e
diately t r e a t e d . A l u m i n i u m foil is useful for w r a p
ping small samples t o prevent contamination and t h e
w r a p p e d samples can b e safely t r a n s p o r t e d in plastic
bottles. Cloth or p a p e r is to b e avoided since fibres
are likely to be shed into t h e sample.
I m p r e g n a t i o n of unconsolidated sediments in t h e
field provides a later opportunity to e x a m i n e fabric
details using thin sections or t h e S E M . F o r suggest
ed sample p r e p a r a t i o n see Section 8.5.2.
Consolidated rock material is generally collected
in t h e traditional geological m a n n e r by use of a
h a m m e r . H o w e v e r , such violence can have t h e effect
of producing cracks, fracturing grains and crushing
p o r o u s material. Samples must b e sufficiently large
to avoid such effects and (unless it is t h e object of
(c)
Fig. 8.9. Backscattered electron images and element distributions, (ac) Growth of carbonate cements within a specimen
of Dactylioceras cf. commune from the Toarcian of NE Yorkshire, (a) Backscattered electron image of polished, carboncoated thin section. Cement stages are interpreted in (b) in which S is a section of an ammonite septum defined by apatite
rims and with associated pyrite framboids. Cement growth stages: (1) high Mg calcite (filling fracture in septum); (2) low
Mg calcite; FeS ; (3) high Mg, Fe calcite; (4) high Fe calcite; (5) high Mn, Fe calcite (replaces septum) fills void, (c)
Histogram and X-ray intensity ( a element abundance) map showing the different concentration of Mg across part of the
area of (a). Cement growth stages are clearly picked out in the elemental map (black and white print derived from a colour
image, hence both high and low Mg concentrations appear pale in this image).
(dh) Chemical variations in a dolomite crystal from the Pendleside Limestone, Lower Carboniferous, Bowland Basin,
northern England, (d) Subhedral dolomite crystal in silicified limestone. The light zones rimming the crystal suggest the
presence of elements with higher atomic: numbers compared with the dull core. Note the irregular contact between the dull
and light zones. Scale bar = 50 \ t m . Back-scattered electron photomicrograph (BSEM). (e) DIGIMAP of view in (d) for
Ca. Note relatively uniform distribution. Scale bar = 25 \ i m (same for f - h ) . (f) DIGIMAP of view in (d) for Mg. Depletion
in Mg in the crystal rim relative to the corgis-indicated by the darker nature of the rim. (g) DIGIMAP of view in (d) for Fe.
Note the very low Fe content in the black core compared with the grey rim. (h) DIGIMAP for Mn showing similar
distribution to Fe (g).
2
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N.H. TREWIN
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8.5 S A M P L E T R E A T M E N T
8.5.1 Porous r o c k s t o be viewed o n
fractured surfaces
T h e following p r e p a r a t i o n techniques a r e generally
used for viewing b r o k e n surfaces of porous rocks
which fracture a r o u n d grains rather t h a n through
grains. T h e m e t h o d of p r e p a r a t i o n of material can
have a m a r k e d effect o n t h e fabric of delicate clays
such as filamentous illite present within p o r e space.
M c H a r d y , Wilson & Tait (1982) have shown how
critical-point drying can preserve features which
would be destroyed by air-drying and freeze-drying
techniques. T h e value of using critical-point drying
is that the technique prevents the passage through
t h e p o r e s of an airliquid interface or an interface
242
N.H. TREWIN
AIR-DRIED SAMPLES
Samples previously air dried and which contained
water as the p o r e fluid can be examined without
further t r e a t m e n t , but it is frequently advisable t o
wash the specimen with distilled water t o r e m o v e
any chlorides or other soluble salts which may have
crystallized in p o r e space d u e to the evaporation of
saline p o r e water. This is best achieved by soaking a
sample, not m o r e than 1 cm thick, in distilled water
until it is chloride free. ( T h e time t a k e n will d e p e n d
on permeability and salinity of the e v a p o r a t e d p o r e
water.) This technique is also useful for m o d e r n
m a r i n e sediments and rock material collected from
shore sections.
A i r drying, combined with removal of water solu
ble material, is also a technique which can b e used to
study t h e soluble salts and t h e effects of their re
moval. This has applications in the study of weather
ing of rocks and t h e formation of evaporites.
If delicate material such as fibrous illite is suspect
ed to exist in p o r e space and either time or lack of
a p p a r a t u s precludes use of critical-point drying, bet
ter results may b e o b t a i n e d by air drying samples
from amyl acetate. T h e advantage of this m e t h o d is
that amyl acetate has a much lower surface tension
than water and so the forces exerted at t h e liquid
gas interface as the specimen dries a r e r e d u c e d .
OIL-SATURATED SAMPLES
Rocks that are oil-saturated, or which contain oil
residues after evaporation of lighter h y d r o c a r b o n s ,
must have t h e hydrocarbon r e m o v e d prior to S E M
examination. If oil is n o t r e m o v e d it is vaporized by
t h e electron b e a m and will m a k e t h e S E M column
dirty and reduce picture quality. Oil also prevents
t h e efficient coating of t h e sample with gold, result
ing in charging of t h e specimen and p o o r resolution
pictures.
Oil can be r e m o v e d by use of solvents such as
a c e t o n e , xylene, t o l u e n e , chloroform and trichlor o e t h a n e . Chloroform and trichloroethane are the
FREEZE DRYING
Freeze-drying techniques a r e used extensively on
biological material and have been applied success
fully to claywater systems in soils. This m e t h o d is
favoured by E r o l , L o h n e s & D e m i r e l (1976) for
preparation of swelling clays such as Na-montmorillonites. It does not involve replacement of water
with an organic liquid which could cause swelling
and ion exchange in the clays.
Method. T h e m e t h o d described by M c H a r d y et
al. (1982) used 10-mm pieces of rock (Jurassic,
Magnus Field reservoir from t h e N o r t h Sea) which
were either directly frozen with the contained p o r e
water or frozen after the samples were washed free
of chloride. Samples w e r e plunged into liquid nitro
gen or freon for at least 30 m i n u t e s , they were t h e n
vacuum-dried from the frozen state in an E d w a r d s
M o d u l y o freeze-drier. T h e drying p h a s e takes sev
eral days.
F o r the m e t h o d to b e a success t h e specimen must
be cooled very rapidly so that the water is frozen in
place and ice crystals d o not form. T h e rate of
cooling required is several h u n d r e d degrees p e r
second and this will only be accomplished on t h e
o u t e r surface of t h e rock, and possibly to a d e p t h of
only 0.1 m m (Greene-Kelly, 1973). A n o t h e r prob
lem is e n c o u n t e r e d in t h e drying p h a s e w h e n it is
necessary t o w a r m t h e specimen t o a t e m p e r a t u r e
greater than 40C t o achieve sublimation of t h e ice
in a reasonable time, but at this t e m p e r a t u r e rapid
growth of ice crystals will occur which will displace
matrix clays.
T h e main applications of freeze-drying of samples
a r e in t h e study of soils and swelling clays. M c H a r d y
et al. (1982) found this m e t h o d inferior to criticalpoint drying for preservation of delicate illite in p o r e
space.
CRITICAL-POINT DRYING
T h e advantage of t h e critical-point drying technique
is that it eliminates t h e surface-tension forces ap
plied to delicate crystals during t h e drying stage by
avoiding t h e passage of an airwater interface
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N.H. TREWIN
8.5.2 Non-porous r o c k s
Rocks which have low porosity or in which grains
and cement give similar resistance to fracturing, as is
t h e case in many quartz-cemented sandstones and
well-cemented limestones or dolomites, may not
reveal much information when rough b r o k e n sur
faces are examined. In such cases it is frequently
necessary to view a polished and etched surface to
obtain useful information.
This technique is particularly useful in t h e ex
amination of c a r b o n a t e c e m e n t e d sandstones, lime
stones and dolomites, since by suitable choice of
etching agent different minerals can be attacked and
their role as grains or c e m e n t elucidated. T h e tech
nique can also b e used on unconsolidated sediments
which have been resin-impregnated in t h e field or
laboratory.
GENERAL METHODS
A slice of t h e rock t o be examined is cut to a suitable
thickness (say 35 m m ) . T h e specimen can thus be
oriented in any required m a n n e r and part of t h e
rock slice used to m a k e a thin section or polished
section for examination by other techniques.
T h e rock slice or chip should be polished t o a
reasonable standard with respect to t h e features
required to t h e viewed (polishing details in Lister,
1978). T h e specimen slice should be cut or b r o k e n to
t h e required size for insertion in the S E M c h a m b e r
and mounted on the stub prior to etching to minimize
t h e possibility of d a m a g e to the delicate etched
surface. S o m e S E M c h a m b e r s will a c c o m m o d a t e a
polished thin-section; this enables t h e same area t o
be examined using a variety of techniques and is an
obvious advantage.
T h e etching process can be varied to suit the
particular situation. F o r limestones, dilute hydro
chloric, acetic or formic acid can be used for lowrelief etching. It is best to use as dilute a solution as
possible to avoid vigorous gas generation which
could damage delicate features. Sandberg & Hudson
(1983) used 0 . 2 5 % formic acid and an etch time of
6090 s to reveal aragonite relics in calcite-replaced
shells. H a y et al. (1970) used 1% HC1 and found 30 s
of etching sufficient to reveal the ultrastructure of
fine c a r b o n a t e grains of biogenic origin. Despite
t h e above examples of gentle etching, Wilkinson,
J a n e c k e & Brett (1982) used 5 0 % glacial acetic acid
SURFACE T E X T U R E S OF GRAINS
It is generally considered that only small n u m b e r s of
detrital quartz grains n e e d be examined from a
sample to obtain representative surface textures
(Krinsley & M c C o y , 1977). T h e m e t h o d described
by Krinsley & D o o r n k a m p (1973) and used by
W a n g , Piper & Vilks (1982) is as follows.
Five grams of the sample are boiled for 10 min in
c o n c e n t r a t e d HC1 and then washed .With distilled
water. If iron oxide coatings are present t h e grains
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N.H. TREWIN
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8.6 S A M P L E M O U N T I N G , C O A T I N G
AND STORAGE
8.6.1 General considerations
W h e n t h e required p r e p a r a t i o n techniques have
b e e n performed on t h e sample it may be of suitable
size and s h a p e for m o u n t i n g directly on t o a stub for
examination o r it may r e q u i r e s o m e final shaping.
Prior to m o u n t i n g t h e sample t h e stubs to b e used
must b e labelled; this is simply d o n e by scratching or
engraving a n u m b e r o n t h e side or u n d e r s i d e of t h e
stub.
Specimens a r e usually individually m o u n t e d on
10-mm d i a m e t e r stubs designed t o fit t h e particular
m a k e of machine being o p e r a t e d but larger 25-mm
stubs can be used to t a k e several specimens. It is
generally possible to design an a d a p t o r to m a k e
different stubs transferable b e t w e e n machines if this
becomes desirable.
It is useful to have a k n o w n reference point o n t h e
stub surface so that the sample can be placed in a
k n o w n orientation in t h e sample holder within the
247
248
N.H. TREWIN
T H I N S A M P L E (5 c m x 5 c m x 1 c m ) C U T F R O M O R I E N T A T E D B L O C K
15
1
CRITICAL POINT
O R F R E E Z E D R Y I N G IF D E S I R E D
S A M P L E P L A C E D IN M O U L D A N D C O V E R E D W I T H E P O X Y
USING A R A L D I T E A Y 18
A Y 18
5 0 % by vol
HY18 HARDENER
4 8 % by vol
N-DIBUTYL PHTHALATE
RESIN
(a)
Incorrect
2 % by vol ( P L A S T I C I S E R )
ZEZ
S A M P L E P L A C E D U N D E R V A C U U M O F 60 - 70 c m Hg
FOR 3 - 6 H O U R S TILL FULLY I M P R E G N A T E D
~ z z
R E S I N C U R E D IN O V E N A T 80"C F O R B E T W E E N O N E A N D T W O D A Y S
z z z
j ^ ^ ^ ^ z
C U B E (1 C M X 1 C M x 1 C M ) C U T F R O M I M P R E G N A T E D S A M P L E A N D
E T C H E D IN D I L U T E H Y D R O C H L O R I C A C I D O R O T H E R D E S I R E D A C I D
FOR T W O TO THREE DAYS
(b)
Correct
Z Z
C U B E W A S H E D A N D D R I E D T H E N I T IS B R O K E N T O E N A B L E A
FRACTURE SURFACE FREE FROM SURFACE ARTEFACTS
TO BE VIEWED
~ T ~
SPECIMEN MOUNTED A N D COATED FROM SEM STUDY
o
o
O o
II
(a) Vl
Fig. 8.12. (a) Stub with simple orientation marks and grid
engraved on surface to facilitate location of specific grains,
(b) Modifications of specimen stubs to permit viewing of
greater proportions of the surfaces of spherical grains
(modified from fig. 6.2.1 of Smart & Tovey, 1982).
used to ensure an a d e q u a t e sample of grains for t h e
intended project.
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249
r
250
N.H. TREWIN
8.7 P R O B L E M S O F S E M O P E R A T I O N
8.7.1 General
It is not possible or desirable t o a t t e m p t to provide a
trouble-shooting m a n u a l for t h e S E M o p e r a t o r in a
short chapter such as this. Details differ b e t w e e n
machines of different m a k e s , and technology is ad
vancing so rapidly that any technical specifications
will soon b e o u t of d a t e . It is therefore assumed that
all machine functions are operating correctly, and
only those features most commonly found to affect
image quality a r e listed h e r e . In all cases t h e o p e r a
tion m a n u a l supplied by t h e m a k e r s of t h e S E M
should b e followed in t h e setting u p and running of
t h e m a c h i n e . It much be stressed at t h e outset that
many of t h e problems e n c o u n t e r e d in day t o day
running of an S E M a r e a direct result of lack of
cleanliness and p o o r specimen quality.
(f) Astigmatism
effects. If at high magnifications
( x 10,000) t h e r e is distortion giving oblique
elongation of features when the focus is adjust
ed the astigmatism controls are probably in
n e e d of adjustment. Serious astigmatism may be
d u e t o p o o r alignment of the column or dirt in
o n e of t h e column a p e r t u r e s .
(g) Extraneous 'noise' problems.
Many buildings
are n o t particularly stable and vibration due to
traffic, o t h e r machinery, high wind and the S E M
p u m p itself can be a p r o b l e m . T h e S E M should
be set u p in t h e most stable and quiet environ
m e n t possible. If vibration is suspected com
p a r e operation at different times of day and
place t h e p u m p as far from t h e machine as
possible. Vibration results in straight edges
having a saw-tooth a p p e a r a n c e at high
magnifications.
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251
Increase brightness
100 A S A
ff11
V
Increase contrast
EXAMPLES AND
8.8.1
REVIEWS
introduction
SURFACE
% GRAINS SHOWN
IG
FEATURE
QUARTZ GRAIN
SURFACE
TEXTURES
8.9.1 Introduction
T h e main impetus in the study of surface textures of
quartz grains is t h e belief that e n v i r o n m e n t a l inter
pretations can b e m a d e o n t h e basis of characteristic
ABUNDANT
[]
COMMON
25 - 75
[o]
SPARSE
25 - 75
RARE
ex.
8.9
[]
>75
<5
FEATURE
| 30 CRYSTALLINE OVERGROWTH
| 29 SILICA PELLICLE
I 28 SILICA FLOWERS
| 27 SILICA GLOBULES
| 26 SCALING
| 25 SOLUTION CREVASSES
| 24 SOLUTION PITS
| 23 ANASTOMOSING ETCH PATTERN
| 22 ORIENTED ETCH PITS
| 21 HIGH RELIEF (>10p)
| 20 MEDIUM RELIEF
| 19 LOW RELIEF (<0.5jj)
| 18 ROUNDED OUTLINE
| 17 ANGULAR OUTLINE
| 16 V ' s
| 15 CURVED SCRATCHES
| 14 STRAIGHT SCRATCHES
| 13 MEANDERING RIDGES
| 12 ADHERING PARTICLES
| 11 IMBRICATED GRINDING FEATURES
| 10 PARALLEL STRIATIONS
| 9 FRACTURE PLATES/PLANES
I 8 ARCUATE STEPS
| 7 STRAIGHT STEPS
'.J
| 6 LARGE CONCHO I DAL FRACTURE (>1 OOf.)
| 5 MEDIUM C0NCH0IDAL FRACTURE
| 4 SMALL C0NCH0IDAL FRACTURE (<10fi)
| 3 LARGE IRREGULAR PITS (>100p)
| 2 MEDIUM IRREGULAR PITS
I 1 SMALL IRREGULAR PITS (<10 )
8.14);
(f) Vibration.
