Clay Minerals (1986) 21, 937-947

COMPARISON OF S E D I M E N T A R Y CHLORITE
COMPOSITIONS BY X - R A Y D I F F R A C T I O N AND
ANALYTICAL TEM

C. K . W H I T T L E *

Department of Geology, University of Sheffield, Mappin Street, Sheffield, $1 3JD

(Received 10 April 1986; revised 25 August 1986)

A B S T R A C T : Authigenic chlorites occurring as pore linings in reservoir sandstones have been

investigated by XRD and TEM/EDAX. Both methods identified the Ib (fl = 90~ polytype.
TEM/EDAX analyses suggest that the chlorites are Al-rich, Mg-chamosites with Fe/(Fe + Mg)
> 0.47. Octahedral AI exceeds tetrahedral A1, resulting in octahedral totals of less than the
theoretical 12-0. Compositions were estimated from XRD data using the equations after
Brindley (1961) and Shirozu (1958). XRD-determined compositions are relatively enriched in
tetrahedral A1 and octahedral Mg, giving Fe/(Fe + Mg) < 0-4 and suggesting that the chlorites
are Al-rich clinochlores. XRD estimates plot in the same compositional area as authigenic Ib
(fl = 90~ chlorites of Hayes (1970), but also within the compositional area of metamorphic
chlorites. Caution should be exercised when estimating the composition of sedimentary chlorites
by XRD as results appear to overestimate Mg content because of the excess of octahedral R 3+
over tetrahedral R 3+.

By the nature of their grain size, the chemical analysis o f ' c l a y ' minerals presents a problem to
the geochemist. Mineral separates cannot be guaranteed free from impurities, and analyses
performed by routine methods such as wet chemical analysis and X-ray fluorescence are
susceptible to contamination by fine-grained impurities.
X-ray diffraction (XRD) m a y be employed to estimate compositions of clay minerals, as
certain cell dimensions can be related to composition. This largely removes the problem of
contamination. Further, results can be obtained rapidly with the m i n i m u m of sample
preparation. In most situations a minor amount of accessory material will not affect the
strength or position of reflections. However, kaolinite and berthierine can create difficulties
when present with chlorite. Several empirically-derived equations for the estimation of
chlorite composition are available in the scientific literature and have been reviewed by
Bailey (1972). Variations in basal spacing (001) reflect the degree of A1 for Si substitution in
the tetrahedral sheet, whilst the (060) reflection gives an indication of the amount of Fe 2+ in
t h e octahedral sheet.
The electron microprobe (Boles & Franks, 1979; Iijima & Matsumoto, 1982) and analytical
transmission electron microscope (TEM) (Ireland, et al., 1983; A h n & Peacor, 1985) have
recently proved to be valuable tools in the microanalysis of phyllosilicates. The latter
technique is particularly useful due to the optical control and resolution of the electron beam.
Textural information from the analytical T E M can be combined with structural and
chemical data obtained from single crystals < 1 p m in length.
* Present address: Esso Exploration and Production, UK Limited, Biwater House, Portsmouth Road,
Esher, Surrey KT10 9SJ.
9 1986 The Mineralogical Society
938 C. K. Whittle
Authigenic chlorites from a variety of reservoir sandstones have been investigated by
X R D and analytical T E M by Whittle (1985); here, an attempt is been made to compare the
chemistry of sedimentary chlorites using these two techniques.

SAMPLES STUDIED

Most materials analysed were reservoir sandstones in the form of core plugs. Samples were
obtained from the Tuscaloosa sandstones, Belly River sandstones, Falher sandstone, and
sandstones from the North Sea. Most were arkosic with a moderate component of lithic
fragments. Additional samples of metamorphic chlorites were obtained from an arkosic
sandstone and a slate. Details of samples studied are given in Table 1. Each sample of
reservoir sandstone was specifically chosen because of its content of authigenic pore-lining
chlorite. Petrographic examination revealed fringes of pale green chlorite, 10 15 ~m in
length, growing perpendicular to the substrate grains and lining the pores (Fig. la).

TABLE l. Samples studied, with depths.

