ONWl-21

GEOTHERMAL ALTERATION OF CLAY MINERALS

AND SHALES: DIAGENESIS

TECHNICAL REPORT

July 1979

OflWl

Office of Nuclearwaste Isolation

DISCLAIMER
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DISCLAIMER
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MASTER
ONWI-21
GEOTHERMAL ALTERATION OF CLAY MINERALS
A N D SHALES: DIAGENESIS

P
TECHNICAL REPORT

.
july 1979

Charles E. Weaver
Georgia Institute of Technology
Atlanta, GA 30332

This report was prepared by Georgia Institute of Technology under Subcontract E514-00400 with
Battelle Project Management Division Office of Nuclear Waste Isolation under Contract No.
ET-76-C-06-1830 with the U.S. Department of Energy. This subcontract was administered by the
Battelle-0 f f ice of Nuclear Waste Isolation.
2

i
CONTENTS
Page
EXECUTIVE SUMMARY

CONCLUSIONS AND DISCUSSION

SMECTITE

24

Conversion to Mixed-Layer Phase

24

Other Complications

30

Experimental

34

Chemistry

36

Release of Interlayer Fluids

42

Water

42

Oil
-

45

High Pressure

53

Water Chemistry
ILLITE

57
64

Chemistry

65

H2

68

Illite-Phengite Relation

70

Hydrothermal Studies

71

Polymorphic Forms of Illite

72

Crystallinity (Sharpness)

75

Illite in Sandstonei

85

Paragonite

86

Feldspar

86

KAOLINITE

88

-Shales

88

Sandstones

90

Experimental

93

ii
CONTENTS, continued

Ld
Page

CHLORITE
Polytypes and Composition

96

96

r
Mode of Formation

100

Soils

100

Marine

101

Evaporites

101

Carbonates

102

Ironstones

102

Sandstones

103

Shales

103

Diagenesis

103

Sandstone

104

Shales

106

K-Bentonites

110

Hydrothermal
ORGANIC MATERIAL

111

112

Coalification Process

112

Shales

117

Hydrocarbons and Temperature

118

Conodonts

123

Relation of Mineral Diagenesis to

Organic Metamorphism

127

Clay Minerals

129

Carbonates

138

Zeolites

139

iii

CONTENTS, continued

LJ

Page

1Ic

THERMODYNAMIC INVESTIGATIONS

141

REFERENCES

152

FIGURES
Page
t

Figure 1.

Relation of diagenetic-metamorphic changes in clay

18

minerals and organic matter to temperature

Figure 2.

Temperature of conversion of smectite layers to il-

25

lite as a function of time

Figure 3.

Montmorillonite contraction profile for typical Gulf

31

Coast well
Figure 4.

Changes in chemical composition of mixed-layer illite-

39

montmorillonite as a function of percent illite layers

Figure 5.

Changes in chemical composition of mixed-layer illite-

40

montmorillonite as a function of temperature

Figure 6.

Typical shale pore water curve for early Tertiary Gulf

46

Coast section
Figure 7.

Relation of initial collapse of montmorillonite layers

48

and first occurrence of "stable" mixed-layer phase (4:l)

to number of producing fields in the Gulf Coast Tertiary
Figure 8.

Relation of temperature of intense oil generation to

50

smectite conversion to mixed-layer illite-smectite

Figure 9.

Percentage (dry weight of sample) of cations in the

62

interstitial water and exchange cations as related

to increase in percent of contracted layers
Figure 10.

Aluminum distribution in dioctahedral 2:l clay minerals

67

Figure 11.

Relation of K20 content of "illites" to sharpness

79
1

ratio of 10 A x-ray peak

Figure 12.

Relation of K 0 content of "illites" to crystallinity

2
index of 10 A x-ray peak

80

L'

FIGURES, continued
Page

s
Figure 13.

Relation of K20 content of "illites" to asymmetry

82

ratio of 10 A x-ray peak

Figure 14.

Organic metamorphic stages of petroleum generation

122

Figure 15.

Map showing conodont color alteration index (CAI)

125

in Ordovician rocks in the Appalachian basin

Figure 16.

Regional relation of oil and gas occurrence to coal

128

rank in Upper Paleozoic strata of the eastern United

States
Figure 17.

Schematic relation of diagenetic-metamorphic stages

to

Figure 18.

130

coal rank

Relation of percent illite layers in mixed-layer

135

-%

illite-montmorillonite to vitrinite reflectance and

temperature

Figure 21.

The system HC1-H20-A1203-K20-Na20-Si02 at 60 C

The system HC1-H20-A1 0 -K O-Na20-Si02 at 300 C
2 3 2
Stability diagram for the system Na20-A1203-Si02H20

147

Figure 22.

Phases found between the compositions muscovite-pyro-

149

Figure 19.
Figure 20.

144
145

phyllite
Figure 23.

Possible general phase relations for illite and associated phyllosilicates

150

vi
TABLES

Page
Table 1.

The different stages of coalification and their dis-m

114

tinction on the basis of different physical and chemi-

cal rank parameters

Table 2.

Relation of coal rank to burial temper a ture

116

Table 3.

Munsell s o i l colors of conodont alteration indexes

124

Table 4.

Organic metamorphism indexes

126

LJ

EXECUTIVE SUMMARY

The o b j e c t i v e of t h i s r e p o r t i s t o perform a c r i t i c a l review of t h e d a t a

on t h e mineral and chemical a l t e r a t i o n s that occur during diagenesis and lowgrade metamorphism of shale and other clay-rich rocks--conditions

similar t o

those expected from emplacement of heat-producing r a d i o a c t i v e waste i n a geol o g i c repository.

The conclusions drawn i n t h i s document are t h a t t h e following

types of a l t e r a t i o n s could occur:

Smectite a l t e r a t i o n

- Because

of t h e i r high water content (20 t o 40 per-

cent) and r e l a t i v e l y r a p i d r e a c t i o n rate a t low temperatures, smectites are

t h e c l a y minerals most l i k e l y t o be a f f e c t e d by heat.

Water l o s s and mineral-

ogic changes caused by an i n c r e a s e i n temperature w i l l increase t h e p o r o s i t y

and permeability of t h e shale.

This should i n c r e a s e t h e rate of water move-

ment and decrease t h e s t r u c t u r a l s t a b i l i t y of t h e shale.

smectite w i l l presumably move towards t h e heat source.

The pore water i n

I n t e r l a y e r water w i l l

then be released from smectites a t temperatures encountered i n a r e p o s i t o r y

f o r high-level r a d i o a c t i v e waste.

This water w i l l be t r a n s f e r r e d t o t h e pores

and may i n i t i a l l y cause an i n c r e a s e i n p o r o s i t y and p l a s t i c i t y .

As t h e o r i -

g i n a l and new pore water moves i n t o t h e r e p o s i t o r y t h e thermal conductivity

of t h e s h a l e w i l l decrease and t h e temperature increase; f r a c t u r e s may develop
and s e t t l i n g may occur.

The s t r u c t u r a l s t a b i l i t y of t h e s h a l e s i n t h e immedi-

ate v i c i n i t y of t h e r e p o s i t o r y i s l i k e l y

to

be weakened.

Only minor chemical

and mineralogical changes should occur i n t h e dehydrated shale; however, where

i.I

water is present chemical and mineralogical changes (conversion t o i l l i t e and

c h l o r i t e ) could begin a t temperatures as low as 4OoC and continue t o temperat u r e s i n excess of 3OO0C.

of a few years o r less.

Some of t h e s e changes may t a k e place over a period

These mineral transformations w i l l i n c r e a s e t h e g r a i n

s i z e of t h e c l a y minerals.

This should cause a n i n c r e a s e i n p o r o s i t y and per-

meability, f a c i l i t a t i n g t h e movement of water through t h e shale.

Ion mobilization

- Permeability

b a r r i e r s and high p r e s s u r e zones may b e

created i n s h a l e when ions p r e c i p i t a t e from s o l u t i o n .

but i n t h e long term could be b e n e f i c i a l .

This may create problems

The heat generated by r a d i o a c t i v i t y

w i l l increase t h e s o l u b i l i t y of t h e minerals and accelerate chemical changes.

This should cause a n i n c r e a s-e i n t h e i o n concentration of t h e s h a l e pore waters.
The mobilized ions (Si, Mg, Fe, K, C a y Na) w i l l migrate along t h e temperature
gradient and a t various i n t e r v a l s p r e c i p i t a t e and cause a decrease i n t h e porosi t y and permeability of t h e s h a l e and interbedded sandstones and s i l t s t o n e s .
This could lead t o t h e development of high pressures i n t h e v i c i n i t y of t h e
r e p o s i t o r y and increase t h e p o s s i b i l i t y of rock f a i l u r e .