Vibration at high magnifications
results in a wavy image on t h e screen; sharp knocks
t o t h e i n s t r u m e n t while a p h o t o g r a p h is being t a k e n
can result in fault-like dislocations in pictures as in
Fig. 8.14.
(g) Dirty photo-screen. In some instruments t h e r e
is a strong tendency for t h e photo-screen t o b e c o m e
electrically charged and attract dust particles which
a d h e r e to the surface. T h e patches w h e r e dust
a d h e r e s a p p e a r as diffuse d a r k e r areas o n p h o t o
graphic prints since t h e dust h a s cut o u t s o m e light
from t h e c a m e r a . T h e photo-screen should b e in
spected and cleaned regularly to prevent t h e accum
ulation of dust.
8.8
253
N.H. T R E W I N
S U B A Q U E O U S
252
SOURCE ROCK
r LOW ENERGY
.,
1 MEDIUM ENERGY
FLUVIAT1LE
HIGH ENERGY
I TORRENTIAL
r
SUBAERIAL
MARSH
DELTAIC
( LANDWARD
CHANNEL < MEDIAL
I SEAWARD
MARINE
/ INTERTIDAL
"
\ SUBTIDAL
' COASTAL
AEOLIAN
<y HOT DESERT '
GLACIAL
f SILICA
. / TEMPERATE :
J DISSOLVED '.\ TROPICAL
PED0L0GIC
| SILICA
'/'TEMPERATE.';'
I PRECIPITATED \ IRC'ICAI
SUBSURFACE D I A G E N ;T .J-.C :
CRYSTALINE
r
l r
A K 1 N t
o
O
o
O
Fig. 8.15. Quartz grain surface textures characteristic of various sedimentary environments. Redrawn from Higgs (1979).
http://jurassic.ru/
N.H. TREWIN
Tendency
T3
CD
surface
textures
during Ion
transport
O
~
uniformity
of acquire
C CD
CO cj
E S r n
Production of
large overgrowths,
solution surfaces,
and grain con tact
points
Grains with i
different sur
features botl
inherited am
acquired
resulting
254
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Si. =3
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256
N.H. TREWIN
- 1
8.9.4 Ancient d e p o s i t s
T h e vast majority of p a p e r s on surface textures
utilize material from c o n t e m p o r a r y e n v i r o n m e n t s .
Extension of t h e technique to the interpretation of
ancient sedimentary environments requires that t h e
surface texture survives diagenesis, probably in
cluding s o m e d e g T e e of lithification. In most cases
quartz solution, overgrowths and cementation will
have destroyed surface textures produced during
transport but m a n y examples d o exist, such as aeolian
textures preserved on Triassic sand grains (Krinsley,
Friend & Klimentidis, 1976), and R e h m e r &
H e p b u r n (1974) recovered grains with typical glacial
textures from t h e Palaeozoic S q u a n t u m 'Tillite' of
Massachusetts.
8.9.3 Experimental w o r k
S o m e experimental work has been d o n e to repro
duce surface textures in the laboratory. Krinsley &
D o o r n k a m p (1973) report the reproduction of tex
tures similar to those on glacially transported grains
by freeze and thaw e x p e r i m e n t s , and the production
of V-shaped pits and grooves by water transport.
Most experimental work has been performed on the
production of aeolian surface textures. Kaldi,
Krinsley & Lawson (1978) m o u n t e d individual grains
from different e n v i r o n m e n t s on a stub together with
crushed quartz and p r o d u c e d the characteristic ' u p
turned p l a t e ' textures on the grains in only 24 h o u r s
of abrasion by q u a r t z in a 'wind bottle' with a 'wind
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257
8.9.5 C o n c l u s i o n
T h e study of surface textures has certainly been
shown to be of practical value, but a great deal m o r e
controlled experimentation with source rock dis
integration, weathering and transport media still
needs to be d o n e . M o r e comparative studies of
experimental and natural systems using the same
starting material would also be most useful. Perhaps
t h e greatest need is for a new 'atlas of surface
textures' to provide a fresh impetus to the studies. It
is a p p a r e n t that many workers have evolved their
own t e r m s which are not adequately defined. A t
t e m p t s have b e e n m a d e to redefine features, such as
t h e proposed terminology for cracks and hollows of
Baynes & D e a r m a n (1978), but unless a generally
accepted and m a n a g e a b l e list is adopted the tech
nique will possibly die or remain in the hands of a
few faithful a d h e r e n t s .
For the practical sedimentologist the grain surface
texture technique is a useful adjunct to other studies
leading to environmental discrimination. It should
be used in conjunction with detailed grain size and
258
N.H. TREWIN
8.10.2 Practical c o n s i d e r a t i o n s
IDENTIFICATION OF MINERALS
8.10 S A N D S T O N E D I A G E N E S I S
8.10.1 General
T h e S E M with E D S is an essential tool for t h e
examination of p o r o u s sandstones. I m p r e g n a t e d and
stained thin sections, and X R D analysis of clays,
feldspars a n d c a r b o n a t e s can provide much infor
mation, but to investigate the morphologies and
detailed textures of grain overgrowths and diagenetic
minerals t h e S E M is essential. Details of fine-grained
clays a n d o t h e r grain coatings a n d pore-fillings can
not generally b e obtained from thin sections. W i t h
t h e S E M , mineralogy, textures a n d diagenetic
sequences can b e b e t t e r elucidated a n d porosity a n d
permeability can b e related to diagenetic a n d d e
positional textural features. It is the study of oil and
gas reservoir rocks which has provided t h e greatest
boost for S E M studies in t h e past ten years a n d t h e
S E M studies have now sparked off considerable
experimental diagenesis w o r k .
Burley et al. (1985) h a v e provided a useful review
of clastic diagenesis which clearly shows t h e impor
tant role of S E M studies a n d their relation to other
essential experimental m e t h o d s . T h e contribution of
t h e S E M in studies of sandstone diagenesis a n d t h e
essential use of o t h e r techniques t o provide a bal
anced study is well illustrated by H u g g e t t (1984b,
1986) on t h e controls a n d diagenetic sequence of
Coal M e a s u r e s sandstones, Kantorowicz (1985) on
t h e M i d d l e Jurassic of Y o r k s h i r e a n d Burley (1986)
o n Jurassic sandstones of t h e Piper a n d T a r t a n fields
of t h e N o r t h Sea. Increasing use is being m a d e of
c o m b i n e d S E a n d B S E studies of sandstones as illus
t r a t e d by Pye & Krinsley (1986a) on Rotliegend
sandstones, and of combined B S E a n d c a t h o d o
luminescence ( R u p p e r t et al., 1985 a n d Fig. 8.8).
F u t u r e progress will involve m o r e e x p e r i m e n t a l
work and comparison of natural and laboratoryproduced features in a t t e m p t s to simulate diagenetic
conditions. H u a n g et al. (1986) d o c u m e n t e d experi
m e n t s o n the conversion of feldspar to illite, a n d
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260
N.H. TREWIN
DISSOLUTION AND R E P L A C E M E N T OF
GRAINS
Dissolution and replacement features are c o m m o n
in sandstones and most frequently involve feldspar,
carbonates and clays.
Dissolution of feldspar grains resulting in creation
of secondary porosity (Schmidt & M c D o n a l d , 1979a,
b) may leave small etched relics of feldspar or a
skeletal relic of clays. A l t e r a t i o n of feldspar to
aggregates of kaolinite is frequently responsible for
t h e patchy distribution of kaolinite seen in thin
section and with the S E M . Dissolution of ferromagnesian minerals such as amphibole (hornblende)
and pyroxene (augite) is well d o c u m e n t e d by W a l k e r
et al. (1978) and W a u g h (1978a) w h o illustrated
spectacularly etched crystals.
C a r b o n a t e s frequently c e m e n t sandstones and
also replace detrital grains. T h e replacement is fre
quently highly selective resulting in replacement of
particular minerals. Feldspar and quartz are most
frequently affected, but many examples exist w h e r e
o n e or t h e o t h e r is attacked preferentially. Replace
m e n t features of c a r b o n a t e - c e m e n t e d sandstones
can be revealed by etching the carbonate to reveal
surfaces of replaced grains and relics of part re
placed grains (Fig. 8.18c). Burley & Kantorowicz
(1986) illustrated features of quartz grain surfaces
resulting from replacement textures caused by car
b o n a t e c e m e n t s , so allowing recognition of some
sandstone from which c a r b o n a t e cement had been
Fig. 8.18. (a) Detrital grain (right) with amorphous coating containing Si, Al, K, Mg and Fe. Mg-chlorite rosettes grow on
the grain coating and pre-date development of isolated euhedral authigenic quartz. Permian aeolian sandstone, Corrie
Shore, Arran, Scotland.
(b) Sandstone with amorphous Fe-rich coatings on detrital grains from which illite has grown into pore space. Quartz grain
contact solution surface at top left. Rotliegend aeolian sandstone. Lower Permian, southern North Sea.
(c) Cut and acid-etched surface of calcite cemented sandstone. Cut grains stand out from the (darker) etched calcite
cement. Detail shows two grains extensively replaced by calcite but with preserved illitic clay rims. Carboniferous
sandstone, Canning Basin, West Australia.
(d) Solution contact between detrital mica and quartz grains; the platy mica is broken away to reveal the smooth flat
contact-solution surface of the quartz grains beneath. Upper Jurassic sandstone, Claymore Field area, North Sea.
(Photograph by I.S.C. Spark.)
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261
MECHANICAL
DEFORMATION
262
N.H. TREWIN
E V I D E N C E OF O R D E R OF D I A G E N E T I C
EVENTS
T h e o r d e r of d e v e l o p m e n t of authigenic minerals is
usually stratigraphically based on the assumption
that the younger phases grow on the older. C o m
plications arise in t h e case of grain r e p l a c e m e n t s
w h e n it is not always possible to tell w h e n replace
m e n t took place relative to o t h e r diagenetic events.
D e s p i t e t h e simplicity of the basic premise t h e r e are
several factors which can combine to produce ambig
uous evidence of t h e o r d e r of diagenetic events.
T w o mineral phases may grow at the same time and
a later mineral p h a s e may grow to enclose previous
ly formed material. S o m e minerals have favoured
substrates for growth and diagenetic minerals will
not be evenly distributed on grain surfaces; thus
grains both with and without a particular overgrowth
or coating may occur in close proximity.
In rocks with low permeability diagenetic phases
a r e not evenly distributed, possibly d u e t o differing
local flow rates and chemistry of p o r e water, ion
availability from altered grains, or substrate avail
ability. Such variations can occur on a large scale as
with the obviously different diagenetic histories be
t w e e n c a r b o n a t e c e m e n t e d concretions in sand
stones and the adjacent u n c e m e n t e d rock. T h u s a
wide study of m a n y specimens is required t o establish
a full diagenetic sequence for a particular formation.
DIAGENETIC SEQUENCE
T h e S E M is an essential tool in the elucidation of
diagenetic sequences involving the d e v e l o p m e n t of
authigenic minerals. H u r s t & Irwin (1982) have
summarized s o m e of t h e sequences recorded in re
cent years and their s u m m a r y illustrates well t h e
variation to be found in the o r d e r in which authigenic
minerals develop u n d e r different circumstances.
H u r s t & Irwin listed important factors influencing
diagenesis; their list can be modified as follows:
RED BEDS
1
2
3
Temperature
Pressure
Detrital mineralogy, roles of stable and unstable
grains
4 O r g a n i c geochemistry
5 Availability of c a r b o n a t e , both biogenic and
non-biogenic
6 P o r e water composition, migration of p o r e fluids
and gases, and evolution
7 S e d i m e n t t e x t u r e , porosity and permeability
8 Sedimentary facies, including enclosing forma
tions
9 Tectonics
10 T i m e
In view of the n u m e r o u s variable influences, pro
jects involving interpretation of diagenetic sequence
require a great deal of background information.
Evidence should certainly be sought o n t h e follow
ing p o i n t s :
Depositional e n v i r o n m e n t . M a r i n e or fresh water
and if fresh water, vadose or phreatic? Likely initial
p o r e water type, and later p o r e water modifications?
Mineralogy. Is t h e original detrital mineralogy
preserved or recognizable; what major changes have
t a k e n place?
T e x t u r e . W h a t was t h e original texture (grain
size, sorting) and how has it been modified? H o w
has porosity and permeability b e e n altered?
Burial history. W h a t is t h e burial history.ln terms
of maximum burial d e p t h , when did this occur, and
h a s m o r e than o n e cycle of burial t a k e n place?
P o r e fluid and gas. H a s the rock been flushed by
different pore fluids at any t i m e , what was the final
p o r e filling prior to collection (e.g. air, gas, oil, fresh
water, saline water?
F r o m these considerations it may be possible in
well-explored areas to estimate likely pressures and
t e m p e r a t u r e s and reconstruct with s o m e accuracy
t h e geological history of t h e formation.
Diagenetic studies can be organized to examine
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WWII!
263
'MARINE' SANDSTONES
Sandstones with original m a r i n e p o r e waters have
varied diagenetic histories (Hurst & Irwin, 1982)
which may c o m m e n c e with illite/smectite (Hawkins,
1978) or chlorite (Tillman & A l m o n , 1979) or con
cretionary c a r b o n a t e , but frequently are c e m e n t e d
by quartz overgrowths. T h e earliest phase of quartz
c e m e n t , particularly in sandstones adjacent to shales,
may be of randomly oriented microquartz crystals
on grain surfaces (Fig. 8.17f), which subsequently
inhibit the formation of quartz overgrowths (Spark
& Trewin, 1986).
Following establishment of a rigid frame, dissolu
tion of unstable grains may result in secondary
porosity or production of kaolinite by feldspar alter
ation. T h e kaolinite in m a r i n e sandstones frequently
forms p o r e filling c e m e n t s of well formed euhedral
crystals of 4 - 1 0 um size ( H u r s t & Irwin, 1982).
C a r b o n a t e is frequently introduced after the initial
quartz overgrowth phase both as cement and as
grain replacement, particularly of feldspars, and this
p h a s e of diagenesis may eliminate most porosity.
D e e p e r burial may, however, result in carbonate
dissolution producing secondary porosity (Schmidt
& M c D o n a l d , 1979a, b) which can be available for
occupation by migrating hydrocarbons. Production
of organic acids during the maturation of organic
matter is frequently thought responsible for second
ary porosity d e v e l o p m e n t by silicate (frequently
feldspar) dissolution.
E n t r y of h y d r o c a r b o n s effectively stops diagenetic
reactions (Hawkins, 1978) but reactions can con
tinue in adjacent water-saturated sandstones to pro
duce further q u a r t z , kaolinite or illite cements,
resulting in diagenetic contrasts at oilwater
contacts.
'FRESHWATER'
SANDSTONES
264
N.H. TREWIN
P O R O S I T Y A N D ^ P E R M E A B I LITY
T h e permeability of a sandstone is related to the size
and shape of p o r e throats which connect larger p o r e
volumes in a s a n d s t o n e , the tortuosity of pores, and
t h e specific surface area within p o r e space. T h e
S E M is ideal for examination of pore geometry by
m e a n s of p o r e casts and also ideal for viewing t h e
factors which serve to reduce porosity and p e r m e
ability in sandstone. O n e of the most obvious exam
ples of permeability reduction by t h e formation of
authigenic minerals within p o r e space is that pro
vided by the illite diagenesis of the Rotliegend sand
stone of the southern N o r t h Sea where delicate illite
crystals bridge and block p o r e throats (Fig. 8.18b),
so reducing permeability. T h e Brent Sandstone
(Middle Jurassic, North Sea) displays similar fea
tures with illite also responsible for permeability
reduction (Hancock & Taylor, 1978; Blanche &
W h i t a k e r , 1978), and t h e M a g n u s reservoir ( U p p e r
Jurassic, N o r t h Sea) is similarly affected ( M c H a r d y
et al., 1982). Kaolinite is not usually so detrimental
to permeability as illite since it has a larger grain
size, and smaller surface area (Fig. 8.17c) so that
p o r e tortuosity and water absorption o n t h e clay
surface are not so great. Kaolinite also tends to be
m o r e patchy in its distribution in the rock. S E M
studies can be valuable in the assessment of microporosity in reservoirs as in t h e case of p o r c e l a n e o u s
c e m e n t of opal, microquartz and montmorillonite
described from M i o c e n e turbidite sandstones of t h e
Los Angeles Basin by Sears (1984).