A02 Falher Formation (L. Cretaceous), Demmit Township, Alberta, 1958.8 m. Fine-grained litharenite
B02 North Sea sandstone (age unknown), location unknown, 3575.8 m. Medium-grained arkose
B03 North Sea sandstone (age unknown), location unknown, 3576.8 m. Fine-grained arkose
B05 North Sea sandstone (age unknown), location unknown, 3551-0 m. Fine-grained lithic arkose
B06 North Sea sandstone (age unknown), location unknown, 3560-0 m. Fine-grained arkose
S04 Batlachulish Slate (Appin Group, Dalradian), Baltachulish, Argyll, surface. Black pyritiferous slate
M33 Hasandong Sandstone (U. Cretaceous), Goryeong, Daegn, S. Korea, surface. Coarse-grained arkose

Details of other samples studied are given in Curtis et al. (1985).

METHODS

X-ray diffraction
Clay separates were obtained from the poorly-cemented sandstones by gently applying
pressure to separate the framework grains and then rolling under distilled water using an
agate pestle and mortar. Disaggregated clays were collected from suspension by centifuging.
Fine clay separates, i.e. <0.2/~m fractions, were not obtained as individual crystals were
approximately 1/~m in length. Samples were prepared in the form of highly oriented smear
mounts. Traces were obtained using Cu-K~ radiation at a scanning rate of 1~ 20 min between
3~ and 65 ~ 20; additional slow scans were made at l/2 ~ 20 min for polytype determination.
Samples were run air-dried (approximately 4 5 ~ r.h.), glycolated (60~ 1 h above ethylene
glycol) and heated (550~ 1 h).
All sandstones contained chlorites with well-developed integral reflections (Fig. 2). Basal
spacings were calculated from the (004) reflection and have a restricted range between 1.411
and 1.415 nm. All samples of sedimentary chlorite apart from A12 had (002) reflections
considerably more intense than the (001), suggesting an Fe-rich composition (Brindley &
Brown, 1980, table 5-7). Details of basal spacings and integral peak ratios from the air-dried
traces are given in Table 2. Glycolation produced no effect, apart from in sample A12, which
showed limited swelling properties. The (001) reflection of A12 at 1.42-1.44 nm divided after
glycolation to give an additional peak at ~ 1.6 nm. In all samples, heating resulted in
 Sedimentary chlorite compositions 939

a b
FIG. 1. (a) Petrological photomicrograph of sedimentary chlorites from the Tuscaloosa
sandstone (sample A06). Chlorite exhibits pale green body colour in plane light and grey-yellow
birefringence in polarized light. Crystals grow perpendicular to the substrate grains to form pore
linings approximately 10 #m thick. (b) TEM photomicrograph of sedimentary chlorites from
the Tuscaloosa sandstone (sample A02), Individual blades reach lengths of 1/~m. Arrows
indicate areas with diffraction contrast. C = chlorite, H = hematite, P = porosity,
R = resin.

enhancement of the (001) reflection intensity and a slight contraction of the position to
1.38 nm. In contrast, the (002) and (004) reflections were significantly reduced in intensity.
Polytype identification was possible from some of the slow-scan air-dried traces. Wherever
a determination was possible, the chlorite Ib (/~ = 90 ~ polytype was indicated by the
diagnostic (202) reflection at 0.25 nm (Hayes, 1970).
The regression relationship of Brindley (1961 ) is frequently used for determining the degree
of A1 and Si substitution (x) in the tetrahedral sheet of chlorites (half-cell basis). The equation
is here converted from angstroms to nanometres:

d(001) = 1.455 - 0.029x

The equation of Shirozu (1958) relates the b parameter to the (060) reflection and estimates
the amount of Fe (y) in the octahedral sheet (half-cell basis). Shirozu's equation has also been
converted for nanometres:

b = d(060).6
b = 0-921 + 0-0037y
Values for (x) and (y) for the sedimentry chlorites have been estimated and inserted into the
940 C. K. Whittle

o/
I I I
0'353 0.7 1-0 1.4 n m
FIG. 2. X R D traces of authigenic pore-lining chlorite from North Sea sandstone, sample (B09).
(a) air-dried; (b) glycol vapour, 60~ 1 h; (c) heated, 550~ 1 h. Chlorite 004 reflection
identified at 0.353 n m was used to determine basal spacing.