As t h e temperature

of t h e r e p o s i t o r y decreases t h e p o s s i b i l i t y of problems a r i s i n g from t h e formation of high pressures should decrease.

Ultimately a permeability b a r r i e r

should be b e n e f i c i a l because it w i l l i n h i b i t t h e flow of water i n t o and out of

t h e repository.
I l l i t i c shales

It is u n l i k e l y t h a t heat generated by r a d i o a c t i v e waste

w i l l cause any major chemical o r mineralogical changes i n s h a l e s with a high

content of i l l i t e .

I n i l l i t i c s h a l e s t h e p o s s i b i l i t y of rock f a i l u r e and w a t e r

migration w i l l be minimal.
c

Most i l l i t e - r i c h shales have been exposed t o b u r i a l

temperatures of 2 0 d t o 300" C f o r m i l l i o n s of years and contain c 5 percent

pore water and c 5 percent water-bearing c l a y l a y e r s .
Kaolinite reactions

- The porosity

and permeability of t h i n sandstone and

s i l t s t o n e beds i n s h a l e s can be modified, probably decreased, by t h e formation

of k a o l i n i t e .

Moderate ( 5 @ t o l O d C) i n c r e a s e s i n temperature, p a r t i c u l a r l y

i f organic material is present, w i l l cause k a o l i n i t e t o form from pre-existing

GC

u
I)

minerals.

K a o l i n i t e i s a minor component of most s h a l e s and though i t can be

a l t e r e d i n t h e temperature range of 80 t o 22OoC, t h e a l t e r a t i o n should have

l i t t l e e f f e c t on t h e physical p r o p e r t i e s of t h e shale.
Chlorite reactions

Porosity and permeability, i n both s h a l e s and i n t e r -

bedded sandstones and s i l t s t o n e s can be decreased by t h e formation of c h l o r i t e .

C h l o r i t e can form by t h e a l t e r a t i o n of other c l a y minerals a t temperatures as
low as 7OoC.

A t approximately 200C i o n s can be mobilized t o t h e e x t e n t t h a t

c h l o r i t e may grow i n f r a c t u r e s and other voids t h a t might develop a f t e r t h e

temperature i s increased.
Organic r e a c t i o n s
repository.
ed.

Methane and C02 could create pressure problems i n t h e

For t h i s reason, rocks with a high organic content should be avoid-

Most s h a l e s contain 1 t o 3 percent organic material.

When t h e temperature

i s increased, s t a r t i n g a t <50 C, organic material w i l l decrease i n p o r o s i t y

't

and moisture content and methane and CO w i l l be released.

2

O i l may be gener-

a t e d i n t h e temperature range of 65 t o 150 C; condensate, w e t gas, and methane

may be produced a t higher temperatures.

If t h e shale has been previously ex-

posed t o high b u r i a l temperatures t h e s e r e a c t i o n s w i l l not occur.

Paleotemperatures

It is e s s e n t i a l t h a t t h e maximum temperature t o which

a shale has been exposed be determined before i t is considered f o r a reposit o r y site.

Knowing t h i s , i t should be p o s s i b l e t o p r e d i c t t h e r e a c t i o n s t h a t

w i l l occur when t h e s h a l e s are exposed t o a d d i t i o n a l heat.

Changes i n both

organic material and c l a y minerals can be used t o determine t h e maximum paleotemperature t o which
rh.

rock has been exposed; however, t h e r e a c t i o n rates f o r

organic materiallare more time dependent than those f o r t h e c l a y minerals.

Thus, t h e c l a y minerals should be a more a c c u r a t e geothermometer.
Low temperature s h a l e s

- When s h a l e s are subjected

t o temperatures of 2000

t o 3OO0C f o r hundreds of years, chemical, physical, and mineralogical changes

4
w i l l occur.

The extent of t h e s e changes w i l l depend l a r g e l y on t h e maximum

b u r i a l temperature t o which t h e s h a l e s have previously been exposed.

m o r i l l o n i t i c s h a l e s and s h a l e s with mixed-layer illite-montmorillonite

Mont-

chi
t

con-

t a i n i n g a high content of montmorillonite l a y e r s have not been exposed t o high

U

b u r i a l temperatures and w i l l undergo t h e most extensive changes.

The most

s e r i o u s change w i l l probably be t h e release of i n t e r l a y e r w a t e r and t h e development of shrinkage cracks and f r a c t u r e s .

meability and decrease t h e rock strength.

This w i l l increase p o r o s i t y and perBench tests and f i e l d tests w i l l

need t o be conducted t o determine t h e seriousness of t h i s problem; however,

because of t h e e f f e c t s of t i m e on t h e r e a c t i o n s , t h e tests may have l i m i t e d
p r e d i c t i v e value.

Though montmorillonite may be dehydrated i n a few minutes,

i t may r e q u i r e s e v e r a l years, o r considerably longer, t o convert i t t o i l l i t e .

HiPh temperature s h a l e s

I l l i t e - c h l o r i t e s h a l e s , l a r g e l y of Paleozoic age,
t

which have been subjected t o b u r i a l temperatures i n excess of 208C w i l l undergo only minor changes when exposed t o heat t h a t produces temperatures of 200
t o 30OOC.

The heat w i l l have r e l a t i v e l y l i t t l e e f f e c t on t h e adsorption prop-

erties of i l l i t e .

Water problems w i l l be minimal and s t r u c t u r a l s t r e n g t h should

n o t be decreased.

Additional bench and f i e l d tests w i l l have t o be made t o

confirm t h e s e conclusions.

Because shallow buried s h a l e s commonly contain

f r a c t u r e s and s u r f a c e waters i t may be necessary t o conduct f i e l d tests a t a

depth of approximately 300 m (1000 f e e t ) t o o b t a i n realistic data.
Phase equilibrium

Theoretical and experimental phase equilibrium s t u d i e s

provide an i n s i g h t t o t h e phase changes which occur i n s h a l e s as temperature and

pressures change.

However, because of k i n e t i c restraints, information from

such s t u d i e s can be considered only a crude approximation a f what happens i n

t h e n a t u r a l system where time is a major f a c t o r i n overcoming sluggish r e a c t i o n s .

hi
s

Experimental phase equilibrium studies of shales rather than individual clay

minerals could possibly provide information that would be useful i n predicting
the long term e f f e c t s of heat on in-place shales.

ki

CONCLUSIONS AND DISCUSSION

Shales and other rocks containing a high content of c l a y minerals (Weaver,

1977) have a number of p r o p e r t i e s t h a t make them a n a t t r a c t i v e host rock f o r

a r a d i o a c t i v e waste repository.

These p r o p e r t i e s include low p o r o s i t y and

permeability, good s o r p t i v e c h a r a c t e r i s t i c s , low s o l u b i l i t y , and t h e p o t e n t i a l

f o r p l a s t i c flow.

These p r o p e r t i e s would a l l be modified by t h e heat gener-

a t e d by r a d i o a c t i v e waste i f a r a d i o a c t i v e waste r e p o s i t o r y w e r e e s t a b l i s h e d
i n a s h a l e deposit.

The n a t u r e of t h e short-term response of t h e rocks t o

heat can be established by laboratory and f i e l d s t u d i e s ; however, t h e response

of c l a y minerals and associated minerals t o heat depends on time and can b e s t
be established by examining t h e d i a g e n e t i c r e a c t i o n s t h a t have occurred i n
t h e n a t u r a l system.
The a v a i l a b l e d a t a i n d i c a t e t h a t t h e heat (200"-300"C) from r a d i o a c t i v e

waste could probably cause some l a y e r c o n t r a c t i o n i n montmorillonite i n a few

months.

Layer c o n t r a c t i o n due t o diagenesis (permanent dehydration) w i l l be

a major f a c t o r over a s h o r t time i n t e r v a l only i f appreciable pore water i s

present; however, i f t h e pore water is removed, t h e l a y e r s w i l l c o n t r a c t due
t o thermal dehydration.

I n t h e l a t t e r case, t h e contracted l a y e r s w i l l have

t h e capacity t o rehydrate.

This type of dehydration could occur a f t e r t h e

c l a y s are exposed t o temperatures of 100" t o 200C f o r several hours. I n eit h e r case, t h e c a t i o n exchange capacity w i l l be considerably reduced.

Con-

t r a c t i o n w i l l i n c r e a s e with time and extend outward a hundred meters o r so

from t h e repository.

The release of i n t e r l a y e r water and t h e development of

new pore volume and pqre water w i l l be g r e a t e s t i n t h e v i c i n i t y of t h e reposi t o r y and decrease outward.

water w i l l go.