As oil migrates into a reservoir diagenesis is arrest
ed as in the case of the B r e n t Sandstone ( H a n c o c k &
CONCLUSION
8.11.2 Examples
CARBONATE GRAINS
8.11 L I M E S T O N E S A N D D O L O M I T E S
8.11.1 General
Utilization of t h e S E M for t h e study of limestones is
most valuable in the examination of fine-grained
p o r o u s limestones such as chalk (Scholle, 1977) and
for tracing t h e evolution of cement and r e p l a c e m e n t
fabrics in Recent to sub-Recent carbonates (Bathurst,
1975; F o l k , 1974a; J a m e s et al., 1976; Wilkinson
et al., 1982). In studies of m o d e r n fine-grained car
b o n a t e sediments the morphologies and origins of
grains can be d e t e r m i n e d ( H a y et al., 1970) and
detail of biogenic particles m o r e easily recognized.
Textures and p o r e geometry of dolomitized and
dedolomitized sediments a r e also suitable for ex
amination as in examples of Silurian dolomite dia
genesis in the L o c k p o r t F o r m a t i o n , U S A (Shukla &
F r e i d m a n , 1983), dolomitized C r e t a c e o u s chalk of
E u r o p e ( J o r g e n s e n , 1983) and recent Australian
C o o r o n g dolomites (Von D e r Borch & Lock, 1979).
F o r a general discussion of c a r b o n a t e petrology,
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265
CEMENTATION OF C A R B O N A T E S
T h e r e are many cases in which early cementation of
c a r b o n a t e s occurs in m a r i n e subtidal and intertidal
conditions and in freshwater phreatic and vadose
situations. T h e morphology of the cements pro
duced can ideally b e examined using the S E M and
much m o r e detail obtained than is possible in thin
section. In freshwater solutions with low M g
con
centrations there is a tendency for simple r h o m b s to
grow, but in solutions with a high M g
concentra
tion sideways growth of t h e crystals may b e poi+ +
+ +
266
N.H. TREWIN
267
Fig. 8.20. Examples of cementation and dissolution in RecentPleistocene oolitic rocks and sediments from Shark Bay,
West Australia.
(a) Blocky clacite cement concentrated at grain contacts as a meniscus cement in a oolite cemented in the vadose zone.
Lithified sub-Recent oolitic aeolian dune deposit. Carbla Point, Hamelin Pool.
(b) Oolite with aragonitic ooids largely dissolved to leave secondary oomoldic porosity, some primary intergranular
porosity remains within blocky calcite cement. Pleistocene oolitic aeolian dune sand below calcrete crust. Hutchison
Embayment.
(c) Bladed aragonite cement. Recent submarine cementation of oolitic hardround in Hamelin Pool.
(d) Aragonite cement evenly coating grains in a recent oolitic hardground. Enlargement (marked scale x 5) shows etched
quartz grain surface beneath an ooid rim. Some borings present in ooid surfaces. Hamelin Pool.
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268
N.H. TREWIN
DOLOMITIZATION
Dolomitization of limestones frequently results in
t h e creation of useful interconnected porosity as
discussed and illustrated by W a r d l a w (1976),
W a r d l a w & Cassan (1978) a n d Davies (1979). D o l o
mite formation has been attributed to a variety of
processes in early diagenesis (summaries in Bathurst,
1975 and Z e n g e r , D u n h a m & E t h i n g t o n , 1980).
Dolomitization frequently affects only specific
c o m p o n e n t s of a limestone, as for e x a m p l e w h e n
bioclasts a r e dissolved and cementing calcite dolo
mitized. Figure 8.22 shows an example from t h e
subsurface Devonian of West Australia (geology of
area summarized by Playford, 1980) w h e r e ooids
have b e e n dissolved and t h e c e m e n t dolomitized,
and also an e x a m p l e with diagenetic illite a n d k a o
linite developed in p o r e space of t h e d o l o m i t e during
freshwater invasion of a marine limestone following
its dolomitization. In these examples dolomitization
probably took place by mixing of fresh and marine
water.
Dolomitization of chalk from t h e N o r t h Sea
(Jorgensen, 1983) results in t h e production of dolo
mite r h o m b s of 1030 urn size which clearly over
grow original texture and fossils. D o l o m i t e forms
only 28% of t h e rock and appears to have formed
early in diagenesis. M o r e extensive dolomitization
of limestones is described by Shukla & F r i e d m a n
(1983) from the Lockport Formation (Middle Silurian)
of N e w Y o r k State w h e r e early incipient dolomitiza
tion of micrite took place in a supratidal environ
m e n t . Successive stages of dolomitization resulted in
dolomitization of all the g r o u n d m a s s , dolomitization
of g r o u n d m a s s and allochems a n d finally totally
obliterative dolomitization. S E M examination of
269
8.12 E N O O L O T H I C M I C R O B O R I N G S
8.12.1 General
T h e S E M has played an i m p o r t a n t role in t h e study
of microborings in c a r b o n a t e substrates, since it
enables t h e three-dimensional forms of micron-sized
borings t o be examined in detail.
Bioerosion is now recognized as a most i m p o r t a n t
factor in t h e reduction of c a r b o n a t e grains a n d
substrates, particularly in t h e shallow m a r i n e en
vironment. G o l u b i c , Perkins & L u k a s (1975) re
viewed t h e history of t h e study of microborings and
provided an extensive reference list. T h e larger
borings p r o d u c e d by echinoids, g a s t r o p o d s , bivalves,
polychaetes a n d sipunculids ( s u m m a r y in W a r m e ,
1975) a r e n o t studied using t h e S E M , b u t detailed
features of t h e walls of t h e borings can provide
useful information. T h e smaller borings d u e t o
sponges (particularly Cliona) are of suitable size for
S E M examination of fine detail a n d of s e d i m e n t
p r o d u c e d , but t h e greatest contribution of t h e S E M
is in the study of algal, fungal and possible bacterial
borings in grains and rock surfaces. O t h e r small
borings such as s o m e of those due to cirripedes,
bryozoa and foraminifera can also b e usefully ex
amined with the S E M .
8.12.2 Methods
P r e p a r a t i o n m e t h o d s are described in Section 8.5.
Study of recent borings should involve identification
of t h e organism responsible, b u t iii d e a d and fossil
material all that remains is a cavity or filled boring
which must b e p r e p a r e d by a suitable impregnation
or etching t e c h n i q u e . Considerable t a x o n o m i c
p r o b l e m s exist with respect t o endolithic algae and
fungi which a r e beyond t h e scope of this w o r k .
8.12.3 Sedimentological f a c t o r s
Bioerosion is of the greatest i m p o r t a n c e in car
b o n a t e e n v i r o n m e n t s and o n coastlines with exposed
carbonate-rich rocks, b u t is by n o m e a n s confined
Fig. 8.21. (a) Resin pore-cast of interparticle porosity; carbonate aeolian dune sand, Pleistocene, Shark Bay, West
Australia.
(b) Resin pore cast of secondary oomoldic porosity in the same rock as in Fig. 8.20(b). Calcite has been dissolved, but a
dolomite rhomb remains within the pore cast at lower centre of picture.
Fig. 8.22. (a) Coarse dolomite with intercrystalline porosity containing books of kaolinite; small illite plates and ribbons
are also present on dolomite surfaces.
(b) Dolomite with oomoldic porosity due to dissolution of ooids, some intergranular porosity remains.
Both from Yellow Drum Formation, Upper Devonian, Canning Basin, West Australia.
to such situations. T h e organisms responsible for
microborings have specific ecological r e q u i r e m e n t s
and t h u s a zonation of such organisms can be recog
nized with respect to factors such as water d e p t h ,
tidal r a n g e , light p e n e t r a t i o n and climate. T h u s t h e
identification of borings can lead to interpretations
(Fig. 8.23) on the d e p t h ranges of boring algae and
fungi (Golubic et al., 1975; L u k a s , 1979). L i m e s t o n e
coasts are generally subject to intense bioerosion,
with distinctive zones of bioerosion leading to d e
velopment of features such as a biogenic notch w h e r e
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270
N.H. TREWIN
cellular activity, thus only 2 - 3 % of the substrate is
dissolved, t h e rest contributing to sediment produc
tion. Typical sediment chips and wall features of t h e
boring are illustrated in Fig. 8.25. In early coloniza
tion stages N e u m a n n (1966) found that Cliona des
troyed 57 kg limestone m in 100 days, but since
Cliona ceases t o b o r e after reaching a particular
d e p t h this figure is well in excess of t h e n o r m a l r a t e
which Rutzler (1975) calculated to be 250 m g of
sediment p e r m p e r year in B e r m u d a , which can
account for up to 4 1 % of sediment in m u d pockets
within a coral framework. F u t t e r e r (1974) found
sponge excavated particles to constitute 3 0 % of
Fanning Island (Pacific Atoll) lagoonal sediments,
and 2 3 % of samples from t h e A r a b i a n Gulf and
t h e Adriatic. H e also illustrated typical grains and
showed how the edges b e c o m e r o u n d e d by abrasion.
A c k e r & Risk (1985) calculated rates of bioerosion
by Cliona caribbaea in t h e shallow terrace zones off
271
2
G r a n d C a y m a n ( B . W . I . ) to b e 8 k g limestone m
p e r a n n u m , most of which is rapidly transported
d o w n s l o p e . S E M p h o t o g r a p h s of fine fractions ( 3 4 c[>) w e r e used for estimation of a b u n d a n c e of
sponge-produced chips.
High t i d e /
A i
Low t i d e / ^
ENDOLITHIC ALGAE
Endolithic algae have b e e n r e p o r t e d to b o r e at rates
varying from 0.3 t o 36 um/day (data s u m m a r y in
L u k a s , 1979) but most can only reach a d e p t h of a
few millimetres d u e to light r e q u i r e m e n t s . Their
activity m a k e s t h e rock o r grain surface w e a k a n d
p o r o u s and thus m o r e subject t o mechanical erosion,
but it is t h e activities of grazing animals such as sea
urchins, gastropods, chitons and fish which rasp
away the algae infested rock which result in most
sediment production. Grazing activity r e m o v e s the
surface layer and allows t h e algae to b o r e d e e p e r
Table 8.2. Examples of processes, mechanisms, traces produced, and habitats of some organisms responsible for
bioerosion (modified from Schneider, 1976)
Microboring
organisms
Destruction process
Mechanisms
Algae, blue-green,
green,red
Boring, internal
corrosion
Chemical solution?
Lichens
Chemical solution by
organic acids
Fungi
Boring, internal
corrosion
Chemical solution
Sponges,
e.g. Cliona
Boring
Chemical loosening of
small chips of
15100 um size by
acids and enzymes
SPONGES
Traces
Network of fine
Littoral to lower limit of
borings with specific
photic zone, mostly to
patterns. Up to 800
only 100 m depth,
urn deep. Tubes 1
extreme 370 m +
urn to 100 um but
most frequently
210 um. Various
rock surfaces
Various rock surfaces, Intertidal and supratidal
disintegration of
surface into small
particles
Very fine borings up to Intertidal and below to
2 mm deep.
1000 m +
Frequent 1-3 urn
hyphae with
sporangea 2 - 5 0 \im
but can be 812 urn
diameter tubes
From biological notch
Regular chamber
near low tide
system in rock with
downwards
openings to surface
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Jjjliil
Habitat
i i i liilh,
272
N.H. TREWIN
ACKNOWLEDGMENTS
T h e a u t h o r wishes t o thank D r I.J. Fairchild for Fig.
8 . 8 ( a - c ) , A . H o g g , E . Sellier and Total C F P for
Fig. 8 . 8 ( d - f ) , A . T . Kearsley for Fig. 8 . 9 ( a - c ) , and
R . L . G a w t h o r p e for Fig. 8 . 9 ( d - h ) . Figs 8.17(c, d)
and 8.22(a, b) were taken by the author at the
Fig. 8.25. Cliona borings in the bivalve Tridacna. Heron Island lagoon, Great Barrier Reef, Queensland, Australia.
(a) Typical sculpture of wall of boring, with two chips excavated by Cliona lying on the surface and showing the
characteristic convex outer surface (wrt the sponge).
(b) Typical concave etched facets of the inner surface of a chip.
and so continue t h e bioerosion process. F a r r o w &
Clokie (1979) illustrated typical effects of grazing by
limpets and chitons on algal-infested shells and t h e
consequent production of sediment. T h e r a t e of
destruction of c a r b o n a t e rock surfaces in various
environments is of the order of 1 m m y r (Schneider,
1976). Algal endoliths Have a long history extending
at least to t h e late P r e c a m b r i a n ( C a m p b e l l , 1982).
Typical algal endolithic borings are illustrated in
Fig. 8.24. T h e rate of c a r b o n a t e dissolution by micro
boring organisms was investigated in t h e lagoon of
Davies Reef, Australia, by T u d h o p e & Risk (1985).
Using t h e S E M , and observing i m p r e g n a t e d b o r e d
grains, the p e r c e n t a g e of borings could b e point
counted within grains. E x a m i n a t i o n of t h e surface
uncoated and u n d e r a weak vacuum p r o d u c e d high
contrast between resin-filled borings and c a r b o n a t e ,
and simplified point-counting.
_ 1
FUNGI
Fungal borings are difficult to distinguish from algal
borings, t h e r e being n o simple criteria for their
MICRITE ENVELOPES
Boring by endolithic algae and fungi o n loose car
b o n a t e grains is responsible for the formation of
micrite envelopes (Bathurst, 1966,1975). A b a n d o n
ed borings are filled by fine aragonite or high-Mg
calcite. Margolis & R e x (1971) illustrated t h e rela
tion b e t w e e n endolithic algae and micrite envelope
formation in B a h a m i a n oolites. Endolithic algae can
extensively colonize new substrates in w e e k s or
m o n t h s ( L u k a s , 1979 for s u m m a r y ) and thus repeat
ed abrasion and grain-size reduciton must occur d u e
to t h e activities of sediment ingesting organisms in
c a r b o n a t e environments (e.g. fish, holothurians).
T h e r e is a great deal of scope for use of t h e S E M in
examination of c a r b o n a t e grain surface textures d u e
to endolithic borers and their destruction by organic
and physical processes. T h e production of micrite
envelopes by boring is frequently t a k e n t o b e a
shallow water p h e n o m e n o m , but t h e d e e p water
fungal borings described by Zeff & Perkins (1979)
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ii
iimiiii
273
GENETIC
COMPONENTS
fT\
fT\
9.1
INTRODUCTION
aims
reference
chapter
of
have
275
t h e limitations of t h e d a t a d u e t o t h e sampling
p r o c e d u r e and analytical techniques used and an
ability t o assess t h e feasibility of b o t h chemical a n d
geological processes.
[y
..
VJ
rj
phases
e.g. sandstone
chemical/biological
e.g, shell gravel,
precipitates
primary evaporite
diagenetically transformed e.g. secondary
rock
dolostone
requires
Identification of component chemistry Interpretation
assumptions about
is straightforward
components' chemistry
TABLE OF ANALYTICAL
STRATEGIES
9.2 O B J E C T I V E S
Whole-rock
analysis
1
Objective
Successful a p p r o a c h e s t o problem-solving by
chemical analysis of sedimentary rocks a r e illu
strated in Fig. 9 . 1 . T h e potential presence of four
is illustrated: unmodified terri
genous detritus, leached or otherwise chemicallyw e a t h e r e d terrigenous detritus, chemical o r biologi
cal precipitates in t h e sedimentary e n v i r o n m e n t , and
authigenic (diagenetic) phases. A rock with, all four
c o m p o n e n t s is shown as a circle, otherwise t h e
a p p r o p r i a t e quarter-circles a r e depicted.