TABLE 2. Basal spacings and integral peak ratios of sedimentary chlorites

obtained from X R D traces of air-dried material.

(d) n m * (001) (002) (003) (004) (005)

A0I 1-4I 3 I,i 10 2-0 4-9 I-0

A02 1,411 1.7 10 2-0 4,9 3-0
A03 1.413 1.6 10 1.0 5-5 1.0
A07 1,412 1.3 10 2.0 6.4 1.0
A12** 1-412 . . . . .
A14** 1.411 . . . .
A15** 1.413 . . . . .
AI7 1.412 2.2 10 1.0 4.9 1.0
A20 1,412 1.6 10 1.0 4.5 --
B01 1,413 1.2 10 0-6 5.9 --
B02 1,414 1.0 10 1.2 8,1 --
B03 1,413 1.2 10 1,0 7,0 --
B05 1,413 1.6 10 0.9 7,0 --
B06 1,415 0.9 10 0.8 7-4 0-9
B07 1.414 1.3 10 0.8 6.1 0.5
B08 1.413 1.4 10 0.7 4.9 --
B09 1.413 1.3 10 0.8 5.4 0.5
B10 1.414 1.1 10 0.8 6.0 0.6

* Basal spacing calculated from (004) reflection.

** Intensity ratios could not be determined due to chlorite (002) reflection being
obscured by kaolinite (001) reflection. Presence or absence of kaolinite
determined from (002) reflection.
 Sedimentary chlorite compositions 94I
general formula:
(Mgl 2 - 2x- 2y Fe2+2y A12x)[(Sis _ z~ Al2x)O20 ] ( O H ) I 6
The compositions derived by calculation are given in Table 3.

Analytical transmission electron microscopy

Normal uncovered petrographic thin-sections mounted with soluble adhesive were used in
the preparation of the ultrathin sections required for TEM examination. The material was
thinned using a Gatan 600 ion-mill, following the procedures of Phakey et al. (1972) except
that the ion-beams impinged upon the specimens at a lower angle of 12~ Specimens were
examined in a Philips 400T electron microscope fitted with an energy-dispersive X-ray
analysis (EDAX) system, as described by Curtis et al. (1985).
Approximately 20 chlorite analyses of single crystals were obtained from several individual
pores in each sample. Spectra were processed using proportionality constants (kAsi values)
according to the 'ratio technique' of Cliff & Lorimer (1975). Chlorite analyses were calculated
to mineral formulae on the basis of 36 anions, i.e. 20(0) + 16(OH). Single-crystal analyses
from individual samples were plotted as molar oxide proportions on triangular Si-A1-Fe and

TABLE 3. Sedimentary chlorite compositions estimated from XRD traces.

Fe/(Fe + Mg)

A01 (Fe2~6AI2.9Mg6.5)[(Sis.iAlz.9)O20] (OH)I 6 0.29

A02 (Fe2.3A13.oMg6.7) [(Si5.oA13.o)O2o] (OH)I 6 0.26
A03 (Fe:.9A12.gMg6.2) [(Sis.iA12.9)Ozo] (OH)I 6 0-32
A07 (Fe3.6A13.0Mgs.4) [(Si5.0A13.0)O2o] (OH)I 6 0.40
A12 (Fe2.6A13.:Mg6.2) [(Si4.8A13.9020] (On)l 6 0.30
A14 (Fe2,sA13.0Mg6.5) [(Si5.0A13.0)O2o](on)16 0.28
A15 (Fe3.6A13.0Mgs.4) [(Si5.0A13.0)O20] (OH)I 6 0"40
A17 (Fe2.6Al2.8Mg6.6) [(Si5.2A12.8)O2o](OH)16 0.28
A20 (Fe2.6A12,gMg6.5) [(Si5.jA12.9)O2o] ( o n ) l 6 0.29
B01 (Fe2.9A12.9Mg6.2)[(Si5.1A12.9)O2o](OH)16 0.32
B02 (FeE.3AI2.sMg6.9) [(Si5.2A12.8)O2o] (OH)I 6 0"25
B03 (Fe2.gA129Mg6.2) [(Si5.1A12.9)O2o] ( o n ) l 6 0.32
B05 (Fe2.6A12,gMg6.5)[(Sis.iAl~.9)Ozo](OH)16 0.29
B06 (Fe2,6AI2,sMg6.6) [(Sis,zAlz.8)Ozo] (OH)j 6 0-28
B07 (Fe2.6AI2.sMg6.6) [(Si5.2A12.8)O20](OH)16 0.28
B08 (Fe2.6A12.9Mg6.5)[(Sis.iA12,9)Ozo] (OH)I 6 0.29
B09 (Fe3.6A12.9Mgs.5)[(Sis.iA12.9)Ozo] (OH)I 6 0-40
B01 (Fe3.2Al2.sMg6.0) [(Sis.2A12.s)Ozo] (OH)I 6 0-35