It has not been established e x a c t l y where t h i s

Temperature w i l l i n c r e a s e towards t h e r e p o s i t o r y , and p o r o s i t y

(&'

gd
5

and permeability w i l l decrease i n t h e opposite d i r e c t i o n .

up could occur.

A pressure build-

I f t h i n but continuous sandstone o r s i l t s t o n e beds are pres-

ent, they could serve as channels through which some of t h e hot water o r

steam can move; however, porous beds of wide lateral e x t e n t are rare i n t h i c k
s e c t i o n s of shale.

The development of new pore space (10 t o 30 percent) and

pore w a t e r (from i n t e r l a y e r water) should i n c r e a s e t h e p l a s t i c i t y of t h e shale

and cause o r increase p l a s t i c flow.

The subsequent l o s s of pore water w i l l

cause a decrease i n thermal conductivity and could lead t o consolidation and

t h e development of f r a c t u r e s .
Under n a t u r a l conditions, t h e A 1 content of montmorillonite l a y e r s has
s t a r t e d t o increase, probably by t h e l o s s of S i , a t temperatures of 40" t o
6OOC.
*

This i s accompanied by t h e release of i n t e r l a y e r water t o t h e pores,

l a y e r contraction, and t h e f i x a t i o n of K (from K-feldspar)

between t h e con-

tracted layers.

The l a y e r s are c a l l e d i l l i t e .

d i s t r i b u t e d contracted l a y e r s are formed.

'F;

I n i t i a l l y , only a few randomly

Chemical modifications and l a y e r

c o n t r a c t i o n continue a t a r e g u l a r raie u n t i l 70 t o 80 percent of t h e l a y e r s

are.contracted.

A t t h e same time, some Mg and Fe m a y be released from t h e

octahedral l a y e r t o form c h l o r i t e .
t h e reaction.

The degraded K-feldspar may e n t e r i n t o

The released S i i s believed t o form quartz.

The exchange capa-

c i t y i s decreased.
The temperature a t which 70 t o 80 percent c o n t r a c t i o n i s reached ranges
from 90" t o 160C.

II

There i s l i t t l e f u r t h e r l a y e r c o n t r a c t i o n u n t i l tempera-

t u r e s are increased t o i n excess of 208C; however, chemical changes may contime. A r e l a t i v e l y high l a y e r charge i s needed t o c o n t r a c t t h e f i n a l 20
t o 30 percent expanded l a y e r s .

The temporal d i s t r i b u t i o n of mixed-layer i l l i t e -

montmorillonite and hydrothermal experiments i n d i c a t e s t h a t r e a c t i o n rates are

8
r e l a t i v e l y rapid and t h a t time is not a major f a c t o r .

This i s i n c o n t r a s t

t o organic diagenesis, where time i s as important as temperature.

Calculated

a c t i v a t i o n energies i n d i c a t e t h a t a t 12OoC, 80 percent of smectite l a y e r s

would be converted t o i l l i t e i n approximately 5,000 years.

I n laboratory

experiments, t h e same amount of c o n t r a c t i o n w a s obtained i n 167 days a t 25OoC.

High pressures could develop i n montmorillonitic s h a l e s due t o t h e format i o n of permeability b a r r i e r s similar t o those e x i s t i n g i n t h e Cenozoic of t h e
Gulf Coast.

Water released from between t h e montmorillonite l a y e r s has a higher c a t i o n

concentration than normal pore w a t e r .

Some of t h e released i n t e r l a y e r c a t i o n s

(Na, C a , M g ) and t h e S i , Mg, and Fe released during t h e modification of t h e

montmorillonite l a y e r s , along with CO

from organic material and S i and A1

from t h e degraded f e l d s p a r , presumably migrate with t h e pore water.

As t h e

temperature decreases, both as a function of d i s t a n c e and time, secondary

minerals such as calcite, s i d e r i t e , a n k e r i t e , dolomite, quartz, c h l o r i t e , and
k a o l i n i t e ( i f conditions are a c i d ) are deposited i n t h e shale, and i n sands t o n e and s i l t s t o n e beds, causing a decrease i n p o r o s i t y and permeability.
Calcite, k a o l i n i t e , and quartz (or opal) can form a t temperatures as low as

5OoC.

Ankerite and c h l o r i t e develop a t temperatures s l i g h t l y i n excess of

lOO"C,

though some varieties of c h l o r i t e can form a t temperatures of 60C.

Under b a s i c conditions, i l l i t e can form i n t h i n sandstone and s i l t s t o n e

beds causing a decrease i n permeability and possibly porosity.

It can form

from t h e a l t e r a t i o n of f e l d s p a r o r possibly from i o n s derived from t h e adjac e n t shales.

From t h e standpoint of w a s t e storage, i t i s important t o e s t a b l i s h t h e

maximum paleotemperature t o which a s h a l e has been exposed,

Even though some

bi

h.l
5

expanded water-bearing l a y e r s are present, i f t h e s h a l e has been subjected t o

temperatures on t h e order t o ZOOo t o 300'C f o r m i l l i o n s of years i t i s u n l i k e l y
t h a t t h e h e a t generated by r a d i o a c t i v e waste w i l l cause any major chemical o r

'3

mineralogical changes; however, thermal dehydration could s t i l l occur.

The

problems caused by dehydration w i l l depend on t h e volume of expanded l a y e r s

t h a t are present.
Pure 10 A i l l i t e i s not l i k e l y t o be a f f e c t e d much by temperatures encountered i n a repository; however, Paleozoic i l l i t i c shales commonly contain
from 5 t o 30 percent mixed-layer illite-montmorillonite

(4:l t o 9:l).

The

f i n a l 20 percent of expanded l a y e r s i n t h e mixed-layer illite-montmorillonite

i n s h a l e s can p e r s i s t t o temperatures i n excess of 220C.

A t t h e s a m e tempera-

t u r e , a s s o c i a t e d sandstones can contain c l a y s with 40 percent expanded l a y e r s .

The cQmposition of montmorillonite l a y e r s i s v a r i a b l e .

Some presumably have

e-

a s u f f i c i e n t l y high A 1 content s o that they convert t o i l l i t e a t 40'

Other l a y e r s have compositions s t r i k i n g l y d i f f e r e n t from i l l i t e .
s

rr

temperatures are required t o convert t h e s e l a y e r s t o i l l i t e .

t o 60'C.

Much higher

The geometry

of t h e charge d i s t r i b u t i o n a l s o r e q u i r e s t h a t t h e f i n a l l a y e r s a t t a i n a higher
charge and undergo more chemical modification t o cause c o n t r a c t i o n than t h e
l a y e r s t h a t are contracted a t lower temperatures.

Chemical c o n s t r a i n t s , l a c k

of K and A l , may i n h i b i t l a y e r contraction.

When t h e Na/K r a t i o i s s u f f i c i e n t l y high, paragonite can form a t temperat u r e s as low as 200'C

(anchizone) and can be used as a n i n d i c a t o r of miminum

temper a t u r e.
rc-

A t temperatures of 200' t o 3OOOC about t h e only changes t h a t would t a k e

p l a c e i n a n i l l i t i c s h a l e t h a t had not previously been heated t h a t high would

be some s l i g h t m o d i f i c a t i o n o f t h e s t r u c t u r e and f a b r i c of t h e shale.

In the

Ti

-W

n a t u r a l system, an i n c r e a s e i n temperature i s u s u a l l y accompanied by an Ancrease

10
i n pressure, and i l l i t e diagenesis produces a decrease i n p o r o s i t y and a n increase i n s h a l e density.

I n t h e v i c i n i t y of a r e p o s i t o r y , overburden pressure

bj
t

should remain constant and t h e e f f e c t of heat on i l l i t e might be t o cause a

s l i g h t i n c r e a s e i n porosity.

Exchange capacity should be s l i g h t l y reduced

by t h e changes that occur a t high temperatures.

The more obvious changes t h a t t a k e place i n i l l i t i c c l a y s with increasing
b u r i a l temperature occur i n t h e 2M/lMd r a t i o , t h e sharpness r a t i o , and t h e
c r y s t a l l i n i t y index.

The relative proportion of 2M i l l i t e i n c r e a s e s w i t h in-

creasing temperature, but i t has not been e s t a b l i s h e d whether 2M i l l i t e s form

before a l l expanded l a y e r s are converted t o i l l i t e .

The d a t a are c o n f l i c t i n g .

As t h e proportion of expanded l a y e r s (most "illites" contain 2 t o 5 perc e n t expanded l a y e r s o r more) decrease with increasing temperature, t h e width
of t h e " i l l i t e " peak decreases.

These changes are measured i n terms of peak

I

width ( c r y s t a l l i n i t y index) and peak shape (sharpness r a t i o ) .