In t h e tabular part of Fig. 9.1 t h e analysed portion
of each rock is r e p r e s e n t e d by a blacked-in region.
C o l u m n s 1 and 2 refer respectively to whole-rock
analysis ( e . g . by X-ray fluorescence s p e c t r o m e t r y )
and selective analysis (e.g. by m i c r o p r o b e or by
analysis of t h e solute after dissolution of a particular
mineral). It is assumed in these cases that the mine
rals p r e s e n t can b e obviously assigned t o o n e of t h e
four petrographic c o m p o n e n t s of the rock and that
t h e e l e m e n t s of interest a r e obviously sited in par-
genetic components
Selective
analysis
2
Whole-rock or
selective analysis
3
*>,
Source-rock
chemistry
Chemical parameters
and transformational
processes of
sedimentary
environment
c
VI /
Chemical/physical/
biological parameters
of depositional
environment
Chemistry of diagenetic
fluids and/or nature
of diagenetic
processes
Elemental
cycling
:F
f *7
to
1\
274
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IIHIIH11
W H 1 W
276
277
9.3 C H E M I C A L P R I N C I P L E S
Since only a skeletal t r e a t m e n t is possible h e r e ,
particularly of t h e m o r e standard physical chemistry,
t h e r e a d e r is referred to the following texts for
further enlightenment: Krauskopf (1979) or B r o w n low (1979) for general geochemical background and
m o r e specific d a t a on sedimentary geochemistry;
Raiswell et al. (1980) and O p e n University (1981)
for an introduction to surface geochemical pro
cesses; G a r r e l s & Christ (1965) for an extensive
introduction to t h e practical application of t h e r m o
dynamic relations in a q u e o u s systems; B e r n e r (1980)
for a most r e a d a b l e introduction t o chemical p r o
cesses occurring in early diagenesis together with a
m o r e advanced mathematical t r e a t m e n t ; B e r n e r
(1971) for a wider but m o r e concise overview of
chemical sedimentology (excluding most sedimen
tary petrological aspects). T h e chemistry of natural
waters are well reviewed by Holland (1978), D r e v e r
(1982), and the somewhat less r e a d a b l e advanced
text of S t u m m & M o r g a n (1981), while t h e p a s t s t a t e
of t h e oceans and a t m o s p h e r e is t h e subject of a
masterly book by Holland (1984). T h e practical pre
diction of mineral stability in a given solution can now
be u n d e r t a k e n most easily and precisely by using
interactive c o m p u t e r p r o g r a m s such as phreeqe
(pH-REdox-EQuilibrium-Equations) which was devel
oped at t h e U n i t e d States Geological Survey and is
freely available (Parkhurst, T h o r s t e n s o n & Plumm e r , 1980; Fleming & P l u m m e r , 1983; P l u m m e r &
Parkhurst, 1985).
A basic understanding of t h e behaviour of ele
ments can b e achieved by considering their ionic
potential (Fig. 9.2). This is t h e charge (z) of t h e
a p p r o p r i a t e positive ion of t h e element divided by
its radius (r). W h e r e zlr is less than 3 , t h e r e is
Soluble complex
anions
i
3
4
Ionic charge
Fig. 9.2. Ionic potential of elements (modified from Blatt et al., 1980).
relatively little affinity of the element for oxygen in
water molecules: the e l e m e n t forms simple cations
in solution surrounded by loosely-bound water mole
cules (water of h y d r a t i o n ) . With zlr between 3 and
12, the affinity for oxygen is greater and hydroxides
of t h e element readily form. W h e n zlr is greater
than 12, t h e affinity for oxygen is so great that
oxyanions result. B o t h t h e electropositive e l e m e n t s ,
forming hydrated cations, and the electronegative
elements forming anions, t e n d to remain in solution
at relatively high concentrations, whereas inter
m e d i a t e elements tend to be readily removed from
solution as hydroxides or m o r e usually by adsorp
tion on to solids (Li, 1981). W h e r e a s t h e elements
with very high or very low ionic potential tend to
occur in sediments as relatively soluble salts and
intermediate elements as unaltered or chemicallymodified detritus, all also occur as reactive metastable phases and b o u n d o n the surface of solids.
T h e behaviour of each element is therefore highly
variable, d e p e n d i n g on precisely which minerals and
dissolved species a r e p r e s e n t .
7:i
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- 1
- 1
- 1
- 1
- 1
2 +
_ 1
2 0
278
I.J. FAIRCHILD e t a l .
a, = Y,m,
(2)
- 1
7 = |Sm,(z,)
(3)
a p
= K
(5)
(11)
A G = -RT
In K
(6)
10
(V)
+ AG7
- AG
/ B
- AG
/ C
(8)
(4)
= K
w h e r e K is t h e (activity) solubility
product.
In a given solution, t h e Ionic Activity
Product
( I A P ) can b e d e t e r m i n e d :
+ cC~
(9)
K =
(*B )(fi -)
C
(10)
http://jurassic.ru/
IAP =
(a )(a -)
B
(12)
or t h e %
(13)
saturation:
% saturation =
IAP
t
(14)
r~.
N B s o m e a u t h o r s define Q as l o g ( I A P / K ) . If
Q = 1, t h e solution is at equilibrium (the salt tend
ing neither t o dissolve n o r t o precipitate) a n d is
said t o b e just ( 1 0 0 % ) saturated. With Q > 1, then
t h e solution is s u p e r s a t u r a t e d a n d o u g h t t o b e p r e
cipitating t h e salt, conversely an u n d e r s a t u r a t e d
solution ( Q < 1) should b e dissolving t h e salt.
T h e correct formulation of a n equilibrium con
stant for solid solutions h a s b e e n u n d e r d e b a t e with
particular reference t o magnesian calcites and clay
minerals. T h r e e different approaches have been
p r o p o s e d . Using magnesian calcites as an example,
fractional e x p o n e n t s can b e used ( e . g . T h o r s t e n s o n
& P l u m m e r , 1977):
10
K = (a )(a -)
where a
= activity of D raised t o t h e p o w e r d e t c . ,
and K is t h e thermodynamic
equilibrium constant for
t h e reaction. K varies only with t e m p e r a t u r e a n d
pressure. Sometimes t h e relationship is formulated
in t e r m s of concentrations (K becomes K ), but K
will vary with solution composition a s well as t e m
p e r a t u r e and pressure.
E q u a t i o n (5) expresses t h e relative stability of t h e
chemical species: t h e degree t o which reaction (4)
goes t o t h e right or left. A second way of expressing
relative stabilities of chemicals is by t h e c h a n g e in
free energy accompanying t h e reaction. T h e free
energy of a substance is t h e energy it possesses t o d o
work. F o r any reaction:
AG" = A G
9.3.2 Equilibrium
a t
( a
2
C
(15)
y - * ( a
2
M
y ( a
2
C
- ) -
^ ( C a , M g ) C 0
( C a
) (
C O ,
^ s ( C a C O , ) -
M g
>co
2
3
--
(17)
280.
+ OH .
(18)
- 1 .
(H XOH-)
+
OH
O H
pH = -log (fl ).
1 0
(20)
H C0
2
? H
HCO-T ^
+ HCCV
+
+ C0
2
3
(21)
".
Ac = m ~
+ 2m o "-
HCO
(23)
co
(22)
B ^ B"
n+
ne + C
B + C
+ ne
(half-reaction)
(24)
^ C
(half-reaction)
(25)
(overall reaction)
(26)
^ C + B "
HCO
1 0 3
2-
+ ^4
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282
2+
Fe
2 +
3 +
2+
Fe
F e
2 +
2+
Fe
- 2
2 +
3 +
R = K(Q
- 1)"
(31)
2 +
9.3.3 Departures f r o m e q u i l i b r i u m
2 +
- l)
(30)
For dissolution, we h a v e :
R = K(l
(32)
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3 _
_ 1
J = CU.
(34)
+ CU = 0.
(35)
284
(36)
_ 1
- 1
_ 1
_ 1
_ 1
(37)
oi
^r = constant
(38)
2 +
2 +
a d s
9.3.4 A d s o r p t i o n
e c
W h e n A G i is d o m i n a n t , t h e adsorption process
is relatively non-specific, that is, it d e p e n d s m o r e on
t h e charge of t h e ions being adsorbed t h a n o n any of
their o t h e r properties. H e r e t h e G o u y layer concept
applies, for which t h e r e a r e various detailed m a t h e
matical models ( P a r k s , 1975; van O l p h e n , 1977).
W h e n AGeiec < s u b o r d i n a t e , t h e adsorption is
specific to the adsorbent and the solid concerned.
F o r e x a m p l e , s o m e large organic molecules a r e ad
sorbed because t h e process of V a n d e r Waal's bond
ing contributes m u c h loss of free energy. B o r o n is
k n o w n to adsorb strongly and specifically to illite,
presumably by chemical b o n d i n g of B ( O H ) ~ groups
to sites o n t h e mineral surface (Couch & G r i m ,
1968). I n fact any solute species which is capable of
forming particularly strong complexes in solution, or
insoluble c o m p o u n d s with s o m e c o m p o n e n t of t h e
solid, will potentially show strong adsorption. It
should b e emphasized t h a t all gradations exist b e
tween specific and non-specific adsorption.
T h e sign a n d m a g n i t u d e of t h e surface charge on
most solids d e p e n d s o n the solution chemistry. For
e x a m p l e , considering hydroxides, they will either
b e c o m e positively charge by reactions such as:
e
e c
MOH + H
MOH
+
2
c h e m
h y d
Solid
Gouy
layer
Gouy layer
o r negatively charged:
normal solution
fixed
layer
Gouy
layer
normal
solution
m m
0
0 O
0 0 0
o 0 0:
0
(a)
(b)
Fig. 9.4. Schematic illustration of adsorption processes. For simplicity, the surface charge of the solid is shown as if
owing to lattice substitutions (as in clays) rather than because of adsorption of potential-determining ions (see text).
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285
286
MOH MO" + H .
+
2+
2-
Ca
K =
(flA
sol
s o l
(40)
sol
(41)
sol
e c
a d s
+ B
a d
^ B
+ A
ec
(42)
(B )(Aad)
+
(43)
)(Bad)'
Xft
= K'
(44)
B
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287
288
2 +
2 +
2 +
2 +
(45)
K
m_
Cr
T r
C r
Xln
("&)'
(46)
{mcrY
m +
^ TrM(ss) + C r
m +
m +
^ C r M (YTr )
m +
K =
(exp(-Ap/i?r)
(47)
m +
^TrM ( Y C r )
ar
where K
* d K-n-M are the solubility products of
t h e e n d - m e m b e r s of the solid solution, Y T r
and
Ycr
are t h e activity coefficients in a q u e o u s solu
tion, R is the gas constant, T t h e absolute t e m p e r a
ture and A p is a m e a s u r e of the d e p a r t u r e (in t e r m s
of free energy gain) of the real solid solution from
an ideal o n e .
If o n e could ignore the last two t e r m s in equation
CM
m+
m +
Sr
m +
289
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290
3500 \r
2 +
2 +
3000
RA
RB'
1 3
3 4
1 2
1 8
1 6
3 2
b(x) = 1000
Fig. 9.5. Summary of the results of Pingitore & Eastman
(1986) concerning Sr incorporation in calcite. Low values
of partition coefficient K result from high Sr or addition
of Ba or Na to the solution (see paper for quantitative
aspects). Even with Na present in solution, a high value
for K can be restored by increasing growth rate.
(R
R )
ST<J
(50)
R. s t d
2 +
2 +
(4a)
<*A-B
s t
1000(a _
A
- 1) or
10001na _
6A -
or
(51)
(52)
(53)
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291
CARBON
I 3
J 3
1 3
1 3
1 3
292
1 3
1 3
HYDROGEN
l s
I 8
l s
1 8
l s
l s
OXYGEN
l s
SULPHUR
ISOTOPE REFERENCE
i 8
, s
l 8
- 2 0
- 1 0
18
S 0%o
+ 1 0
+ 2 0
SMOW
1 6
ls
http://jurassic.ru/
STANDARDS
293
l s
1 8
1
294
I.J.
F A I R C H I L D ef
al.
CHEMICAL ANALYSIS O F S E D I M E N T A R Y R O C K S
Table 9.1. Characteristics of stable isotopes important in sedimentary systems (data from Hoefs, 1980)
Element
Isotope
abundance
International reference
materials ('standards')
Ratio
used
'H 99.9844%
D = H 0.0156%
D/H
12
13
13
16
17
l s
32
33
34
36
C 98.89%
C1.11%
0 99.763%
0 0.0375%
O 0.1995%
S
S
S
S
12
C/ C
1 8
3 4
95.02%
0.75%
4.21%
0.02%
1 6
3 2
V-SMOW
(Vienna Standard Mean
Ocean Water)
PDB
Cretaceous Belemnite
SMOW or V-SMOW
(Vienna) Standard Mean
Ocean Water. PDB often
used for carbonates
CD troilite
(troilite from the Canon
Diablo meteorite)
8 0 - S M O W = 1-03091 8
1 8
1 8
p d b
+ 30.91
1 8
p d b
= 0.97002 5 0 - S M O W - 29.98.
V
scales.
9.4 G E O L O G I C A L S A M P L E
COLLECTION
T h e starting point for t h e chemical analysis of any
geological material is t h e collection of t h e s a m p l e . If
this collection is not carefully planned and executed
any geological conclusions d r a w n from t h e analysis
are suspect and t h e errors introduced at t h e sampling
stage cannot be subsequently rectified, no m a t t e r
how skilled t h e analyst or sophisicated t h e equip
m e n t . T h e old c o m p u t e r aphorism of 'garbage in
garbage o u t ' applies equally well to geochemistry.
F r o m the point of view of sampling strategy, t h e r e
Range of variation
in sedimentary systems
8D = -430 to +50%o
,3
5 C = - 9 0 to + 2 0 %
18
5 0 = - 4 5 to + 4 0 % SMOW
8 S = - 4 0 to + 5 0 %
34
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295
296
9.5 P R E P A R A T I O N F O R C H E M I C A L
ANALYSIS
F r o m t h e time a geological sample is chosen for
collection considerable care must be t a k e n to mini
mize contamination. This can be present locally
from industrial activity, agricultural chemicals, as
part of natural processes, for example from salt
water spray, from t h e tools used to r e m o v e t h e
sample or from the materials used for storage.
T h e containers used t o transport and store t h e
material may add or r e m o v e e l e m e n t s , especially
>-
- 9 -
o-
<)
>
1>
<1
>
>
(1
<>
(>
-9
ee e
Traverse sampling
Traverse sampling
oo
1 'i
.
11
<>
(>
c'
(>
>
<1
<>
>
(a)
<>
<>
e
Areal sampling
<)
o
o
()
(b)
L2
CO
o
O
<)
o
o
tr
297
o
o
o
.
o o
Areal sampling
Traverse sampling
9.5.1 C r u s h i n g
In any subsequent processing of sediment or rock
samples, contamination is inevitable although it may
be possible t o reduce t h e effect t o insignificant levels.
T h e m e t h o d ( s ) chosen should b e dictated by t h e
type of chemical analysis and elements required,
and by any further investigations which may follow.
Areal sampling
(0
Fig. 9.7.(a) Example of traverse and areal sampling using a regular grid. The spacing is determined by the expected size
of the target.
ROCK SAMPLES
Different approaches are required d e p e n d i n g on
analytical strategy. W h e r e o n e spatial c o m p o n e n t of
the sample is to be analysed, sawing and thin section
ing should precede analysis. Whilst microbeam tech
niques m a k e use of polished sections, o t h e r m e t h o d s
require a p o w d e r e d sample which can be chipped or
drilled from sawn surfaces and then ground in an
(b) Example of simple random sampling along a traverse and over an area. There may be a clustering of sample sites in
parts of the area and gaps left elsewhere. Note that it is possible that one site will be sampled more than once.