A1-Mg-Fe diagrams (see fig. 1 in Curtis et al., 1985). A mean chlorite analysis for each
sample was obtained by averaging approximately six single-crystal analyses central to the
composition fields in both triangular diagrams. Mean chlorite analyses for several samples
have been published previously (Curtis et al., 1984, 1985). Structural formulae calculated
from additional analyses are presented in Table 4.
Electron diffraction patterns of single chlorite crystals were easily obtained only for (001)
planes. Frequently crystals showed only limited diffraction contrast (Fig. lb) and failed to
942 C. K. Whittle
TABLE4. Structural formulae of chlorites calculated from TEM/EDAX analyses.

Sedimentary chlorites

A20 B02 B03

Si 6'18"~r 5.64"~ 5.84-~.

AI (IV) 1.82..I 8.00 2.36.) 8'00 2.16.) 8.00
A1 (VI) 2.96"] 3.061 3.20"]
Ti 0.03/ o.ooI o.oo1
Fe(III) 0.56 ~. 0.42 ~. 0.45 ~.
Fe(I1) 5.08 1 11'00 3.81 / 11'14 4.07| 11.18
Mn 0.00 / 0.01| 0"09/
Mg 2'373 3"84.1 3"37J
Ca 0.09-] 0.19"] 0.09"]
Na 0.00 ~" 0.15 0.09 ~" 0.03 0.00 ~" 0.24
K 0.06.) 0.12.) 0.15.)
Fe + Mg 8.01 8.07 7.88
Fe/(Fe + Mg) 0.70 0.52 0.57
Sedimentary chlorites Metamorphic chlorites

B05 B06 S04 M33

Si 6.02"~ 8.00 5.77"~ 8.00 5.20"~. 8.00 5.88"~. 8.00

AI (IV) 1.98,,I 2-23.) 2.80.,I 2.12.)
3. 51 .871 .751 3.12l
Ti 0.03/ 0.01[ 0.03/ 0.00/
Fe (III) 0.40 ~. 10.98 0.50 (. 11'33 0'45 (. 11-69 0'29 (. 11-20
Fe (If) 3"58/ 4"47/ 4"01| 2-62|
Mn 0-01 1 0.00 1 0.05 / 0-00|
Mg 3-71.) 3.48.) 4.41-) 5.17.)
Ca 0.04-] 0.03"] 0.00 1 0.00`]
Na 0.03 ~" 0.32 0-05 ~" 0.18 0.07 ~" 0.12 0.12 ~" 0-33
K 0.25J 0-10.) 0.05.) 0.21 .)
Fe + Mg 7.68 8.44 8.87 8.08
Fe/(Fe + Mg) 0.52 0.59 0.50 0.36

produce electron diffraction patterns. This may indicate poor crystaUinity despite the well-
crystallized appearance in thin-section. Where chlorite blades were in appropriate
orientations it was sometimes possible to obtain and index diffraction patterns. In each case
the polytype was determined as Ib (fl = 90 ~ (see fig. 2 in Curtis et al., 1985).