Both of t h e s e

measurements demonstrate that t h e width of t h e (001) x-ray peak decreases

through t h e b u r i a l temperature range of
schist facies).

looo

t o approximately 4OO0C (green-

A t lower temperatures, t h e peak width and spacing r e f l e c t s

t h e proportion of expanded o r c h l o r i t i c l a y e r s i n t e r s t r a t i f i e d with 1 0 A i l l i t e

layers.

A t higher temperatures, t h e peak width can be influenced by c r y s t a l -

l i n i t y , f l a k e s i z e , and t h e d e s t r u c t i o n of non-10 A l a y e r s .

It i s not known

which o r i f a l l of t h e s e f a c t o r s are important.

Numerous authors have used c r y s t a l l i n i t y values and sharpness r a t i o v a l u e s
t o c h a r a c t e r i z e t h e s t a g e s of diagenesis and low-grade metamorphism.

The t h r e e

widely used d i v i s i o n s are t h e diagenesis zone (montmorillonite t o " i l l i t e " ) ,

anchizone, and epizone (greenschist f a c i e s ) .

i.

The boundary values used by

v a r i o u s authors are not c o n s i s t e n t , and l i t t l e attempt has been made t o relate

t h e boundaries t o temperature.

6.1'

11
The 1 0 A / 5 A r a t i o can be used t o measure a chemical rearrangement that
t a k e s place within a shale.

The r a t i o i s apparently a measure of t h e amount

of K t h a t moves from K-feldspar t o i l l i t e and t h e amount of Fe and Mg t h a t

moves from i l l i t e t o form c h l o r i t e .

This rearrangement shourd cause a change

i n t h e physical p r o p e r t i e s of t h e shale.
The 10 A / 5 A r a t i o of i l l i t e tends t o decrease with increase i n grade of
diagenesis and of metamorphism and presumably of temperature.

The r a t i o de-

crease is caused by a n i n c r e a s e i n K and/or a decrease i n Fe (accompanied by

Mg).

Both chemical changes i n d i c a t e an i n c r e a s e i n t h e "muscovitic character"

of t h e i l l i t e .

A t temperatures less than 2OO0C, where a mixed-layer phase

e x i s t s , t h e 10 A/5 A r a t i o i s s t r o n g l y influenced by t h e mixed-layer r a t i o

and i s of questionable chemical significance.
When t h e 1 0 A/5 A r a t i o is p l o t t e d versus t h e c r y s t a l l i n i t y index, t h e r e
i s a g r e a t d e a l of scatter; however, i n t h e Conasauga s h a l e t h e r e i s a good
l i n e a r r e l a t i o n between t h e r a t i o and t h e depth of b u r i a l .

This may be be-

cause t h e samples were from one formation and t h e o r i g i n a l composition of t h e

i l l i t i c c l a y s w a s r e l a t i v e l y uniform.

When t h e samples are from one forma-

t i o n t h e r a t i o can possibly be used as a geothermometer.

The f a c t o r s c o n t r o l l i n g t h e d e s t r u c t i o n of k a o l i n i t e are so complex that
i t i s u n l i k e l y t h a t k a o l i n i t e can be used as a geothermometer.

I n most shales

k a o l i n i t e i s a minor component and i t s d e s t r u c t i o n o r a l t e r a t i o n i n a reposit o r y s h a l e i s l i k e l y t o cause only minor physical changes.

with k a o l i n i t e b i l l occur i n t h e sandstones and s i l t s t o n e s .

The major problem

Elevated tem-

p e r a t u r e s could accelerate t h e formation of CO from organic material, c r e a t i n g

2
t h e a c i d conditions which favor t h e formation of k a o l i n i t e .

The newly formed

k a o l i n i t e should decrease t h e p o r o s i t y and permeability; t h e d e s t r u c t i o n of

12
feldspar, rock fragments, and possibly some quartz would cause an increase
in porosity and permeability. The net effect could be complex. Porosity and

6.
t

permeability will likely decrease in some portions of the beds and increase
in nearby areas.

Kaolinite in shales may be destroyed at temperatures as low as 8OoC but

can persist to temperatures in excess of 220C under some conditions. In
part the temperature of alteration is a function of time, but the organic
content (pH) and the composition of the associated clay minerals are probably
more important factors. In clay beds associated with coal seams it is believed
that kaolinite converts to illite and chlorite when the semianthracite stage

(200C) is reached. In shales it is suggested that the Mg and Fe released

from the mixed-layer illite-montmorillonite react with kaolinite to form
chlorite. Kaolinite may also alter to an Al-rich dioctahedral chlorite or
supply the Al, with the release of Si, for the formation of higher-charged
illites. Where kaolinite is abundant in shales, it can be converted to pyrophyllite at temperatures as low as 200C.
Most sandstones and siltstones interbedded with shales contain more kaolinite than the associated shales. Most of the kaolinite is secondary and
formed from feldspar and clay minerals under acid conditions, commonly created
by the breakdown of organic material. Kaolinite can start to form at surface
temperatures, but formation is probably accelerated with increasing temperature.

The kaolinite can convert to dickite at temperatures as low as 7OoC,

but this is not common. Kaolinite can also persist to temperatures of 325O
to 375OC. Experimental hydrothermal studies indicate that in the presence
of K, kaolinite readily forms illite.
It can be expected that the heat generated by radioactive waste will

cause some chlorite to be formed in nearly any type of shale that has not been

hi*

13

Lj
*-

preheated to near 300OC.

This may cause some minor textural changes. At

temperatures slightly below 3OO0C, chlorite porphyroblasts and veins may form.
This chlorite could conceivably fill fractures and other voids that might

develop in the shale. In sandstone and siltstone beds, secondary chlorite

would tend to decrease permeability but possibly not porosity.

It is also

possible that low-temperature chlorite will be destroyed when exposed to

higher temperatures.
Chlorites can form at surface temperatures when either Mg or Fe are readily available.

In soils, Al and Fe hydroxides precipitate between expanded

layers to form a chlorite-like material and limited data suggest that minor
amounts of chlorite are forming in the present ocean. Authigenic Mg-rich
chlorites and mixed-layer chlorite-smectites are relatively abundant in evaporite rocks and tidal carbonate rocks.

Fe-rich chlorites and chamosites are

commonly present in ironstones.

In shales, chlorite is believed to form as a by-product when montmoril-

"u

lonite layers are converted to illite. This reaction can start at temperatures
as low as 7OOC.

Chlorite is also believed to form from kaolinite when Mg and

Fe are present.

The formation temperature ranges from 150 to 200OC.

Chlor-

ite may also form during the late stages of diagenesis, 200 to 3OO0C, from
material released during the final stages of illite recrystallization. This
material usually forms porphyroblasts or veins.

In hydrothermal areas, chlor-

ite has first been encountered at temperatures ranging from 130' to 220OC.
At higher temperatures it converts to chlorite or trioctahedral mica.
T

Corren-

site, regular mixed-layer chlorite-montmorillonite, can form in shales at a

temperature of approximately 100C and persist to temperatures near 300OC.
Chlorite forms at relatively low temperatures in sandstones and limestones. The chlorite fills or lines voids and replaces such minerals as

14
f e l d s p a r , b i o t i t e , volcanic material, calcite, and montmorillonite.
s i t i o n s are highly v a r i a b l e .

Compo-

A t a temperature of approximately 15OOC t h e

LJ
t

The source material f o r t h e

c h l o r i t e undergoes a s t r u c t u r a l transformation.

c h l o r i t e is commonly volcanic material, f e l d s p a r , c l a y minerals, and mafic

heavy minerals.

Corrensite may form a t t h e same time.

The compodtion of c h l o r i t e formed during diagenesis i s dependent on

t h e composition of t h e host rock and temperature.

This makes i t d i f f i c u l t

t o use c h l o r i t e as a paleotemperature i n d i c a t o r .

However, once formed, t h e

composition of c h l o r i t e changes with increasing temperature.

The author is

p r e s e n t l y t r y i n g t o measure t h e s e chemical changes and relate them t o paleotemperatures.

The heat from high level r a d i o a c t i v e waste could conceivably generate
methane gas o r o i l from t h e organic material i n s h a l e s , though t h e minimum
time necessary f o r t h e s e r e a c t i o n s t o occur i s not known.
i n very young sediments.

Methane occurs

The o i l i s not l i k e l y t o be a problem, but t h e

methane could produce high pressures and possibly move i n t o t h e repository.

Another problem can arise i n s h a l e s t h a t have not been previously exposed t o
high temperatures.

CO w i l l be generated and carbonate minerals may be pre2

c i p i t a t e d i n t h e s h a l e pores and i n sandstone and s i l t s t o n e beds.

The C02

could a l s o decrease t h e pH t o t h e extent t h a t t h e f e l d s p a r s and o t h e r minerals

would a l t e r t o k a o l i n i t e , causing f u r t h e r changes i n t h e porosity-permeability
system.