(c) Stratified random sampling where a grid of pre-determined size is randomly placed over an area and samples
randomly drawn from each grid cell. This reduces the clustering effect of simple random sampling.
(d) Balanced sampling using a nested hierarchical technique with duplicates collected from each site. Sample site and
analytical variability can both be studied but it is not necessary for every level to be fully replicated. In this example 72
samples would be analysed in duplicate. : (e) Unbalanced sampling using a nested hierarchical design. This produces a considerable saving in analysis with only 36
samples collected. Only one of the field duplicates need be analysed in duplicate.
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298
I.J. F A I R C H I L D ef AL.
O
C H E M I C A L A N A L Y S I S OF S E D I M E N T A R Y R O C K S
oo
o o
0
oo
oo
o oo
o o
oo
oo
0
oo
oo
o
oo
oo
oo
oo
oo
oo
o
oo
oo
o o
oo
Coloured plastic:
Oils:
oo
oo
Containers:
Polypropylene
Polythene
PVC
Brown paper
White paper
Rubber
Crushing:
Steel, iron, hard alloys
Ceramic, alumina
W carbide
Agate
Saws:
Diamond
Abrasive
Sieves:
299
Ti
Ti, Zn, Ba, Cd
Ti, Zn, Na, Cd
Si
Ti, Ba
Zn
Fe, Co, Cr, Mn, Ni, V, Cu, Mo, Zr
Al, Ga, B, Ba, Co, Cu, Fe, Li, Mn, Zn, Zr
W, Co, T i , R E E , Hf,Ta, Cu
Si, Pb
Cu, Fe, Cr, Mn, Ni
Al, Fe
Cu, Zn, Pb, Sb, Sn
Fe, Ni, Cr, Pb, Sn, Sb
Various
Various, Mo
oo
(d)
o
o
o
o
o
o
o
o
o
0
o
o
o
o
o
o
o
o
o
o
(e)
oo
http://jurassic.ru/
300
301
Table 9.3. Test of the contamination introduced during the crushing of an industrial silica sand in three separate Tema
swing mill barrels (ten 50 g samples in each). Milling time 1 min at high speed for W carbide and steel, 3 min for agate.
Analysis by XRF of duplicate 15 g powder pellets. Oxides as percentages, elements as ppm. The low value for Ni crushed
in carbide is caused by a W background interference. The difference in mean Zr values for carbide and agate can be
explained by sampling errors
W carbide
Fe 0 *
MnO
CaO
K 0
Ni
Cr
Zr
Sr
Pb
W
2
Agate
Range
Range
Range
0.259-0.284
0.002-0.004
0.156-0.209
0.107-0.137
1-2
14-23
48-107
12-13
2-4
751-1855
0.267
0.003
0.193
0.125
1.5
18
70
12.6
3.0
1430
0.01
0.001
0.03
0.01
0.6
3.8
25.6
0.6
0.7
457
0.233-0.994
0.002- 0.003
0.161-0.206
0.107-0.159
4-7
8-24
50-137
11-13
48-134
<2
0.268
0.003
0.195
0.133
4.8
15
88
12.0
90
0.02
0.001
0.02
0.02
1.3
6.3
33.6
0.7
37
0.290-0.344
0.003-0.006
0.176-0.202
0.119-0.146
4375-7163
629-962
84-126
11-14
2-4
<2
0.311
0.005
0.189
0.133
5588
775
102
12
2.8
0.02
0.001
0.01
0.02
1194
143
18
1.3
0.8
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Steel
302
303
Table 9.4. Errors introduced by sampling different masses and grain sizes of minerals of differing densities (g) using the
method of Moore (1979) (see Section 9.5.2). The 95% confidence limit is approximated to 2s. Note that the ranges are as
ppm of the mineral
60
x = 318
s = 313
n = 388
0)
Zircon
ZrSi0
4.7
Cassiterite
Sn0
?7
Gold
Au
gl9.3
40
Apatite
Ca F(P0 )
3.2
cr
CD
Mass
20
(g)
500
LU nnrin n
1000
o n
1500
Tin (fig g )
10
5
1
0.5
0.1
Cof V
%
5.7
8.0
18.0
25.4
56.8
Range at
95%
confidence
ppm
17.7
16.8
12.8
9.8
22.3
23.2
27.2
30.2
42.8
Cof V
%
3.4
4.8
10.8
15.3
34.3
Range at
95%
confidence
ppm
Cof V
%
18.6
18.1
15.7
13.9
6.3
21.4
21.9
24.3
26.1
33.7
2.8
4.0
8.9
12.6
28.1
561
88
52
48.7
31.1
26.6
21.5
1109
139
64
38
22.8
13.5
3.1
Range at
95%
confidence
PPm
CofV
%
Ran; *e at
95%
confidence
ppm
18.9
18.4
16.4
15.0
8.8
21.1
21.6
23.6
25.0
31.2
2.3
3.3
7.3
10.4
23.2
19.1
18.7
17.1
15.9
10.7
20.9
21.3
22.9
24.1
29.3
464
76
46
35.3
29.1
22.7
21.3
915
114
53
32
18.8
11.2
2.6
203
66
41
32.6
27.5
24.5
21.0
20
2248
280
130
78
46
27.4
6.4
1.5
9.0
17.5
919
132
72
51
38.5
31.0
22.5
1354
169
79
47
27.8
16.5
3.8
1.3
8.9
13.4
18.5
9.5.3 Sample d e c o m p o s i t i o n
A l m o s t all m e t h o d s of chemical a n d isotopic analysis
require t h e initial decomposition of t h e sample,
either directly, for example by an electrical arc or
spark as in optical emission spectroscopy, or chemi
cally by acid attack or fusion. Only t h e m e t h o d s
using t h e excitation of characteristic X-rays ( X R F ,
electron p r o b e ) a n d radiation techniques (such as
instrumental n e u t r o n activation analysis, I N A A ) can
on a routine basis employ the finely g r o u n d sample
p o w d e r alone.
In general the samples are presented for analysis
as solutions (in t h e special case of major element
d e t e r m i n a t i o n by X R F as a solid solution in the form
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4.7
10.9
17.3
18.7
7.4
12.5
15.5
19.0
304
D E C O M P O S I T I O N BY M I N E R A L A C I D S
Acid decomposition has b e e n widely used for m o r e
t h a n 30 years, both for major and minor e l e m e n t
analysis. It is now especially i m p o r t a n t for trace
analysis by atomic absorption and inductively cou
pled plasma m e t h o d s w h e r e t h e relatively low salt
c o n t e n t s of flame a n d plasma is a considerable ad
vantage. A further major advantage is t h e purity of
mineral acids. T h e m a x i m u m levels of each element
of interest in all analytical reagents should of course
be carefully checked. For trace analysis Analar
acids are the minimum purity, and it may be necess
ary to use the Aristar g r a d e or in e x t r e m e cases to
re-distill the most p u r e commercially available
material. Potts (1987) described t h e distillation
m e t h o d and lists impurities in nitric, hydrochloric
a n d hydrofluoric acids ( P o t t s , 1987, tables 1.21 and
1.22).
Decomposition vessels are possible sources of
contamination in trace level analysis and these should
be m o n i t o r e d . S o m e workers for e x a m p l e have been
t e m p t e d to use soda glass when digesting c a r b o n a t e s
in cold dilute HC1 only to find that alkali elements
are leached from t h e glass! E v e n borosilicate glass
may b e unsatisfactory and ideally P T F E o r , m o r e
cheaply, polyethylene or polycarbonate should b e
used (after rigorous cleaning). A d s o r p t i o n of s o m e
elements on t h e container walls may be a p r o b l e m
especially in t h e m o r e e x t r e m e decomposition pro
cedures discussed below.
Hydrochloric
B e r n a s (1968). T h e attack at t e m p e r a t u r e s of u p to
180C for 1 h o u r will d e c o m p o s e most resistant
minerals but t h e r e is t h e disadvantage that elements
may be absorbed at pressure by the P T F E . C a r e
should be t a k e n to m o n i t o r t h e possible release of
such elements in subsequent samples. Excess boric
acid is then a d d e d to complex t h e fluoride and it is
preferable to re-heat in t h e ' b o m b ' for ten minutes
at pressure to prevent the formation of insoluble
fluorides. E v e n h e r e s o m e resistant minerals may
remain and the solution should be checked and if
necessary t h e residue fused. This m e t h o d has t h e
disadvantage of producing a solution high in solids
which m a k e s analysis by I C P spectrometry difficult.
It should b e n o t e d t h a t the b o r a t e complexed
solution will still attack glassware!
SAFETY NOTE
Hydrofluoric
acid produces serious burns
requiring
hospital treatment with even minor contact.
Users
must be familiar with all necessary precautions
and
should have their method of work approved by a
Safety
Officer.
Perchloric acid is an extremely powerful
oxidizing
agent and should not be allowed to come into contact
with organic material. In addition, it forms
explosive
metal perchlorates. A scheme of work must again be
followed and the acid only used in an approved
fume
hood with wash-down
facilities.
D E C O M P O S I T I O N BY F U S I O N
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305
fluoride
306
Silica-alumina range
Apatite
Zircon
Limestone
Dolomite
Magnesite
Li metaborate
Li tetraborate
4
0
4
0
0
0
1
3*
1
5*
5*
10
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11111
307
SELECTIVE DISSOLUTION OF
CARBONATES
Analysis of t h e c a r b o n a t e fraction of i m p u r e car
b o n a t e s usually involves a compromise b e t w e e n an
effective dissolution agent and one that does not simul
taneously leach t h e n o n - c a r b o n a t e c o m p o n e n t s . P.
R o b i n s o n (1980) reviewed previous work and found
that for s o m e Palaeozoic carbonates 1M HC1 caused
n o m o r e leaching of M n , Sr o r N a from t h e insoluble
residue t h a n did 0 . 1 M acetic acid, yet was much
m o r e effective in attacking dolomite. I r o n , however,
was m o r e strongly leached. Boyle (1981) found that
finely-divided FeMn oxides were leached even by
Table 9.6. Typical maximum levels of impurity (in %) in
Li metaborate and Li tetraborate fluxes used in X-ray
fluorescence
Si
Ti
Al
Fe
Mn
0.0050
0.0020
0.0050
0.0010
0.0020
Mg
Ca
Na
K
P
0.0020
0.0100
0.0040
0.0020
0.0030
CI
so
F
As
Pb
0.0020
0.0050
0.0020
0.0020
0.0020
308
9.6 A N A L Y T I C A L T E C H N I Q U E S
9.6.1 Introduction
In this section, t h e p o p u l a r techniques for analysing
sedimentary rocks are discussed, notably those in
volving instruments rather than t h e 'classic', mostly
' w e t ' m e t h o d s of rock analysis. Analysis by electron
m i c r o p r o b e , X-ray fluorescence ( X R F ) , atomic ab
sorption spectrophotometry ( A A S ) , inductivelycoupled plasma spectrometry ( I C P ) , instrument
n e u t r o n activation ( I N A A ) and stable isotope mass
spectrometry are described, with t h e emphasis on
how sedimentary rocks are t r e a t e d , r a t h e r t h a n on
t h e details of the technique or instrument itself.
T h e r e are n u m e r o u s textbooks giving full explana
tions of all t h e various techniques (see Potts, 1987,
for o n e of t h e most r e c e n t ) , although these are often
written from t h e point of view of t h e hard-rock
geochemist, mostly concerned with silicate rocks.
Techniques which are not covered h e r e include flame
p h o t o m e t r y coiorimetric m e t h o d s , and those of or
ganic geochemistry, notably gas c h r o m a t o g r a p h y ,
mass spectrometry and pyrolysis.
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309
Filament
Accelerating
anode
Objective
lens
Gas-proportional
counter
(WDS)
Fig. 9.9. Schematic illustration of the elements of an
electron microprobe.
interactions of electrons can be divided into elastic
scattering, which involves a change in direction with
minimal loss of energy, and inelastic scattering. T h e
latter covers a variety or processes leading to energy
loss. F o r example, excitation of lattice oscillations
leads to heat production which is important because
of t h e thermal instability of certain sedimentary
minerals. T h e ejection of low-energy ( < 5 0 e V )
secondary electrons from t h e o u t e r parts of elec
trons is a n o t h e r inelastic scattering process, obvi
ously important in forming specimen images in t h e
S E M . A n o t h e r process, i m p o r t a n t in s o m e materials,
is t h e release of long-wavelength p h o t o n s : c a t h o d o
luminescence ( C h a p t e r 6). Also t h e r e is t h e deceler
ation of electrons by charge interaction with a t o m s ,
leading to the production of X-ray p h o t o n s whose
310
= 10 keV
= 20 keV
30 keV
secondary
fluorescence
X-rays
Fig. 9.11. Schematic illustration of the regions in the
specimen within which electrons are emitted or reflected
and X-rays generated. Scale depends on accelerating
voltage, and average atomic number of specimen (see Fig.
9.10).
Fig. 9.10. Simulation (by a Monte Carlo procedure) of electron paths (above) and K X-ray photons (below) in copper.
Note the emergence of backscattered electrons. The effects of atomic number are illustrated by the fact that equivalent
diagrams (at 20 keV) for gold and aluminium resemble the left and right diagrams respectively. From Heinrich (1981).
D E T E C T O R SYSTEMS
T w o alternative m e t h o d s of analysing t h e X-ray
spectrum are available: wavelength-dispersive sys
tems ( W D S ) and energy-dispersive systems ( E D S ) .
T h e original, and most analytically-sensitive ar
r a n g e m e n t ( W D S ) is t o m a k e use of a Bragg spectro
m e t e r in which t h e X-rays are diffracted by a crystal
and h e n c e s e p a r a t e d by wavelength (see also C h a p t e r
7). T h e crystal has a curved surface t o i m p r o v e
intensities of X-rays. B r a g g ' s law applies:
2d sin 9 = rik
w h e r e d interplanar spacing of t h e
diffracting
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311
STANDARDS
T h e intensities of characteristic lines in t h e speci
m e n ' s X-ray spectrum a r e c o m p a r e d with line inten
sities from material of k n o w n composition in order
to obtain a quantitative analysis. Ideally t h e refer
ence materials (standards) would be of very similar
composition to t h e mineral analysed so that electron
b e a m - m i n e r a l interactions would b e t h e s a m e , eli
minating t h e need for a correction p r o c e d u r e . This
a p p r o a c h is impractical w h e r e various minerals are
to be analysed. Normally geological m i c r o p r o b e
laboratories utilize a set of reference materials (ele
m e n t s , oxides a n d silicates) which a r e used in con
junction with a correction p r o c e d u r e for silicate and
oxide analysis, and often c a r b o n a t e and sulphide
analysis as well. E x a m p l e s of suitable materials are
312
A n electrically-conducting coating, 2 0 0 - 4 0 0 A
thick, usually of carbon, is applied to avoid t h e build
u p of charge on the surface of non-conducting
materials. Standards m u s t h a v e t h e s a m e thickness
of coating as t h e specimens: this is most easily
obtained by coating both at t h e same time.
OPERATING CONDITIONS
10
Energy (keV)
Fig. 9.12. Plot of the energy of the X-ray emission lines observed in the range 0,75-10 keV by energy-dispersive X-ray
spectrometry (simplified from Fiori & Newbury, 1978). ESC indicates escape peak. An example of peak overlap would be
the KfJ peak for Mn (element 25) and the Ka peak for Fe (element 26): both have the same energy. If Mn abundance Fe,
then Mn K(5 will have a similar strength to Fe Ka.
SPECIMEN PREPARATION
periclase (for M g ) , quartz (Si), jadeite ( N a ) , wollastonite (Ca) and metals for first series transition
elements. Synthetic glasses are also used and are
particularly useful for r a r e r elements with which t h e
glass can be ' d o p e d ' , b u t care has t o b e t a k e n
because of decomposition u n d e r t h e electron b e a m .
M o r e accurate analysis should in principle b e
achievable by using e n d - m e m b e r s of solid-solution
series, e.g. p u r e siderite for F e in calcite (Moberly,
1968; Jarosewich & M a c l n t y r e , 1983). U s e of other
than t h e normal laboratory reference materials
should be ^considered for study of, for e x a m p l e ,
m i n o r elements in carbonates or minerals with un
usually high concentrations of u n c o m m o n e l e m e n t s .