RESULTS
The chemical data determined by T E M / E D E X showed that all authigenic pore-lining
chlorites had a relatively restricted compositional range. Substitution of Al for Si in the
tetrahedral sheet occurred to only a moderate degree, with AI occupying 1.82 to 2.36 of the 8
 Sedimentary chlorite compositions 943
tetrahedral sites (full-cell basis). Fe and AI were important octahedral cations together with
relatively small amounts of Mg. The Fe 2+ :Fe 3+ ratio was determined as > 6 : 1 by wet
chemical methods and mineral formulae were calculated with an assumed ratio of 9 : 1. All
ratios of Fe/(Fe + Mg) were moderately high at > 0.47. The majority of chlorites would be
described as Al-rich, Mg-chamosites according to AIPEA nomenclature (Bailey, 1980),
whereas those with Fe/(Fe + Mg) < 0.50 would be Al-rich, Fe-clinochlores.
Octahedral totals for the sedimentary chlorites were generally less than the theoretical 12.0,
ranging from 10.80 to 11.54. Foster (1962) showed that octahedral totals tend to be lower than
the theoretical 12-0 total by half the excess octahedral R 3+ cations. In the sedimentary
chlorites analysed by TEM/EDAX the principal octahedral R 3+ cation was A1, which
exceeded tetrahedral R 3+ by 0.64 to 1.27 sites. The apparent octahedral deficiencies may be
attributed to the significant amount of A1 present in the octahedral sheets.
The structural formulae in Table 4, derived from T E M / E D A X analyses, indicate that
interlayer K is present, occupying 0-05-0.25 sites. In the theoretical model of chlorite there is
insufficient space between the 2 : 1 layers for large cations such as K, hence the absence of K
in the XRD estimates of chlorite composition in Table 3. It is possible to interpret the
presence of a micaceous component in the T E M / E D A X analyses and recalculate the chlorite
component on a mica-free basis to exclude K. T E M / E D A X single crystal analyses were taken
from blades 6-10 layers thick identified by electron diffraction and lattice-imaging
techniques as chlorite. The TEM/EDAX analyses represent the average chemistry of a
chlorite blade and have not been recalculated to exclude K. The presence of K may represent
remnant interlayer material in a replacement series of Al-rich trioctahedral smectite --*
'swelling' chlorite --, Ib chlorite (Curtis et al., 1985; Whittle, 1985).
Sedimentary chlorite compositions calculated from XRD data differ from those obtained
by TEM/EDAX. Estimates of tetrahedral A1 accounted for 2.8-3.2 sites in all samples, which
is significantly higher than for values obtained from TEM/EDAX. Fe 2+ was estimated to
occupy only 2.3 to 3.6 octahedral sites, resulting in considerably lower Fe/(Fe + Mg) ratios of
0-25-0.40. These chlorites are classified as Al-rich clinochlores according to Bailey (1980).