It would be d e s i r a b l e t o select a host s h a l e with a minimum amount

of organic material and preferably one t h a t has been exposed f o r a considera b l e time t o temperatures i n excess of 25OOC.

Most major chemicalmodifica-

t i o n s of organic material appears t o be complete by 2500C, though some d r y

gas may be generated a t higher temperatures.

Y-

15
Shales commonly contain 1 t o 3 percent organic material.

Because t h i s

material i s continuously changing character as a function of increasing temperature, i t i s necessary t o determine what r e a c t i o n s might be expected.
Further, considerable d a t a have been accumulated r e l a t i n g s t a g e s of organic
metamorphism t o temperature.
During c o a l i f i c a t i o n t h e r e i s a decrease i n p o r o s i t y and moisture cont e n t and CH

4 and

CO

are released.

particularly pertinent.

Numerous o t h e r changes occur but are not

Coal rank, peat through meta-anthracite,

determined by temperature, but time i s a l s o a major f a c t o r .

is primarily

Temperatures

of 60C t o 150C w i l l normally produce bituminous c o a l and 200C a n t h r a c i t e .

Anthracite can be formed a t temperatures ranging from

looo

t o 3OO0C, depend-

ing on t h e l e n g t h of time t h e material has been subjected t o t h e p a r t i c u l a r

c
Y

temperature.
C o a l i f i c a t i o n of organic material i n shales commonly r e s u l t s i n t h e
formation of hydrocarbons, p a r t i c u l a r l y i f t h e organic material w a s derived

"u

from lower organisms (algae, animal plankton, and b a c t e r i a ) .

Various at-

tempts have been made t o relate hydrocarbon generation t o c o a l rank and temperature.

Because time i s a f a c t o r , t h e temperature values are not c o n s i s t e n t .

Methane gas i s produced during t h e e a r l y s t a g e s of c o a l i f i c a t i o n .

Oil

generation commonly starts a t temperatures of 65" t o 1OoOC and ends a t temp e r a t u r e s of 1300 t o 150C:

A t higher temperatures, condensate and w e t gas

are produced, followed by t h e formation of dry gas (methane) a t temperatures

g e n e r a l l y i n excess of 1600C.

The l i q u i d hydrocarbon zone generally coin-

c i d e s with t h e high v o l a t i l e bituminous and t h e upper p o r t i o n of t h e medium

v o l a t i l e bituminous c o a l zones.

V i t r i n i t e r e f l e c t a n c e values f o r t h e hydro-

carbon zone range from 0.5 t o 1.3.

16
Organic material and clay minerals both progress through diagenetic and
metamorphic changes with increasing temperature. Attempts have been made to

LJ
t

correlate the changes that take place in the two materials, but correlation
is difficult becuase the changes in the organic material are more time depen-

dent than those that occur in clay minerals and the changes in the clay minerals are dependent on rock and water chemistry. The data suggest the clay
minerals are more reliable than organic material as paleotemperature indicators.

A comparison of coal rank and metamorphic mineral facies suggests that

the boundary between the diagenesis zone and the anchizone coincides with
the change from semianthracite to anthracite coal (V.R. 2 . 5 , V.M. 8 percent).
On the basis of coal studies, this change in coal rank occurs at an average
temperature of 200C.

The boundary between the anchizone and the epizone

(greenschist facies) falls somewhere near the boundary between low-rank and
high-rank meta-anthracite.
40OoC.

This change occurs somewhere between 3000 and

As anthracite can form at temperatures ranging from 1000 to 3000C,

its relation to specific mineral facies is not good.

For example, kaolinite

is commonly destroyed at temperatures higher than 200C and is considered to

be destroyed in the anchizone, yet it is commonly present, along with pyrophyllite, in Carboniferous anthracite coals. The persistence of kaolinite
in high-rank coals is probably due to the absence of other silicate minerals
and a restricted chemistry.
In clay-rich rocks, the diagenetic-metamorphic zonation is based largely
on the character of illite. The diagenetic zone-anchizone boundary is based

on a crystallinity index of 7 . 5 (or 4 . 0 ) and a sharpness ratio of 2 . 3 , and

it has been suggested that it is equivalent to the semianthracite-anthracite

Cl@

17

u
*

K a o l i n i t e and random mixed-layer illite-montmorillonite are pre-

boundary.

sumed t o be absent i n t h e anchizone s t a g e , and pyrophyllite, a l l e v a r d i t e ,

paragonite, and phengite are presumed t o be formed.

The anchizone-epizone

boundary i s based on a c r y s t a l l i n i t y index of 4.0 (or 2.5) and a sharpness

<

r a t i o of 12.

The e p h o n e o r greenschist f a c i e s i n s h a l e s i s characterized

by t h e presence of,muscovite, c h l o r i t e , and a t a more advanced s t a g e b i o t i t e ;

a l l expanded l a y e r s are gone and Mg and Fe have been removed from t h e i l l i t e ,
converting i t t o muscovite.

However, phengite with an abundance of Mg and

Fe i n t h e octahedral s h e e t commonly occurs i n t h e greenschist f a c i e s .

Most of t h e expanded l a y e r s i n mixed-layer illite-montmorillonite are
l o s t a t a temperature of 120" t o 150"C, i n t h e zone of diagenesis.

However,

t h e f i n a l 20 percent expanded l a y e r s can p e r s i s t t o temperatures w e l l i n

L
w

excess of 2OO0C (upper anchizone boundary based on coal-rank).

The c r y s t a l -

l i n i t y index and sharpness r a t i o of t h e s e samples would p l a c e them w e l l within

t h e d i a g e n e t i c zone even though they have been exposed t o temperatures higher

than 2OOOC.

I l l i t i c c l a y s t h a t have c r y s t a l l i n i t y values ( ~ 7 . 5 ) t h a t would

place them i n t h e anchizone commonly contain only a minor amount (%lo percent) of mixed-layer material; t h i s material contains 5 t o 20 percent expanded
layers.

Thus, i n t h e a r g i l l a c e o u s rock t h e upper boundary of t h e anchizone

i s i n d i c a t i v e of a temperature i n excess of 2OO0C, possibly something on t h e

order of 250C.

The lower boundary of t h e anchizone, upper greenschist f a c i e s

boundary, i s estimated t o occur a t approximately 400C.

I n Figure 1, I have shown t h e c l a y mineral changes which occur i n s h a l e s
15

during b u r i a l and have r e l a t e d t h e s e changes t o temperature.

scale i s a b e s t estimate based on t h e d a t a discussed.

estimated temperature boundaries f o r t h e anchizone.

The temperature

Also shown are t h e

Most of t h e mineral

18

b
% EXPANDED
LAYERS
OC

COAL HYDROCARBONS
100 KAOLINITE CHLORITE CORRENSITEYOUNG-* OLDYOUNG + OLD ZONES

7!

DIAGENES
12!
~

17t

225

S. R. 2.3
C.I. 7.5 mn

275

- ILLITE
ANCHIZON

325

375
S.R. 12
C.I. 4 mm

425
IUSCOVITE
ZHLORITE

EPIZONE
(GREENSCHIST)

475

Figure 1. Relation of diagenetic-metamorphic changes in clay minerals and

organic matter to temperature. Discussion is on the following page.

b?

19

'

Figure 1. This f i g u r e summarizes t h e r e l a t i o n of diagenetic-metamorphic

changes i n c l a y minerals and organic matter i n s h a l e s t o temperature.

Most

mineralogic changes occur over a r e l a t i v e l y wide temperature range; however,

s t r u c t u r a l and chemical changes should prove t o be u s e f u l paleotemperature

indicators.
The f i r s t column shows t h e temperature i n t e r v a l over which smectite
(montmorillonite) is converted t o i l l i t e .

The area with t h e h o r i z o n t a l l i n e s

i n d i c a t e s t h e range i n t h e proportion of i l l i t e l a y e r s t h a t can form a t a

given temperature.

A l l of t h e l a y e r s of montmorillonite are converted t o

i l l i t e a t temperatures of 275

as low as 200 C.

t o 300 C .

Paragonite may form a t temperatures

A t temperatures i n excess of approximately 425 C i l l i t e i s

converted t o muscovite (or phengite) and c h l o r i t e .

The second column shows t h e r e a c t i o n of k a o l i n i t e t o temperature.

Kao-

l i n i t e may be destroyed a t temperatures as low as 100 C but can p e r s i s

temperatures i n excess of 220 C .

to

A t 200 C i t can be converted t o pyrophyl-

l i t e and i f Mg, Fe and K are present, t o mixed-layer illite-montmorillonite

and c h l o r i t e .
Fe-rich c h l o r i t e may be formed from a v a r i e t y of materials a t a tempera-'
t u r e as low as 70 C or lower.
increasing temperature.