It is obviously vital to ensure t h e reference material
is h o m o g e n e o u s on all scales for t h e e l e m e n t s of
interest.
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313
CORRECTION
PROCEDURES
314
A N A L i s i a USING AN SEM
In t h e past t h e r e h a s b e e n very little use of S E M s b y
sedimentologists for quantitative analysis. T h e p r o b
lem is t h a t t h e p r e - e m i n e n t design a i m h a s b e e n
spatial resolution rather t h a n analytical convenience.
Low take-off angles h a v e led t o high absorption
corrections being necessary a n d t h e lack of optical
microscope attachments have led t o difficulties in
specifying t h e area t o b e analysed. This situation has
now changed with t h e introduction of c o m b i n e d
S E M - m i c r o p r o b e s a n d t h e increasing u s e of backscattered electron imagery t o relate chemical a n d
p e t r o g r a p h i c features ( H u g g e t t , 1984a). If speci
m e n s a r e polished as for n o r m a l m i c r o p r o b e work
t h e n t h e situation is t h e s a m e as t h a t described in
t h e previous sections.
U s e of t h e S E M in qualitative analysis (and hence
identification) is widespread in sedimentological
studies a n d is striaghtforward if t h e alternatives a r e
k n o w n a n d chemically distinct. Otherwise m o r e care
is n e e d e d : a n excellent s u m m a r y of guidelines for
qualitative analysis is given in Goldstein et al. (1981,
chapter 6 ) . Often analysis is u n d e r t a k e n o n fracture
surfaces of rock chips: h e r e o n e must b e particularly
aware of possible stray X-rays g e n e r a t e d from ad
j a c e n t minerals or t h e sample holder.
9.6.4 A t o m i c a b s o r p t i o n analysis
A t o m i c absorption s p e c t r o p h o t o m e t r y ( A A S ) h a s
b e e n widely used as a technique for elemental analy
sis of rocks a n d minerals, a n d also w a t e r s , since t h e
1960s. M o r e than 50 useful elements can be detected
and t h e technique has b e e n popular since it is a
relatively simple p r o c e d u r e , t h e instruments a r e
generally sensitive a n d reliable, a n d a basic A A
machines is n o t t o o expensive. Information o n A A S
is presented by A n g i n o & Billings (1972), J o h n s o n
& Maxwell (1981), Potts (1987), a n d others, a n d
most instruction manuals supplied with A A instru
m e n t s give much useful background material, as
well as guidance. H o w e v e r , it is possible that in t h e
future A A S will b e c o m e less widespread in its use as
I C P (Section 9.6.5) becomes m o r e readily available.
T h e principle of A A S is t h e absorption of radiant
energy by ground state a t o m s . W h e n a substance is
dispersed as a n atomic v a p o u r , it possesses t h e pro
perty of absorbing particular radiations, identical in
wavelength t o those which t h e substance can emit,
as w h e n it is h e a t e d for e x a m p l e . If a parallel b e a m
of radiation of intensity I is incident o n a n atomic
v a p o u r , I is t h e intensity of transmitted radiation
a n d v is t h e frequency, t h e n
0
I =
I exp(-K l)
- 2
w h e r e K is t h e absorption coefficient a n d / is t h e
atomic vapour thickness. T h e absorption coefficient
is also p r o p o r t i o n a l t o t h e concentration of t h e free
a t o m s in t h e vapour ( B e e r ' s law):
v
K dv
v
mc
Nvf
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iinmiiiiiiiiiiiiiiiiii]
317
Monochromator
to
Detector
Flame
cathode
to
Hollow
cathode
lamp
Lens
Filter
Slit
anode
Cloud
chamber
Fuel gas =={
(b)
Oxidant gas
Output
Nebulizer
1
CD
Sample
Reference beam
(rj)
Wavelength
Sample beam
http://jurassic.ru/
Flame"
INTERFERENCE
In atomic absorption analysis, interference is not
generally a major p r o b l e m . Spectral interference
can arise w h e r e two e l e m e n t s h a v e r e s o n a n c e lines
at a similar wavelength, resulting in a positive error
as t h e two signals a r e a d d e d together. A n alternative
line t o m e a s u r e can usually be found. S o m e metals
have a low ionization potential so that a smaller
n u m b e r of atoms remain in t h e ground state w h e r e
they can a b s o r b their characteristic radiation. T h i s
ionization interference can be overcome by adding
certain elements to t h e solution to suppress t h e
ionization. Chemical interference results from ele
ments combining to form stable c o m p o u n d s which
do not break down in t h e flame to form ground state
a t o m s . Negative errors arise, or even no absorption
at all occurs. T o overcome this, an excess of a metal
is a d d e d which can c o m p e t e with t h e metal being
d e t e r m i n e d for combination with; t h e interfering
To monochromator
and detector
2 +
SAMPLE PREPARATION
A A S has b e e n widely used in t h e analysis of lime
stones and dolomites since t h e interests h e r e are
318
Inductively-coupled
plasma atomic emission
spectro
metry ( I C P - A E S ) works on the principle that when
atoms and ions are excited t h e n light is emitted, and
t h e wavelengths a n d intensities of t h e light reflect
the elements present in t h e sample. T h e emission
spectra from atomization in the plasma are analysed
with a high resolution s p e c t r o m e t e r within the wave
length range of 170780 n m . T h e general arrange
m e n t of an I C P - A E S machine is shown in Fig. 9.17.
O n e of t h e major advantages of I C P - A E S over A A S
is that many elements can be analysed simultane
ously; s o m e instruments have a polychromator spec
t r o m e t e r capable of a c c o m m o d a t i n g m o r e t h a n 50
spectral lines. O n e of t h e p r o b l e m s with I C P - A E S
has been spectral interferences from overlaps be
N o w t h a t t h e s a m p l e h a s b e e n atomized and
ionized, t h e r e a r e t w o completely different techni
q u e s for measuring t h e concentrations of t h e various
319
Fixed diffraction
grafting
Entrance slits
to
mass spectrometer
for ICP-MS analysis
MS or AES
/
To
emission spectrometer
for ICP-AES analysis
t
Tailflame
Radio frequency
generator
Diffracted lines
Sample
capillary
Fixed exit
slit assmbly
Sample
solution
11
Cloud
chamber \
Waste (-97%)
Mirror
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I
1
I.
320
Name of
standard
Acid-blank
2C
1C
0.5C
0.1C
1.5CM
1CM
0.5CM
0.1CM
CI
C2
C3
C4
Dl
D2
D3
D4
D5
ICP-AES
Carbonate workers are likely to want to use I C P - A E S
in preference to o t h e r solution-based techniques
w h e n e v e r it is available: b o t h because of its rapid
sample t h r o u g h p u t and capability for simultaneous
analysis of m a n y e l e m e n t s , and because of t h e small
sample size (1 10 mg) required. Microsampled
powders can t h u s be analysed for both cations and
isotopes. Since t h e r e is little published on techni
q u e s specific to c a r b o n a t e s , a detailed account is
given h e r e . It also serves to illustrate m o r e generally
an a p p r o a c h t o standardization of chemical analysis
a n d correction of results.
A l t h o u g h d a t a can b e o b t a i n e d using generalp u r p o s e s t a n d a r d s designed for silicate rocks,, con
siderable e r r o r s a r e likely t o result b e c a u s e of t h e
Ion
detector
Pulse
amplifier
ICZH
ICP
torch
Sampling cone
and skimmer
Ion extraction
electrodes
Quadrupole m a s s
filter
Multichannel
analyser
and display
Fig. 9.18. Schematic representation of the inductively-coupled plasma mass spectrometer (ICP-MS).
321
Ca
Mg
Sr
Fe
ppm ( u g g )
Mn
_
800,000
400,000
200,000
40,000
300,000
200,000
100,000
20,000
400,000
400,000
400,000
400,000
200,000
200,000
200,000
200,000
200,000
50
200
500
4,000
50
200
500
2,000
2,000
120,000
80,000
40,000
8,000
200
400
1,000
5,000
120,000
120,000
120,000
120,000
120,000
200
400
1,000
5,000
200
1,000
5,000
20,000
100,000
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Na
- 1
200
400
1,000
5,000
.200
400
1,000
2,000
2,000
40
200
500
2,000
40
200
2,000
10,000
10,000
322
Output
voltage
(peak
minus
background)
region of
ine curvation
Element concentration
(a)
Background
level of
output
voltage
for minor
element
(b)
Output
voltage
for a
given
element
(c)
(no drift)
acid-blank
10
20
30
40
50
Date
User
Analysis nos
Stdwt
Cabkd
Cacorr
Cadrift
Mgbkd
CacorrMgbkd
Mgcorr
Mgdrift
Febkd
CacorrFebkd
MgcorrFebkd
Fecorr
Fedrift
Mnbkd
CacorrMnbkd
MgcorrMnbkd
Mncorr
Mndrift
Srbkd
CacorrSrbkd
MgcorrSrbkd
Srcorr
Srdrift
Nabkd
CacorrNabkd
MgcorrNabkd
Nacorr
Nadrift
30/10/86
ijf
17-44
10
70
49.8
0
82
0.0068
4.6
0
86
0
0.0005
5.1
0
103
0
0.0005
1.17
-0.0028
115
0.023
0
0^0354
-0.000056
175
0.0050
0.0025
1.36
-0.002
323
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lllllUliU
324
1
2
3
4
5
6
7
8
9
10
11
1
Sample
bcs368v
f6962a
f6975a
f6989b
f6890a
m4208b
m3852
f6890b
f6963b
m3855
2
Ca
3731
4112
4858
2865
1287
5917
4102
4910
4314
2282
8
Fin bkd
98
97
102
94
89
103
96
99
98
92
9
p-b
207
5827
5897
10439
2467
3069
5392
6621
2272
6094
15
Stdwt
10
10
10
10
10
10
10
10
10
10
16
Feppm
1090
27263
26616
69141
41932
11950
31247
30979
12200
54529
5
4
3
Febkd
Fe
Mg
86
305
23300
86
22250 5924
86
31330 5999
86
16141 10533
86
6768 2556
86
33200 3172
86
20770 5488
86
26130 6720
86
23070 2370
86
11191 6186
10
Fecorr
5.1
5.1
5,1
5.1
5.1
5.1
5.1
5.1
5.1
5.1
:
11
Fedrift
0
0
0
0'
0
0
0
0
0
0
. - 17
FeCC-3
0.23
5.66
5.52
14.34
8.70
2.48
6.48
6.43
2.53
11.31
6
CacorrFebkd
0
0
0
0
0
0
0
0
0
0
12
Fin corr
5.1
5.1
5.1
5.1
5.1
5.1
5.1
5.1
5.1
5.1
7
MgcorrFebkd
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
0.0005
13
Fe value
1057
29717
30076
53239
12580
15654
27497
33767
11590
31081
14
Weight
9.7
10.9
11.3
7.7
3
13.1.
8.8
10.9
9.5
5.7
. . I
Dolomite
x Calcite
85
90
95
100
Analytical total (%)
http://jurassic.ru/
105
110
1 3
l s
326
Magnet
MASS S P E C T R O M E T R Y
In simple terms a mass s p e c t r o m e t e r m a y b e t h o u g h t
of as an instrument to m e a s u r e relative differences
in t h e a b u n d a n c e of certain isotopes of a given
e l e m e n t . In all cases t h e sample is i n t r o d u c e d as a
gas (e.g. C 0 , S O 2 ) via an inlet system designed t o
allow t h e rapid comparison of t h e sample with a
reference gas p r e p a r e d at t h e s a m e time (Fig. 9.21).
O n c e inside t h e i n s t r u m e n t t h e gas is ionized by
electrical b o m b a r d m e n t in t h e 'source r e g i o n ' , the
ions are accelerated in an electrical field a n d collim a t e d t o e m e r g e as an ion b e a m . T h e ions within
this b e a m a r e then s e p a r a t e d according to their mass
by passage t h r o u g h a magnetic field, e m e r g i n g as a
series of b e a m s , each with a given mass a n d a
c h a r g e . Collectors for e a c h m a s s , usually a r r a n g e d
in t h e form of a metal c u p or F a r a d a y cage, are
placed at t h e a p p r o p r i a t e spot to collect particular
i o n s , which t h e n discharge o n t o t h e m . T h e strength
of t h e discharge, p r o p o r t i o n a l to t h e n u m b e r of ions
of each mass p r e s e n t , is t h e n registered electroni
cally and displayed as a ratio or, normally, trans
ferred automatically for s t o r a g e in a m i c r o c o m p u t e r .
3 4
To high-vacuum
system
a n c
j amplifier
Generally t h e p r e p a r a t i o n t e c h n i q u e s for m e a s u r i n g
sulphur isotope ratios seek t o yield p u r e sulphur
dioxide ( S 0 ) , although s o m e a u t h o r s prefer S F as
a n e n d - p r o d u c t . Sulphides a r e c o n v e r t e d t o S 0 by
reaction with a suitable oxidizing agent such as
C u 0 or V 0 , while sulphates h a v e b e e n tradi
tionally c o n v e r t e d first t o t h e sulphide b y a variety of
chemical m e a n s , a n d t h e n oxidized in a similar m a n
ner. Since a b o u t 1970, h o w e v e r , a variety of t h e r m a l
decomposition m e t h o d s h a v e b e e n d e v e l o p e d which
allow t h e direct reduction of sulphates t o S 0 .
2
B a S 0 - B a O + ?0
4
+ SO .
1 9
2FeS + 10BrF
2
O X Y G E N I S O T O P E S IN S U L P H A T E S
T h e r e are two possible objectives: the analysis of
0 / 0 in t h e sulphate or that associated with inter
stitial w a t e r of crystallization.
In the former case, t h e m o s t widely used p r e p a r a
tion t e c h n i q u e is the graphite reduction m e t h o d of
Rafter (1967). E a r l i e r w o r k by Rafter (1957) had
proved t h e general feasibility of producing C 0 by
reduction with carbon according to t h e reaction:
1 8
1 6
BaS0
+ 2C ^
BaS + 2 C 0
S0
V E R S U S SI
but at t h e t e m p e r a t u r e s involved ( 9 0 0 - 1 0 0 0 C ) a
C 0 - g r a p h i t e reduction reaction also occurred which
c o n v e r t e d some of the C 0 to C O . H e therefore
developed a modified t e c h n i q u e in which t h e first
a p p e a r a n c e of C O caused a pressure change in t h e
vacuum line which induced a high voltage electrical
discharge across two e l e m e n t s ; converting C O to
2
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T h e p r e p a r a t i o n p r o c e d u r e is relatively straight
forward for a p u r e s a m p l e , requiring only the oxida
tion of t h e sample to yield S 0 . U s e of oxygen as t h e
oxidizing agent ( T h o d e et al., 1961) required ex
tremely high t e m p e r a t u r e s (1350C) to hinder frac
tionation by S 0 p r o d u c t i o n , and to avoid formation
of A g S 0 from A g S ( R o b i n s o n & K u s a k a b e , 1975).
N e i t h e r p r o b l e m arises if a solid oxidant is used, as is
now normal.
A range of solid materials a r e utilized including
C u O (Ripley & Nicol, 1981), C u 0 ( R o b i n s o n &
K u s a k a b e , 1975; Kiyosu, 1980) a n d V 0 ( M a k e l a
& V a r t i a i n e n , 1978; G a v e l i n et al., 1960) a n d at
significantly reduced t e m p e r a t u r e s ; generally in t h e
range 6 0 0 - 8 5 0 C . R o b i n s o n & K u s a k a b e (1975)
carried o u t their reactions at 800C producing yields
of 99100% in approximately 10 minutes with con
taminating C 0 being r e m o v e d via an - p e n t a n e liquid nitrogen t r a p .