DISCUSSION
Hayes (1970) investigated the polytypism and chemistry of sedimentary chlorites by XRD
and discovered that a restricted range of polytypes occurs within sediments which have not
been subjected to metamorphism. Hayes suggested an evolutionary sequence from
disordered material Ibd through Ib (fl = 97 ~ and Ib (fl = 90 ~ polytypes. Where sediments
had been subjected to temperatures associated with metamorphism, Ib polytypes were
converted to lib polytypes. Most sedimentary chlorites were found to be the Ib (fl = 90 ~
polytype.
Comparison of TEM/EDAX and electron microprobe analysis of standard material has
shown the TEM analyses to be quantitative (Whittle, 1985). T E M / E D A X analyses are
assumed to be more representative than XRD estimates. Compositions of the sedimentary
chlorites determined by both TEM/EDAX and XRD have been plotted on a {etrahedral AI
vs. Fe/(Fe + Mg) diagram after Brown & Bailey (1962) in Fig. 3. A compositional 'box' for
metamorphic chlorites, based on the review by Foster (1962), has also been outlined on the
plot (for details see Curtis et al., 1985). TEM/EDAX analyses of sedimentary chlorites plot in
a distinct group below the compositional area for metamorphic chlorites due to their
relatively low levels of tetrahedral A1. In contrast, compositions estimated by X R D result in
944 C. K. Whittle
the same material plotting towards lower Fe/(Fe + Mg) ratios and higher tetrahedral A1. The
compositional area of Hayes' (1970) Ib (fl = 90~ chlorites is also included in Fig. 3 and has an
overlap with the Ib (fl = 90~ chlorites investigated by XRD in this study. Both sets of
estimates plot largely within the compositional area of the metamorphic lib chlorites.
Equations used to estimate chlorite compositions have been produced by observations
from large hydrothermal and metamorphic specimens; consequently the calibration curves
are likely to be dominated by the effects of lib polytypes. It is unfortunate that many workers
failed to record the polytypes of their material. However, the investigations of Shirozu (1958)
and Radoslovich (1962) are notable due to the inclusion of several 'ortho-hexagonal'
chlorites, i.e. Ib polytypes.
Bailey (1972) reviewed the determination of chlorite compositions by XRD and applied
several published equations to naturally occurring chlorites. Chlorites of known composition
and polytype were investigated and included:
(i) Ia Cr-clinochlore (the 'kammererite' of Brown & Bailey, 1963).
(ii) Ib (fl = 90~ chamosite (the 'ripidolite' of Shirozu & Bailey, 1965).
(iii) lib Fe-clinochlore (the 'prochlorite' of Steinfink, 1958a).
(iv) lib clinochlore (the 'corundo.philite' of Steinfink, 1958b).
The regression equations of Brindley (1961 ) and Kepezhinskas (1965) allow the estimation of
chlorite tetrahedral compositions to within 10~, or 0.1 ~o AI. The octahedral composition can
also be estimated to within 10~ Fe using the regression equations of Shirozu (1958) or von
Engelhardt (1942), providing the species are trioctahedral. Post & Plummer (1972)
investigated lib chlorites from Flagstaff Hill, California by XRD, DTA and IR spectroscopy
and found that the equation of Brindley (1961) gave a good correlation between tetrahedral
A1 and basal spacing. Considering the range of polytypes used in the review by Bailey (1972),
calculations of chlorite composition would not be expected to be significantly affected by
polytypes.
Fig. 4 is a plot of tetrahedral A1 vs. basal spacing for sedimentary chlorite, together with
the regression curve of Brindley (1961). The value of tetrahedral AI was determined by
TEM/EDAX. In addition to the Ib (fl = 90~) chlorites, there are two samples oflIb chlorites
taken from the metasedimentary Hasandong sandstone and Ballachulish slate (see Table 1
for details and Table 4 for TEM/EDAX analyses). All Ib (fl = 90~ chlorites plot significantly
below the curve, whilst the lib polytypes tend to lie closer to the curve. It would appear that
the estimation of chlorite compositions from XRD data may not be suitable for lb (/~ = 90~
polytypes.
Estimation of chlorite composition by XRD makes the critical assumption that octahedral
AI is equal to tetrahedral A1. The TEM/EDAX chlorite analyses suggest that this is not
normal in sedimentary chlorites and that octahedral AI usually exceeds tetrahedral AI by
> 20~. From Fig. 4, tetrahedral AI in sedimentary chlorites appears to be overestimated by
XRD. However, as octahedral A1 tends to exceed tetrahedral A1 in sedimentary chlorites, (x)
gives a reasonable estimation of octahedral AI content.
After values for Fe and AI have been determined, the remainder of the cation content of
the octahedral sheet is assumed to be Mg, which is made up to the theoretical total of 12-0.
However, TEM/EDAX analyses of sedimentary chlorites suggest that if octahedral AI is in
excess of tetrahedral A1, the octahedral total should be less than 12.0. Assuming an octahedral
total of 12.0 may result in an overestimation of Mg content, giving spuriously low
Fe/(Fe + Mg) ratios, when determined by XRD.
 Sedimentary chlorite compositions 945

I
Clinochlore ~ I - Chamosite

o~ ~
X3 ~"''" s" I \I
CXl ,~_ 9
-~ "--. I /
metamorphic \\ 0 , //
<~ \ I A~- - ~ /
lib chlor , t ~ y ~ - - i ~ - . t
tk .~. 2
t t
"O
(1)
t-- 90*)
t~
J compositional field I
(1) 1 determined by XRD (Hayes, 1970)
9 XRD d a t a
$ T E M / E D A X data I
e u i ! L e i ! !

0 0-1 0'2 0"3 04 0-5 O~ 0-7 0-8 0"9 1-o

Octahedral Fe/(Fe.Mg)
FIG. 3. Composition of pore-lining Ib (fl = 90~ chlorites, determined by TEM/EDAX and
estimated from XRD data. Tetrahedral A1was calculated using the equation of Brindley (1961)
and octahedral Fe was calculated using the equation of Shirozu (1958). The compositional 'box'
of metamorphic chlorites (after Curtis et aL, 1985) and the field of lb (fl = 90~ chlorites as
determined by Hayes (1970) are also shown.