The amount of c h l o r i t e formed i n c r e a s e s with

The c h l o r i t e s become more Mg-rich with increasing

temperature.

Corrensite, mixed-layer chlorite-vermiculite

l o n i t e ) , forms at temperatures i n t h e range of 90

a t least 325
L

t o 350 C.

(or montmoril-

t o 150 C and p e r s i s t s t o

A t higher temperatures i t converts t o c h l o r i t e o r

Mg-rich t r i o c t a h e d r a l mica.

Over a long period of time (old) c o a l can be converted from semi-anthrac i t e t o a n t h r a c i t e a t 100 C.
2

I n younger sediments a temperature of 300 C is

20
required f o r t h e equivalent conversion.

Hydrocarbons have a s i m i l a r time-

temperature r e l a t i o n .
The right-hand column shows t h e zones of diagenesis and low-grade metamorphism.

The boundary between t h e zone of diagenesis and t h e anchizone is

based on a c r y s t a l l i n i t y index (C.I.)

of 2.3.

of 7.5 and a sharpness r a t i o (S.R.)

The boundary between t h e anchizone and epizone (greenschist) i s

based on a C.I. of 4 and a S.R. of 12.

6.I

21
changes are not as temperature s p e c i f i c as indicated, because v a r i a b l e chemi-

c a l and mineral compositions w i l l influence t h e transformation temperature.

The sloping boundaries between phases i n d i c a t e t h e temperature range over
which t h e s e r e a c t i o n s occur and a l s o i n d i c a t e , i n a general way, t h e rela-

t i v e p r o b a b i l i t y of t h e change occurring a t a given temperature.

I n an e f f o r t t o relate t h e s i l i c a t e changes t o some organic changes,
t h e published temperature ranges are shown f o r t h e formation of a n t h r a c i t e
and t h e threshold of i n t e n s e o i l generation.
The c o l o r of conodonts changes from p a l e yellow t o black as t h e tempera t u r e t o which they have been exposed increases from 50" t o 400OC.

The c o l o r

a l t e r a t i o n index (CAI) c o r r e l a t e s reasonably w e l l with t h e v i t r i n i t e r e f l e c t ance v a l u e s of associated organic material.

The CAI i s not p a r t i c u l a r l y

s e n s i t i v e and can be used only t o estimate temperatures t o within a hundred

degrees.

Conodonts occur primarily i n limestones, but i f limestone beds are

present i n a s h a l e t h e CAI can be used t o g i v e a general i d e a of t h e paleatemperature t o which t h e s h a l e has been exposed.
F i n a l l y , i t should be mentioned t h a t t h e z e o l i t e minerals have a diagenetic-metamorphic temperature range similar t o t h e c l a y minerals, i.e.,
t o 400OC.
i n shales.

50"

The z e o l i t e s are abundant i n volcanic rocks and r e l a t i v e l y rare

The z e o l i t e s should be thoroughly evaluated before any s e r i o u s

plans are made t o use volcanic rocks f o r a repository.

I n conclusion, t h e r e i s no doubt t h a t when s h a l e s are subjected t o temp e r a t u r e s of 200 t o 3OOOC forahundreds of years, chemical, physical, and
mineralogical changes w i l l occur.

The e x t e n t of t h e s e changes w i l l depend

l a r g e l y on t h e maximum b u r i a l temperature t o which t h e s h a l e s have previously

been exposed.

Montmorillonitic s h a l e s and s h a l e s with mixed-layer i l l i t e -

22

bj

montmorillonite containing a high content of montmorillonite l a y e r s w i l l

undergo t h e most extensive changes.

The most s e r i o u s change w i l l probably

be t h e release of i n t e r l a y e r water.

Bench tests and f i e l d tests w i l l need

t o be conducted t o determine t h e seriousness of t h i s problem; however, because of t h e e f f e c t s of time on t h e r e a c t i o n s , t h e tests w i l l have l i m i t e d

p r e d i c t i v e value.
I l l i t e - c h l o r i t e shales, l a r g e l y of Paleozoic age, which have been subj e c t e d t o b u r i a l temperatures i n excess of 200 w i l l undergo only minor changes
when exposed t o r a d i o a c t i v e h e a t that produces temperatures of 200" t o 3OO0C.
The heat w i l l have r e l a t i v e l y l i t t l e e f f e c t on t h e adsorption p r o p e r t i e s of

illite.

Water problems w i l l be minimal.

w i l l have to be made.

Additional bench and f i e l d tests

It may be necessary t o conduct f i e l d tests a t a depth

of approximately 300 m t o o b t a i n r e a l i s t i c data.

Theoretical and experimental phase equilibrium s t u d i e s provide a n ins i g h t t o t h e phase changes which occur as pressure and temperature change.
However, because of k i n e t i c r e s t r a i n t s , t h i s i%fonnation can be considered
only as a crude approximation of what happens i n t h e n a t u r a l system where
time i s a major f a c t o r i n overcoming sluggish reactions.

Thermodynamic

c a l c u l a t i o n s of equilibrium r e a c t i o n s r e q u i r e s a knowledge of t h e standard

f r e e energies::of formation and t h e composition of t h e phases involved.

Many

of these d a t a have not been a c c u r a t e l y determined.

A more empirical approach t o constructing phase diagrams is based on

obtaining experimental information and i n t e r p r e t i n g i t on t h e b a s i s of obs e r v a t i o n s of n a t u r a l mineral associations.

The phase changes observed i n

<

23

u
4

laboratory experiments are g e n e r a l l y s i m i l a r t o those observed i n nature;

however, many of t h e rates of r e a c t i o n are slow and i t i s d i f f i c u l t t o d e t e r mine which phases are s t a b l e and which are metastable.

Thus, i t i s d i f f i -

c u l t t o conclude from many of t h e s t u d i e s which phases w i l l develop during

n a t u r a l diagenesis where equilibrium conditions are more l i k e l y t o p r e v a i l .
Laboratory experiments are of s h o r t duration and t h e temperatures a t which
phase changes occur cannot u s u a l l y be projected t o t h e n a t u r a l system with
any degree of c e r t a i n t y .

24
SMECTITE
Conversion t o Mixed-Layer Phase
Smectites, l a r g e l y montmorillonites, are more temperature s e n s i t i v e than
t h e o t h e r c l a y minerals.

Numerous s t u d i e s (Burst, 1959; Powers, 1959; Weaver,

1959; Teodorovich and Konyukhov, 1970; Perry and Hower, 1970; Dunoyer D e
Segonzac, 1970; Weaver and Beck, 1971; Moort, 1971; Foscolos and Kodama, 1974;
Heling and Teichmuller, 1974; Hower e t al., 1976) have demonstrated that with
depth and temperature montmorillonite is transformed t o mixed-layer i l l i t e montmorillonite.

Many authors relate t h e disappearance of smectite t o speci-

f i c depths o r temperatures but i t i s not clear w h a t is meant by t h e "disappearance of smectite".

Generally i t i s assumed t h a t t h e absence of t h e 17 A

x-ray peak, a f t e r t h e sample is t r e a t e d with ethylene glycol, r e p r e s e n t s t h e

absence of smectite.

However, c a l c u l a t i o n s (MacEwan e t al., 1961; Reynolds,

1967) i n d i c a t e t h a t expandable c l a y can contain up t o 60 percent 1 0 A l a y e r s

(40 percent 17 A l a y e r s ) and s t i l l produce a 1 7 A peak.

Thus, d i a g e n e t i c e f f e c t s

s t a r t a t shallower depths and lower temperatures than t h e depths a t which t h e

1 7 A x-ray peak disappears.

The s t u d i e s of Burst (1969), Weaver and Beck (1971),

and Hower e t a l . (1976) show that, i n t h e Gulf Coast, d i a g e n e t i c e f f e c t s can be

detected a t temperatures approximately 26-30C lower than t h e temperature a t
which t h e amount of l a y e r c o l l a p s e is s u f f i c i e n t t o cause t h e 1 7 A peak t o d i s appear (Figure 2).

I n t h e Gulf Coast t h e temperature a t which l a y e r contrac-

t i o n is f i r s t detected ranges from approximately 5OoC f o r t h e Pliocene t o 8 P C

f o r Oligocene sediments.

It is not clear why c o n t r a c t i o n appears t o start a t a

lower temperature i n younger sediments.

The i d e n t i f i c a t i o n of t h e depth of

i n i t i a l l a y e r c o n t r a c t i o n i s s u b j e c t i v e and f u r t h e r is dependent on t h e s i z e
f r a c t i o n analyzed.