A pre-concentration step is needed for the analysis
of disseminated sulphide in a s a m p l e . Ripley &
Nicol (1981) dissolved their s a m p l e in c o n c e n t r a t e d
acid a n d used T h o d e solution (a boiling mixture of
H I , H P 0 and H C 1 , T h o d e et al., 1961) to convert
t h e sulphur to H S , a n d subsequently A g S . Sasaki
et al. (1979) stressed that Kiba r e a g e n t (a mixture of
tin I I a n d H3PO4) was far m o r e rapid than T h o d e
solution in extracting sulphide from pyrite. C a m e r o n
(1983) used Kiba r e a g e n t , but found that since this
also extracted organic S a n d S in B a S 0 a sulphidespecific dissolution stage was n e e d e d first ( D i n u r ,
Spiro & A i z e n s h t a t , 1980).
2
ANALYSIS OF SULPHIDE-SULPHUR
327
328
CO
2 C O -> C 0
+ C.
1 8
1 6
329
CARBONATES
1 8
1 6
1 3
1 2
B o t h 0 / 0 a n d C / C ratios can b e d e t e r m i n e d
in o n e operation by t h e evolution of C 0
from
c a r b o n a t e s . M c C r e a (1950) laid t h e basis for t h e
technique now used. M e a s u r e m e n t s of the ratios of
C 0 with mass 44 ( C 0 ) 45 ( C 0 ) and 46
( C 0 0 ) allows t h e two ratios to b e d e t e r m i n e d
since C and
0 are by far the most a b u n d a n t
isotopes. Successful mass spectrometry of C 0 thus
required a quantitative a n d reproducible extraction
p r o c e d u r e , lacking impurities in t h e mass range 44
46, as well as a lack of opportunity for oxygen
isotope exchange. M c C r e a (1950) found that thermal
decomposition did not give reproducible results, and
e x p e r i m e n t e d with various acids. T h e use of 100%
phosphoric acid ( H P 0 ) at 25C was found to be a
reliable technique for C a C 0 . T h e reaction takes
place in vakuo and t h e gas should be passed through
a cold t r a p of dry ice and m e t h a n o l (safer than dry
ice/actone) t o r e m o v e impurities (particularly H 0 )
before C 0 is frozen in a collection vessel i m m e r s e d
in liquid nitrogen. T h e sample size required will
typically be 10 m g o r less. S o m e laboratories routine
2
1 2
1 6
1 2
1 3
1 8
1 6
1 2
1 6
Fig. 9.22. Reaction system used in the laboratory of N.J. Shackleton to generate C 0 from foraminifera for isotopic
analysis. The whole region illustrated is kept at 50C. Orthophosphoric acid is dropped on to the foraminifera which have
previously been cleaned and vacuum-roasted in the sample thimble within container A. The acid is replenished monthly
and kept pumped so that it does not take up moisture (from Shackleton et al., 1984, with permission of the Ocean Drilling
Program, Texas A & M University).
2
1 6
ISOTOPIC CORRECTIONS
N o a t t e m p t will b e m a d e h e r e to provide a t h o r o u g h
account of t h e various corrections t h a t may b e a p
plied to ' r a w ' isotopic d a t a , since a good n u m b e r are
concerned with machine errors (e.g. inlet valve
leakage) or interference effects which a r e , strictly
speaking, outside t h e scope of this discussion; but
see Craig (1957), D e i n e s (1970) and B l a t t n e r &
H u l s t o n (1978). Since t h e processing of raw d a t a is
usually d o n e by c o m p u t e r , all necessary corrections
may be incorporated within the p r o g r a m and applied
automatically t o yield the adjusted delta value. It is
r e c o m m e n d e d that all correction factors should be
q u o t e d when publishing isotopic d a t a t o g e t h e r with
an approximation of t h e total analytical e r r o r (i.e.
the preparation and machine error combined).
lK
( 0/' 0)co.
~ r n/ rv>
l8
l6
v
'-Vcarbonale.
which results in t h e uncorrected 6 b value being
approximately 10% t o o heavy. This fractionation
1 8
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liiiiimiimiiiiiiifliiiiif
mechanism is t e m p e r a t u r e - d e p e n d e n t , hence it is
i m p o r t a n t always t o perform the acid decomposition
reaction at the same temperature (e.g. 25C or 50C).
S h a r m a & Clayton (1965) provided an account of
this particular correction, while T a r u t a n i , Clayton &
M a g e d a (1969) and R u b i n s o n & Clayton (1969)
outlined additional corrections for Mg calcites and
a r a g o n i t e . R o s e n b a u m & S h e p p a r d (1986) provided
t h e best compilation of d a t a on F e - and Mg-bearing
carbonates at varying t e m p e r a t u r e s . D o l o m i t e poses
particular p r o b l e m s since t h e r e is n o a g r e e m e n t o n
its fractionation factor with phosphoric acid. Most
330
T h e standard p r e p a r a t i o n m e t h o d of M c C r e a (1950)
outlined a b o v e was designed specifically t o c o p e
with calcium c a r b o n a t e , either as calcite o r aragonite
which react readily with phosphoric acid at r o o m
t e m p e r a t u r e . With o t h e r c a r b o n a t e species, how
ever, t h e reaction at 25C is very much slower a n d
can considerably lengthen t h e time to process each
sample. B e c k e r & Clayton (1972) p r e p a r e d samples
of calcite, dolomite, ankerite and siderite at 25C
a n d found t h a t while t h e calcite reaction was c o m
plete in 24 h o u r s , periods of o n e w e e k , two weeks
and two t o t h r e e m o n t h s respectively w e r e required
for t h e r e m a i n d e r . N o t only a r e such e x t e n d e d
periods of reaction inconvenient in routine work but
t h e r e is always a d a n g e r that t h e reaction vessel m a y
leak while not being actively p u m p e d , leading t o
contamination with atmospheric C 0 . F i n e grinding
of t h e sample t o increase t h e total surface a r e a can
b e used to speed u p t h e reaction but such t r e a t m e n t
is time-consuming and may cause isotopic exchange
with the a t m o s p h e r e . M u c h m o r e convenient is t o
increase t h e reaction t e m p e r a t u r e . G o u l d & Smith
(1979), for e x a m p l e , working with siderite, initially
mixed sample a n d acid at 80C and t h e n allowed t h e
mixture to react at 25C for 72 h o u r s . S t a n d a r d cal
cites treated in t h e s a m e m a n n e r showed n o change
in 5 C although 5 0 values were found t o b e t o o
light by 1.2%o and h e n c e all oxygens w e r e corrected
by this a m o u n t (see also G a u t i e r , 1982). Raising t h e
reaction t e m p e r a t u r e is particularly useful w h e n
working with dolomites, which at 50C react t o
completion overnight. B e a r i n g in mind t h e tem
perature-related changes in t h e phosphoric acid cor
rection factor, t h e standards should b e run at t h e
same temperature.
2
1 3
1 8
331
MICROSAMPLING
REMOVAL OF ORGANIC MATTER
T h e presence of organic carbon in samples of car
b o n a t e leads to t h e introduction of volatile sub
stances into t h e mass s p e c t r o m e t e r which form a
variety of reaction products in t h e ionization cham
b e r and interfere with t h e weak mass 45 and 46 ion
beams.
A l t h o u g h p r e - t r e a t m e n t s for t h e removal of
organic m a t t e r a r e most relevant to R e c e n t skeletal
aragonite, which h a s a very high organic content,
it repays to give s o m e t h o u g h t to t h e effect on
ancient c a r b o n a t e s . Charef & S h e p p a r d (1984) n o t e d
that sulphur-rich organic material is particularly
troublesome.
By far t h e simplest technique for removing organic
carbon involves soaking t h e sample in a solution of
sodium hypochlorite ( N a C 1 0 , clorox) or hydrogen
peroxide ( H 0 ) to oxidize t h e organic material
(e.g. Wefer & B e r g e r , 1981; Cummings & M c C a r t y ,
1982). A m o r e e l a b o r a t e p r o c e d u r e was developed
by Epstein et al. (1953) and involved 'roasting' t h e
sample in a continuous stream of helium which
swept away t h e decomposition products of t h e heat
ed organic materials and preserved t h e sample in an
inert a t m o s p h e r e . W e b e r et al. (1976), L a n d , L o n g
& B a r n e s (1977), Durazzi (1977) and Weil et al.
(1981) a r e a m o n g t h o s e t h a t h a v e a t t e m p t e d experi
mental work to quantify the effectiveness of each of
these techniques and any isotopic fractionation ef
fects they may h a v e . T h e general consensus is that
neither t h e c l o r o x / H 0 t r e a t m e n t s n o r high tem
p e r a t u r e roasting a r e capable of removing all organic
carbon and t h e r e is considerable evidence that t h e
former will impart s o m e e r r o r to t h e m e a s u r e d
isotopic value; although provided all samples are
p r e p a r e d in t h e same m a n n e r any errors will be
systematic. B e c a u s e of t h e possibility of some or
ganic carbon remaining even after t h o r o u g h pret r e a t m e n t , W e b e r et al. (1976) devised a rejection
p r o c e d u r e b a s e d o n a careful examination of t h e
reference and sample chart recorder traces that
allowed a n excessive input from organic m a t t e r t o b e
recognized. It should also be n o t e d that roasting is
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SILICATES
Techniques designed for crystalline rocks have been
a d a p t e d for sedimentary silicates. 0 / 0 a n d D / H
ratios are t h e only i m p o r t a n t ones; see D o u t h i t t
(1982) for silicon isotopes.
1 8
1 6
O X Y G E N IN S I L I C A T E S
O x y g e n i s o t o p e ratio m e a s u r e m e n t s a r e performed
exclusively o n C 0 in preference t o 0 because it
lies in a mass region relatively free of background
interference. M o r e o v e r , C 0 is less reactive t h a n 0
and thus less likely to be involved in chemical re
actions with substances within t h e p r e p a r a t i o n linemass spectrometer assembly which could introduce
an isotope fractionation effect. H e n c e , t h e m e t h o d
2
332
I.J. FAIRCHILD ef a l .
l s
1 8
High vacuum
High vacuum
1 6
Reaction tubes
BrF cylinder
5
High
vacuum
1 8
From
BrF line
6
ft
Manometer
scale
Sample
tube
Calibrated
volume
^C0
CO
converter
2
t r a
v*4>
Manometer
1 6
Toepler pumps
1 8
Fig. 9.23. Top: apparatus for reaction pfoxygen compounds with bromine pentafluoride. Bottom: apparatus for
collection of oxygen and conversion to carbon dioxide (from Clayton & Mayeda, 1963).
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334
D/H R A T I O M E A S U R E M E N T S ON
SILICATES
T h e m e a s u r e m e n t is p e r f o r m e d on hydrogen gas
which is p r e p a r e d by a fairly standard t e c h n i q u e .
T h e initial step after out-gassing is to extract h y d r o
gen from t h e silicate structure as molecular w a t e r by
heating t h e sample u n d e r vacuum at high t e m p e r a
t u r e , anywhere b e t w e e n 900C (Savin & E p s t e i n ,
1970) and 1 5 0 0 - 1 7 0 0 C (Godfrey, 1962). Since s o m e
h y d r o g e n is also liberated in t h e molecular form this
is converted to water by reaction with C u O . This
water m a y t h e n b e quantitatively converted to H by
reaction with h o t u r a n i u m (400700C) or h o t zinc
after which it is collected via a liquid nitrogen cold
t r a p (Bigeleisen, Perlman & Prosser, 1952; Craig,
1961a, b ; Godfrey, 1962; C o l e m a n etal., 1983). T h e
evolved H is m e a s u r e d isotopically against a suit
able reference with a correction being m a d e for t h e
H
ion interference effect ( F r i e d m a n , 1953). B e
cause of t h e frequently large deviation from the
s t a n d a r d , 6 D values may b e q u o t e d in p e r cent
r a t h e r than parts p e r mil w h e n necessary.
2
3 +
9.7 A N A L Y T I C A L Q U A L I T Y
9.7.1 Accuracy a n d precision
W h e n chemical concentrations have b e e n o b t a i n e d
it is desirable to know b o t h their internal consistency
and their relation to the ' t r u e ' concentration.
Vc
Cf
C3.
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336
9.7.2 Standardization
All t h e analytical techniques previously described
require calibration, that is comparison of their in
strumental response with that of k n o w n concen
trations of t h e element(s) of interest. Broadly t h r e e
m e t h o d s can be used for calibration: (1) Standard
ization against known weights of extremely p u r e
elements or c o m p o u n d s . (2) Standard addition or
spiking. (3) C o m p a r i s o n with geological reference
materials.
T h e distinction should b e clearly m a d e between
standards and reference materials. T h e former a r e
usually simple c o m p o u n d s of known stoichiometry
and chemical composition, whereas the latter a r e
natural materials for which consensus concentration
values a r e available. D e s p i t e the c o m m o n practice
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338
Reporting a n d d o c u m e n t a t i o n
9.7A
2 +
2 +
3 +
2 +
l s
1 3
1 3
1 8
1 8
9.8
EXAMPLES
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339
340
Residual clays _
Amazon cone muds
Average shale _
Pleistocene varved clays
I
Mineralogy
i i
i i
341
size fraction
/xm
Opal
>35
Feldspar
Quartz
20-35
Bulk clay
5-20
Kaolinite
2-5
Illite
Chemical index of alteration =
1.00 A I Q
Na 0 + K 0
A l , 0 + CaO*
2
Bulk sample
T h e device of using inert chemical c o m p o n e n t s to
m o n i t o r provenance has been explored by various
authors. Strontium has b e e n advocated as an evaluator of t h e geographic siting and type of terrigen
ous input by P a r r a , Puechmaille & Carrkesco (1981).
H o w e v e r , their use of whole-rock analyses causes
p r o b l e m s since t h e r e is a b u n d a n t Sr sited in biogenic
carbonates in their studied sediments. T h e y esti
m a t e d the Sr content of the n o n - c a r b o n a t e fraction
1-2
Smectite
BS
0.5-1
0.2-0.5
<0.2
La Ce Nd Sm Eu Tb
Yb Lu
Fig. 9.25. Rare earth element patterns and mineralogical variation for different size fractions of a Recent sediment from
a site in the Indian Ocean. BS = bulk sample (after Tlig & Steinberg, 1982).
http://jurassic.ru/
Hti
342
complicated by a r a n g e of o t h e r natural p h e n o m e n a .
N o t all clay minerals fix b o r o n at an equal r a t e ,
most research showing that the element has a strong
affinity for illite (Hingston, 1964; Fleet, 1965). H e n c e
it is the concentration of boron in illite that is usually
d e t e r m i n e d , while since grain size also affects t h e
a m o u n t of b o r o n a d s o r b e d it is usual to confine all
m e a s u r e m e n t s t o a single particle size o r r a n g e (e.g.
< 2 u m ) . This also removes the possibility of intro
ducing b o r o n as tourmaline. T o complicate m a t t e r s ,
s o m e research has shown that smectitic clays are
capable of adsorbing as much or m o r e boron than
illite (Tourtelot, Schultz & Huffman, 1961; L e r m a n ,
1966), while successful palaeosalinity interpretations
have been m a d e using kaolinite (Couch, 1971).
Poorly crystallized illites are capable of adsorbing
more boron than well crystallized varieties (Porrenga,
1967), a p h e n o m e n o n apparently reflecting t h e divi
sion of each particle into a 'structurally coherent
silicate c o r e ' with little or n o vacant sites, surround
ed by an ' i n c o h e r e n t rind' or 'frayed e d g e ' with
a b u n d a n t adsorbing sites (Jackson, 1963; G a u d e t t e ,
G r i m & Metzger, 1966; Fig. 9.26). H e n c e , as crystal
linity improves, t h e silicate core occupies a larger
p r o p o r t i o n of t h e illite particle a n d less b o r o n can b e
fixed. T h e reverse is true for poorly crystallized
particles.
E v e n w h e n apparently p u r e illite is isolated, com
positional variations can affect t h e u p t a k e of b o r o n .
C . T . W a l k e r (1962) used t h e concentration of K 0
in illite to d e t e r m i n e t h e n u m b e r of muscovite-type
layers p r e s e n t , deriving what he t e r m e d 'adjusted'
2
Structurally coherent
silicate core
Incoherent 'rind' or
'frayed edge'
Fig. 9.26. The 'core-rind' model of boron incorporation
in illite.
http://jurassic.ru/
343
344
SKELETAL GEOCHEMISTRY
345
T = 347Sr - 32.9.