The intensity ratios of the (001) and (002) reflections of chlorites can be used to estimate the
relative importance of Fe and Mg in the octahedral sheet. Heavy cations, primarily Fe,
accentuate the even-order basal reflections relative to odd-order basal reflections. Mg-rich
species generally have ratios of (001) :(002) of the order of 5 : 10. Lower ratios suggest more
Fe-rich compositions. For sedimentary chlorites, semi-quantitative estimates of this kind
may be misleading, as low (001):(002) ratios are typical and appear to be independent of
composition. Chlorites from the Tuscaloosa sandstones are chamosites with Fe/(Fe + Mg)
of ~ 0.70 and have (001) :(002) in the ratio 1.6 : 10-0: The much more Mg-rich chlorites from
the North Sea, with Fe/(Fe + Mg) of ~ 0.5, have (001) :(002) ratios of 1-2 : 10.0.
In an extreme case of a sedimentary chlorite with high Fe content, it is possible that the
(001) reflection may be so weak that the mineral could be misidentified as a 0.7 nm
berthierine rather than 1.4 nm chamosite. Much caution must be exercised when attempting
identification of Fe-rich species.

CONCLUSIONS
Estimates of the composition of chlorites from X R D data using published equations may be
accurate providing the material is trioctahedral and of the lib polytypes. Compositions
estimated for sedimentary chlorites should be used with caution as published equations may
946 C. K. Whittle

-455nm -0"029x ( a f t e r Brindley, 1961)

x
r
w

<

"-.i %33
. . . . .

"O
r

I--

9 lib p o l y t y p e
9 Ib(8-90 ~ p o l y t y p e
0 |

1"40 1"41 1142 1"43 1"44 1"45

Basal spacing d(O01) nm
FZG.4. Chlorite basal spacings plotted against tetrahedral A1contents, and the regression curve
of Brindley (1961). Basal spacings determined by XRD. Values of tetrahedral AI; (2x)
determined by TEM/EDAX. Pore-lining Ib (fl = 90~ chlorites plot furthest from the curve of
Brindley (1961), whilst the two additional samples ofllb metasedimentary chlorites tend to lie
closer to the curve.

not be as suitable for Ib (fl = 90~ The compositions of the pore-lining Ib (fl = 90 ~ chlorites
derived by calculation from X R D are not the same as compositions of the same material
determined by T E M / E D A X . Major differences occur in the estimated and measured
compositions of both the tetrahedral and octahedral sheets. Tetrahedral A1 appears to be
overestimated by X R D relative to T E M / E D A X . Octahedral A1 generally exceeds tetrahedral
A1 in sedimentary chlorites. The Mg content will be overestimated if no account is taken of
the excess octahedral R 3+ cations and the octahedral total is assumed to be the theoretical
total of 12.0. To derive more reliable estimates of sedimentary chlorite compositions it may be
necessary to produce a revised calibration curve using only the Ib (fl = 90 ~ polytype.

ACKNOWLEDGMENTS
The work was funded by a research studentship from the Natural Enivronmental Research Council.
Additional support was provided by Amoco Production Company, Tulsa Research Centre. Core material was
provided by BP and Amoco petroleum companies. C. D. Curtis and J. A. Whiteman are gratefully
acknowledgedfor their supervision. A. Saxbyperformed the wet chemical analysis, F. G. F. Gibb provided the
electron microprobe analysis of mineral standards, and S. Pearson typed the manuscript. T. P. Young and D.
Wilkinson kindly reviewed an early manuscript.
 Sedimentary chlorite compositions 947

REFERENCES
AHN J.H. & PEACORD.R. (1985) Transmission electron microscopic study of diagenetic chlorite in Gulf Coast
argillaceous sediments. Clays Clay Miner. 33, 228-236.
BAILEY S.W. (1972) Determination of chlorite compositions by X-ray spacings and intensities. Clays Clay
Miner. 20, 381-388.
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