Chemical changes presumably occur before l a y e r c o l l a p s e is

observed by x-ray analysis.

r',

20
O

1'

40
60

80

/
50% COLLAPSE

100
120
140
160
180

200
220
240
260

0 LOSS OF 17 A PEAK
GEOTHERMAL

ILLITE

TOTAL DEPTH, NO ILLITE

1 = <0.1 ptn

2 = 0.5 2 pm

i
25

I
50

I
75

I
100

I
125

A-

150

I
300

325 MILLION
YEARS

Figure 2. Temperature of conversion of smectite l a y e r s t o i l l i t e as a function of t i m e . Upper l i n e

i n d i c a t e s temperature of " i n i t i a l " conversion (20%-30% i l l i t e l a y e r s ) . Bottom l i n e i n d i c a t e s temperat u r e a t which 70%-80% i l l i t e l a y e r s ("stable" phase) are f i r s t encountered. Arrows i n d i c a t e temperat u r e i n t e r v a l over which t h i s l a t t e r phase p e r s i s t s with l i t t l e change. I n no i n s t a n c e w a s montmorill o n i t e completely converted t o i l l i t e . Dashed l i n e i n d i c a t e s temperature t o which 17 A x-ray peak
p e r s i s t s . References i n text.

26
Perry and Hower's (1972) d a t a i n d i c a t e that i n t h e Gulf Coast Oligocene

bj

t h e 17 A peak i s l o s t a t a temperature of approximately 105C and i n t h e Miocene a t approximately 110C.

Pusey (1973b) reported a temperature of 1 2 8 C .

Weaver and Beck (1971) reported t h a t t h e peak is l o s t a t a temperature of

Y

8OoC i n Gulf Coast Upper Miocene sediments; Aoyagi e t al. (1975) found t h a t
i t w a s l o s t a t t h e same temperature i n a Miocene s e c t i o n i n Japan.

I n Creta-

ceous sediments of North Africa t h e 17 A peak is l o s t a t approximately 70C

(Dunoyer d e Segonzac, 1969).

I n t h e Upper Mississippian s h a l e s of Oklahoma

it disappears a t approximately 60C.

Burst's (1969) d a t a f o r 29 Gulf Coast w e l l s i n d i c a t e t h a t t h e temperature
a t which c o l l a p s e of montmorillonite l a y e r s i s " f i r s t " observed (broadening
of 1 7 A peak) ranges from 9O0to 13OOC with a n average of 102OC.

It i s more

l i k e l y t h a t t h e s e values are t h e temperature a t which 60 percent of t h e l a y e r s

c o l l a p s e r a t h e r than t h e temperature of i n i t i a l l a y e r collapse.

I n the off-

l a p sequence of t h e Gulf Coast, many of t h e o l d e r sediments occur a t shallower

depths than younger sediments.

Thus, i n t h e Eocene t h e 1 7 A peak can be gone

a t depths of less than 1,500 m y whereas i t can p e r s i s t t o 3,600 m i n younger

sediments.

Unfortunately, t h e geothermal gradie'nt g e n e r a l l y i n c r e a s e s i n t h e

d i r e c t i o n ( n o r t h and northwest) of increasing age of t h e subcropping sediments.

With t h e present d a t a i t i s not p o s s i b l e t o s e p a r a t e t h e e f f e c t s of t i m e and
geothermal gradient.
I n t h e Oligocene sediments of t h e Rhine Graben, montmorillonite (17 A
peak) disappears a t temperatures ranging from 40" t o 96OC (Doebl e t a l . ,
1974); Heling, 1974), though i n one w e l l i t p e r s i s t s t o a temperature of 1 1 P C .

In t h e l a t t e r case subsidence w a s r a p i d and r e l a t i v e l y r e c e n t and i t w a s suggested t h a t high temperatures d i d not p r e v a i l long enough t o complete t h e
transformation.

The 4 P C c o l l a p s e temperature i s believed by Heling (1974)

Li

27

t o be due t o a high permeability caused by t h e presence of i n t e r c a l a t e d porous

limestones.

If t h e 4OoC value is c o r r e c t , then l a y e r c o l l a p s e must have

- s t a r t e d a t temperatures of 2OoC t o 3 O O C .

This does not seem l i k e l y .

Teodorovich and Konyukhov (1970) observed mixed-layer c l a y s forming a t

'ij

r e l a t i v e l y shallow depths i n t h e J u r a s s i c and Lower Carboniferous sediments

of Russia.
biotite

They believed t h i s was due t o t h e ready a v a i l a b i l i t y of K from

I n t h e S a l t o n Sea thermal area, t h e 17 A peak disappears a t a temperature

of approximately 5OoC (Muffler and White, 1969).

Studies of t h e New Zealand

geothermal area by Eslinger and Savin (1973 a and b) show t h a t t h e a l t e r a t i o n

of montmorillonite t o i l l i t e i s not a simple d i r e c t function of temperature.

I n borehole Br16, smectite p e r s i s t s t o a temperature of approximately 1 5 0 , C ,

where i t g i v e s way t o a mixed-layer illite-smectite containing about 10 per*
*-

cent smectite layers.

of 180C i s reached.

This material p e r s i s t s with depth u n t i l a temperature

No expanded l a y e r s are present a t temperatures higher
4

'";

than 18OoC.

The development of two-layer monoclinic (2M) i l l i t e i s not l i n e a r

with temperature.

A t 895 m (24loC), 2M i l l i t e was detected (80%), but a t

1356 m (27bC) only 35 percent of t h e i l l i t e was t h e 2M v a r i e t y .

None was

detected a t temperatures less than 200C.

I n borehole Br7 a t a depth of 162 m (112OC) t h e mixed-layer c l a y cont a i n s 15 t o 20 percent expanded l a y e r s ; a t 433 m (2090C) i t contains 90 t o
95 percent expanded l a y e r s .

The l a t t e r i s believed t o have formed metastably,

because i n most boreholes t h e upper s t a b i l i t y l i m i t of smectite is 1 3 8 C t o

150C.
-+-

I l l i t e develops a t 750 m (2400C).

I n t h e New Zealand geothermal area, t h e hydrothermal conversion of smect i t e t o i l l i t e i s more complex than normally encountered i n sediments which have
undergone b u r i a l diagenesis.

k.,

I n a l l likelihood t h i s is because ili areas l i k e

28
t h e Gulf Coast t h e o r i g i n a l sediments contain d e t r i t a l montmorillonite and
b e i d e l l i t e , whereas i n t h e geothermal areas t h e rocks are volcanic and are
f i r s t a l t e r e d t o smectite before being converted t o i l l i t e .
The i n i t i a l m o n t m o r i l l o n i t e l a y e r s which are converted t o i l l i t e are
randomly interspersed among t h e montmorillonite l a y e r s .

Random i n t e r s t r a t i -

r.

f i c a t i o n of i l l i t e and montmorillonite l a y e r s continue u n t i l t h e i l l i t e l a y e r s

c o n s t i t u t e approximately 65 percent.

As dehydration and i l l i t i z a t i o n continue,

t h e i n t e r l a y e r i n g becomes ordered (Reynolds and Hower, 1970; Perry and Hower,

1970; and Weaver and Beck, 1971).

The rate a t which t h e i l l i t e l a y e r s form

depends on t h e geothermal g r a d i e n t (Perry and Hower, 1972, and Doebl e t a l . ,

1974) but may not be t i m e dependent.
a r a t i o of 7:3 t o 8:2,

Once an illite-montmorillonite

reaches

l i t t l e a d d i t i o n a l change occurs u n t i l t h e r e i s a con-

s i d e r a b l e i n c r e a s e i n temperature.
I n Gulf Coast sediments t h e c o l l a p s e of mixed-layer illite-montmorill o n i t e with a r a t i o of 1:4 t o t h a t with a r a t i o of 4 : l can occur over a temp e r a t u r e range of approximately 4OoC.

Where t h e geothermal g r a d i e n t i s low o r

i n younger sediments, t h e same amount of c o l l a p s e occurs over a range of 700

t o 90'C.

I n t h e Paleocene-Cretaceous,

of approximately 40'C

(50'

t h e c o l l a p s e occurs over a n i n t e r v a l

t o 90C)(Dunoyer d e Segonzac, 1969).

I n t h e Cre-

taceous of B r i t i s h Columbia (Foscolos and Kodama, 1974), t h i s c o l l a p s e i s

reported t o occur over a temperature range of approximately 6OOC (800 t o
140'C).

I n t h e Upper Mississippian Spring s h a l e s of Oklahoma, t h e equivalent

c o l l a p s e occurs over a temperature range of approximately 6CPC ( 6 8 t o 12oDC).