Upper
Middle
Physical
Diagenetic
1 6
1 8
1 5
Lower
freshwater
brackish
marine
hypersaline
120 m
total
1 8
Environmental
100
200
300
400 ppm
http://jurassic.ru/
346
I . J . FAIRCHILD ef al.
1 6
1 8
1 8
1 3
l s
1 8
1 8
9.8.3 Diagenesis
1 3
1 3
1 6
+4r
+2h
0 o
-VP
cr--
p~-2 o
to
13
-4_
l s
8
'
~~ ^ ^
-8
-6
-4
-2
50 (%o)
+2
+4
18
1 8
http://jurassic.ru/
348
I.J. FAIRCHILD e t a l .
ppm
10
10
,o\
Calcite w
F
Calcitesw
FW
*~
'
rostra
+ p.septa
0%
<1
10
Mn in enclosing rocks
10
ppm
(b)
http://jurassic.ru/
349
Lime
mudstone
Subaerial
and
crust
palaeosol
Vadose
Lime
mudstone
Mixing
zone
13
8 C
Skeletal
packstone
-7
-6 -5
-4
-3 - 2 - 1
8%o PDB
13
13
l s
d e m o n s t r a t e d in Mississippian limestones of N e w
Mexico (Meyers, 1978). Complexly zoned c e m e n t s
and replacements h a v e , h o w e v e r , also b e e n argued
to originate by burial diagenetic processes (Fairchild,
1980b; W o n g & O l d e r s h a w , 1981).
M a n y studies have d e m o n s t r a t e d geochemical
differences between depositional components, earlier
and later c e m e n t s , allowing assignment of the later
cements to burial diagenesis. Dickson & Coleman
(1980) provided a particularly convincing example
on Dinantian limestones from the Isle of M a n ,
E n g l a n d w h e r e a sequence of zoned calcite cements
followed by dolomite and kaolinite cements display
increasingly negative 5 0 values corresponding to
progressively higher t e m p e r a t u r e s (coupled with an
u n k n o w n degree of isotopic evolution of the p o r e
fluid).
Chemical analyses of calcareous oozes have pro
vided i m p o r t a n t evidence supporting t h e prevalence
of pressure solution-reprecipitation as t h e process
of lithification. T h u s Scholle (1977) showed that
5 0 values of Cretaceous Chalks systematically
lighten in m o r e deeply buried, less p o r o u s Chalks
1 8
1 8
350
I.J. FAIRCHILD ef a l .
l s
8 7
l s
1 8
G e o c h e m i c a l interpretation of dolomitization is
particularly complicated by major uncertainties in
partition coefficients as well as the question of t h e
d e g r e e of isotopic a n d m i n o r e l e m e n t interference
from precursor c a r b o n a t e s (if a n y ) . Veizer et al.
(1977', 1978) showed for some Palaeozoic examples
h o w high N a and Sr concentrations a p p e a r t o cor
relate with early dolomitization from m o r e con
tinental waters. G e n e r a l l y , absolute a m o u n t s of N a
a n d Sr a r e liable t o vary particularly given t h e com
plexly variable chemistries of potential dolomitizing
Sl
CaC0
0
1
0.2
2
0.4
3 Mg/Ca x 10
0.6
0.8
1.0
351
1.2
t
1.4
r~i
1.6
1.8 Sr/Ca x 1 0
1A~~r
100
200
300
400
500
O
600
A
A
700
Fig. 9.32. Variations in composition
with depth of pelagic carbonates
from two DSDP drill sites. Data
replotted from Baker et al. (1982).
Site 305 has the slower rate of
sedimentation.
800
900
1000
http://jurassic.ru/
352
I.J. FAIRCHILD ef a l .
9.8.4 Elemental c y c l i n g
T h e geological cycle involves transfer of sediments
between several reservoirs which, on t h e simplest
level, a r e the a t m o s p h e r e , continental waters, sea
water and sediments and rocks. Models of t h e kine
tics of these processes (e.g. G a r r e l s & M a c K e n z i e ,
1971; Veizer & J a n s e n , 1979; B e r n e r , Lasaga &
G a r r e l s , 1983) d e p e n d on the existence of reliable
chemical and mineralogical d a t a from rocks of vari
ous ages. Possible secular changes in t h e composi
tion of these reservoirs are of interest from m a n y
points of view.
A n a l y s e s of terrigenous material should provide
evidence of the composition of t h e u p p e r crust.
Obtaining average estimates of t h e chemical c o m
position of sedimentary sequences of various ages is,
of c o u r s e , r e p l e t e with pitfalls. Schwab (1978) m a d e
an extensive compilation of 'terrigenous' composi
tions and correctly excluded the c a r b o n a t e fraction,
but he did not disregard o t h e r chemical sediments.
A n o t h e r criticism ( M c L e n n a n , 1982) is that h e placed
t o o much emphasis on glacially t r a n s p o r t e d , chemi
cally u n w e a t h e r e d sediments in early Proterozoic
sections (Fig. 9.24). W h e n this is allowed for it is clear
that t h e ArchaeanProterozoic b o u n d a r y m a r k s the
most significant change in t h e sedimentary record
with changes in N a 0 / K 0 , T h , light R E E / h e a v y
R E E (and e m e r g e n c e of a negative E u a n o m a l y in
R E E patterns normalized to chondrites) correspon
ding t o a change from a m o r e mafic t o a m o r e felsic
u p p e r crust (Veizer & J a n s e n , 1979; M c L e n n a n ,
Taylor & Eriksson, 1983; M c L e n n a n , 1982).
Considerable attention continues to be given to
possible changes in oceanic chemistry with t i m e .
B e i n g for most purposes and at most times wellmixed, sea water provides a sensitive indicator of
changes in p a t t e r n s of cycling b e t w e e n o t h e r reser
voirs and itself. P e r h a p s t h e most i m p o r t a n t putative
change was an increase in oxidation state accom
2
87
353
86
86
8 7
1 3
3 4
.7100
.7095
y
.7090
.7085
C/J
%. .7080
CO
CO
<J
i '
.7075
.7070
2 +
2 +
3 4
3 2
1 3
1 2
87
.7065
.7060
V
qI
Tertiary
Cretaceous
100
Jurassic
200
Devonian Silurian
300
Myr
400
Ordovician
500
Cambrian
Pc.
600
86
Fig. 9.34. Plot of Sr isotope variation with age of 744 samples of marine carbonates, evaporites and phosphorites (from
Burke et al., 1982). Data points scatter above the line because of diagenetic alteration and short-lived positive excursions
(e.g. Cretaceous-Tertiary boundary. Hess, Bender & Schilling, 1986).
http://jurassic.ru/
1 1 1 1 It
354
1 8
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355
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lillii
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Mill
2+
l s
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Index
Pages on which figures appear are printed in italic, and those with tables in bold
calcite
cathodoluminescence microscopy
of 182,183,755,186
cement formation by 139,148-149,
152,264-265
iron content of 183,186
magnesium content of 186
manganese content of 186
optical properties of 112-113
preparation of 330
scanning electron microscopy of
236
staining for 99-100
Mg-calcite 99
X-ray diffraction of 208
calcite-dolomite mixtures 224,
226-227,227
carbon
isotope fractionation of 290-291
stable isotopes 294
carbonates
analysis of by inductively-coupled
plasma atomic emission
spectrometry 320-325,321,
322,323,324,325
cathodoluminescence microscopy
of 183,184,186-187
chemical analysis of 328-330
diagenetic processes in 133
examination of slices from 88-89,
89
mixed, preparation of 330-331
recording of 26
selective dissolution of 307-308
stable isotope analysis of 328,329,
330
X-ray diffraction of 220-227
calcite-dolomite mixtures 224,
226-227,227
dolomites
221,222-226,224,
225,226
magnesium in calcite 220221,
221
mixtures of calcium carbonate
minerals 221-222,222,223,
224
387
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388
INDEX
INDEX
thin sections 95
porosity of 123
scanning electron microscopy of
266-267
chamosite
optical properties of 112-113
X-ray diffraction of 219
chemical analysis of sedimentary
rocks 3 - 4 , 2 7 4 - 3 5 4
analytical quality 334-339
accuracy and precision 334335
geological reference materials
337
practical quality control 335336
reporting and documentation
338-339
standardisation 336-337
analytical techniques
atomic absorption analysis
315-318,3/6,3/7
electron beam microanalysis
3 0 8 - 3 1 4 , 3 0 9 , 3 / 0 , 3 / / , 312
inductively-coupled plasma
spectrometry 318-325,318,
319,320,322,322,323,324,
325
instrument neutron activation
analysis 325
stable isotopes 325-334,326,
329,333
X-ray fluorescence 314-315
applications 339-354
diagenesis 347-352,348,349,
350,351
elemental cycling 352-354,353
environmental parameters
342 -347,343,344,345,346
provenance and weathering 182,
185,339-342,340,341
chemical principles 274-294,277
adsorption 284-287,285
concentrations and activities
277-278
departures from equilibrium
282-284
equilibrium 278-282,281
isotope reference standards
293-294,294
lattice incorporation of trace
elements 287-290,290
stable isotope fractionation
290-293,292
geological sample collection
294-296
search techniques 295-296,
297-298
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lIliiiMi
389
390
INDEX
INDEX
hematite
cement formation by 139,148-149,
152
optical properties of 112-113
halite
cement formation by 139,151,152
optical properties of 112-113
halloysite, X-ray diffraction of 218
hematite, X-ray diffraction 208
illites
boron absorption by 343
optical properties of 112-113
scanning electron microscopy of
258,259
smectite-illite transformation 261,
263
X-ray diffraction of 206, 218, 219,
220
individual mineral replacement
fabrics 125, 159-160, 76/, /62
inductively-coupled plasma atomic
emission spectrometry
319-320,3/9
analysis of carbonates by 320325,
309,322,323,324,325
inductively-coupled plasma
spectrometry 318-325,318
induration and weathering, recording
of 17
instrument neutron activation analysis
325
kaolinite
optical properties of 112113
replacement of by illite 261
scanning electron microscopy of
236,259
X-ray diffraction of 207,218,219,
220
bedding of 19,20
determination of organic carbon in
308
dolomitization of 268,269
etching of 97, 243
identification and description of
10-12
microscopical examination of
scanning electron microscopy 244
slices 8 8 - 8 9 , 5 9
thin sections 95
scanning electron microscopy of
carbonate grains 265
cementation of carbonates
265 - 266,267
diagenesis-carbonate porosity
2 6 7 - 268
dolomitization 268,269
limonite, cement formation by
148-149, 152
lithofacies codes, use of 6 , 8 - 9 , 10
lithium metaborate
sample decomposition by 305306
use of in X-ray fluorescence
306-307,306, 307
lithology, identification and
description of 612
conglomerates 6 - 1 0 , 7,89,10,
11,12
evaporites 12
limestones and dolomites 1012
mudrocks 6
sandstones 6
lussatite, see opal-CT
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391
quartz
as Si standard for electron beam
microanalysis 312
cathodoluminescence microscopy
of 185,187-188
cement formation by 139,742,144,
152,167
optical properties of 112-113
scanning electron microscopy of
236,258,259
392
INDEX
INDEX
identification and description of 6
microscopical examination of
slices 88
thin sections 9091
scanning electron microscopy of
243
see also feldspar, quartz
saponite, X-ray diffraction of 206
scanning electron microscopy 3,
229-273
ancillary equipment and techniques
232-238
alpha-numeric displays 234
analytical equipment 234-235,
235,236,239-240
back scattered electron detectors
235,239-240
charge-free anticontamination
system 235,238
image analysis 238
photography 232-234,233
endolithic microborings 268273
sedimentological factors
268 - 273,269,270,271,272
examples and reviews 252
function and operation of SEM
230-232,230
cathodoluminescence mode 232,
237-238
emission and reflection modes
231-232,257
X-ray mode 232
limestones and dolomites 264-268,
265,267
problems of SEM operation
250-252
poor photographs 251-252,257
poor screen image 250251
quartz grain surface textures
252-258
ancient deposits 257
experimental work 256-257
processes, textures and
procedures 253-256,253,254,
255
sample collection 238241
subsurface material 241
surface material and outcrops
238,241
sample mounting
coating and storage 247-250
coating specimens 235 236,249
mounting of grains and loose
sediments 248-249,249
mounting rock chips and slices
247-248,245
156-167,156-157,158,159,
160-161,162-163,164-165
nomenclature 123-124, 726, 127,
725
recording of data 167173,
168-171,172,173
techniques and tools 107-109, 709
sedimentary structures, recognition
and recording of 21 - 2 2 , 21,22
sepiolite, X-ray diffraction of 218,220
shales
preparation of slices from 8788
preparation of thin sections from 95
siderite
cement formation by 139
optical properties of 112113
preparation of 330
scanning electron microscopy of
237
X-ray diffraction of 208
silica minerals, X-ray diffraction of
227 -228,229
silicates
D/H ratio measurements in 334
isotope analysis of 331
oxygen in 331-334,355
siliciclastics
chemical analysis of 337
microscopical examination of 101,
102
slices 2, 86-89
definition of 86
examination of cut faces 88-89
carbonate rocks 8 8 - 8 9 , 5 9
sandstones and siltstones 88
preparation 8788
see also peels, thin sections,
preparation of
smectite
authigenic 347
optical properties of 112113
replacement of by illite 261, 263
scanning electron microscopy of
258
X-ray diffraction of 206,218, 219,
220
sodium borate, sample decomposition
by 305
sodium carbonate, sample
decomposition by 305
sodium hydroxide, sample
decomposition by 305
solution seams, formation of
133-139,736-757,755
stable isotopes, use of in chemical
analysis 325-334
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bioturbation 100-101
stereonets, plotting of orientations on
120
stratigraphic sections, measurement
of 23-25,24,25
stylolites, formation of 133-139,
136-137,138
sulphur
isotope fractionation of 293
stable isotopes 294
393
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t>6
Techniques in Sedimentology
Thes techniques available for the study of sediments and sedimentary rocks form the focus of this
book. While field aspects are included, greater emphasis is placed on the laboratory examination
of sediments. Each chapter provides introductory background material and then proceeds to a
discussion of technique, the equipment, and its limitations. Examples are included of how the
techniques can be used to solve sedimentological problems. Techniques in Sedimentology
will
be an unrivalled textbook for undergraduate and postgraduate students and of great use to many
other geologists.
Deformation of S e d i m e n t s a n d S e d i m e n t a r y
Rocks
Special Publications of the Geological Society No. 29
Foreland B a s i n s
Special Publications of the International Society of
Sedimentologists No. 8
S e d i m e n t a r y P e t r o l o g y : a n Introduction
M.E.Tucker
1981. 260 pages, 180 illustrations
Some 70% of the rocks at the earth's surface are
sedimentary in origin, yet only recently have their
formation processes been appreciated. This book
concentrates on up-to-date information and a concise
account of sedimentary petrology. Each rock group is
examined in turn, with composition, petrography,
sedimentary structures and diagenesis being discussed.
This is a welcome addition to textbooks for first- and
second-year undergraduates.
P a l e o s o l s : their R e c o g n i t i o n a n d
Interpretation
Edited by V.P.Wright
1986. 330 pages, 97 illustrations
This book contains selected reviews and case studies on
paleopedology, including the geological history of soils,
time resolution in alluvial stratigraphy, and Quaternary
pedogenesis. Case studies illustrating the various
approaches to paleosols and their uses in archaeology,
stratigraphy, sedimentology and basin analysis are also
included.
BLACKWELL SCIENTIFIC
P U B L I C A T I O N S LTD
Osney Mead, Oxford 0>
8 John Street, London i
23 Ainslie Place, Edinb
3 Cambridge Center,
Massachusetts 02142, USA
107 Barry Street, Carlton, Victoria 3053, Australia
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Carbonate Sedimentology
M.E. Tucker and V.P. Wright
Early 1990. 496 pages, 394 illustrations
This book covers the generation, sedimentation and
subsequent diagenesis of carbonate sediments in every
major environmental setting. The aim is to explain the
principles underlying the processes which control
carbonate rock generation. Primarily an undergraduate
textbook, it will also be invaluable to teachers and to
geologists in industry.
ISBN
0-b3E-D1375-T
l l
780632"013722