These d a t a (Figure 2) suggest t h a t temperature is considerably more important
than time i n determining t h e rate of l a y e r contraction.
I n t h e Gulf Coast Cenozoic sediments, t h e top of t h e 7:3-8:2

phase has

been observed a t a temperature of 90C i n Upper Oligocene (Hower et al., 1976),

cad-

29

\-hl

120C i n Lower Eocene (Boles and Franks, 1979), 125C i n Oligocene and 1 6 8 C
i n Miocene (Perry and Hower, 1972).

I n t h e s e w e l l s no a d d i t i o n a l change w a s

observed as temperatures increased t o 170" C (maximum temperature reported).

I n another Upper Miocene section, t h i s phase was not reached a t a temperature
n

of 119C (Weaver and Beck, 1971).

I n t h e Cretaceous of B r i t i s h Columbia

(Foscolos and Kodama, 1974), t h e phase f i r s t occurs a t 140C.

I n t h e Upper

Mississippian Springer Shale of Oklahoma, t h e 8:2 phase f i r s t occurs a t

approximately 120C and p e r s i s t s t o a temperature of a t least 22OOC (Shell,
Rumberger No. 5, 7,254 m).

It a l s o persists t o 220C (9,083 m) i n the- De-

vonian of t h e Lone S t a r Badin No. 1 w e l l i n Oklahoma.

For t h e Cretaceous bentonites of t h e Denver Basin (Rettke, 1976), t h e r e
i s a c u r v i l i n e a r r e l a t i o n between i n s i t u temperatures and proportion of
illite-montmorillonite layers.
c
4

A t 60C t h e c l a y contains 20 percent i l l i t e

l a y e r s and a t 100C 50 percent i l l i t e layers.

Extrapolation of t h e curve indi-

cates a r a t i o of 7:3 would be a t t a i n e d a t a temperature of approximately 1600C.

A s might be expected, r e a c t i o n rates are r e l a t i v e l y rapid during t h e i n i t i a l

s t a g e of c o l l a p s e ( i l l i t e l a y e r s i n c r e a s e from 15 percent t o 40 percent over

a temperature range of 600 t o 75C) and then became progressively slower (over
t h e temperature range of 75" t o 1OOOC t h e i l l i t e l a y e r s i n c r e a s e from 40 percent t o 50 percent.
P a r t of t h e reason f o r t h e reported d i f f e r e n c e i n t h e temperatures required t o produce a given illite-montmorillonite
f r a c t i o n s examined.

r a t i o is the different size

Hower e t a l . (1976) show t h a t mixed-layer c l a y i n ' t h e

<0.1 l m ~f r a c t i o n a t t a i n s a r a t i o equivalent t o that of t h e 0.5 t o 2 I.rm f r a c L

c

t i o n a t a temperature of 200 t o 4OOC lower than t h a t of t h e coarser f r a c t i o n .

It i s not clear why t h e f i n e r f r a c t i o n should have a higher percentage of

=w

i l l i t e l a y e r s than t h e coarser f r a c t i o n .

The i n i t i a l montmorillonite f l a k e

30
s i z e i s small, and f l a k e s i z e i s assumed t o i n c r e a s e as t h e proportion of

i l l i t i c l a y e r s increases.

br

The d a t a from Hower e t a l . suggest otherwise.

Dispersion may be a f a c t o r .
Figure 2 summarizes much of t h e d a t a discussed i n t h e preceeding pages.
Considering t h e inherent e r r o r s and t h e subjectiveness of t h e i n t e r p r e t a t i o n t h e r e l a t i o n between t h e amount of l a y e r collapse, temperature, and time
appears reasonable.

Of major i n t e r e s t i s t h e f a c t t h a t t h e temperatures a t

which t h e various c o l l a p s e s t a g e s are reached do not appear t o vary r e g u l a r l y

with time.

This can i n d i c a t e that t h e r e a c t i o n rate i s so slow t h a t time i s

not a major f a c t o r o r t h a t t h e various mixed-layer r a t i o s are temperatures t a b l e equilibrium phases.

However, t h e r e l i a b i l i t y of t h e d a t a i s such t h a t

temperature changes of 20 t o 4OoC, with t i m e , should be d i f f i c u l t t o detect.

T h e ' a v a i l a b i l i t y of K i s another f a c t o r and may determine t h e temperature a t
which t h e mixed-layer c l a y i s converted completely t o i l l i t e .
I n geothermal areas, under hydrothermal conditions, montmorillonite i s
completely converted t o i l l i t e a t approximately 200C; i n s h a l e s , an apprec i a b l e percentage of expanded l a y e r s is present a t b u r i a l temperatures of 220C.
It may be t h a t complete conversion t o i l l i t e i n shgtles may r e q u i r e a tempera-

t u r e c l o s e t o 30OoC.

I t should be noted t h a t porous sands i n geothermal areas

may be completely cemented by secondary quartz a t temperatures of <105OC

(Elders and Bird, 1973).
Other Complications
It i s assumed that t h e r e is a continuous i n c r e a s e i n t h e proportion of

contracted l a y e r s with depth.

A p l o t of t h e mixed-layer r a t i o v e r s u s depth

(Figure 3), f o r core samples, i n d i c a t e s t h a t t h e r e are several reversals.

The d a t a of Hower e t al. (1976), and other s t u d i e s of Gulf Coast w e l l s I have

31

1000

55OC

2000

3000

TOP H. P.

LI

v)

BASE 1 7 A

ki

4000

12OOC

50W

600C

Figure 3. Montmorillonite contraction profile for typical Gulf Coast well

(Weaver and Beck, 1971). Reversals appear to be real. Top H.P. indicates
top of high-pressure zone. Base 17 A indicates maximum depth of occurrence
of 17 A montmorillonite x-ray peak.

32
made, i n d i c a t e t h i s i s a common f e a t u r e .

A r e c e n t study by Boles and Franks

(1979) of Lower Eocene (Wilcox) sediments from southwest T e x a s showed that

t h e s t a b l e 20 percent mixed-layer phase w a s reached a t 12OOC and remained
constant t o 150OC.

There are numerous reversals, with t h e proportion of exc

panded l a y e r s being as high as 40 percent.

This occurs i n both t h e sandstones

and s h a l e s , but t h e c l a y i n t h e sandstones commonly has more expanded l a y e r s .

The number of expanded l a y e r s i n adjacent samples ranges from less than 10
percent t o 40 percent.
It appears t h a t some f a c t o r s o t h e r than depth and temperature can e f f e c t

t h e c o n t r a c t i o n of montmorillonite.

The a b e r r a t i o n s are most l i k e l y due t o

v a r i a t i o n s i n t h e bulk chemistry of t h e shale.

Eberl and Hower (1977) reported

t h a t a t temperatures below 3OOOC Na p l u s g l a s s of b e i d e l l i t e composition produced a mixed-layer c l a y similar t o t h a t of t h e K g l a s s .

temperatures a f u l l y expanded s t a b l e phase formed.

a r e g u l a r mixed-layer phase developed.

However, a t higher

A t even higher temperatures

The reversals i n t h e i n c r e a s e i n t h e

proportion of contracted l a y e r s with depth (Figure 3) could conceivably be

due t o t h e presence of i n t e r l a y e r N a .
r e v e r s a l s occur.

N a i s a t a maximum i n t h e i n t e r v a l where

A deficiency of K would a l s o i n h i b i t contraction.

On t h e b a s i s of v a r i a t i o n i n ease of expandability, Foscolos and Kodoma

(1974) concluded t h a t t h e mixed-layer c l a y i n t h e Cretaceous Buckinghouse
Formation of Canada consisted of mixtures of i l l i t e , montmorillonite, and
vermiculite.

Weaver and Beck (1971) have presented d a t a that suggest some of

t h e montmorillonite l a y e r s are converted t o c h l o r i t e r a t h e r than i l l i t e and

that t h e mixed-layer 7:3 i s a c t u a l l y composed of equal p a r t s of i l l i t e , c h l o r i t e ,

and montmorillonite.
Most r e c e n t i n t e r p r e t a t i o n s of mixed-layer illite-montmorillonite
based on t h e c a l c u l a t e d curves of Reynolds and Hower (1970).

Recently

are

33

W
.t

Tettenhorst and G r i m (1975 a and b) have challenged some of t h e i r i n t e r p r e tations.

Among o t h e r things, they suggest t h e fol-lowing.

Variation i n back-

ground i n t e n s i t y a t low angles i s due t o v a r i a t i o n s i n mean c r y s t a l l i t e thickness r a t h e r than t o i n t e r s t r a t i f i c a t i o n .

When t h e mixed-layer phase contains

90 percent l a y e r s with 1 0 A spacings, t h e x-ray peaks s h i f t p o s i t i o n as t h e

1 7 A l a y e r changes from t h e o u t s i d e of t h e c r y s t a l l i t e t o t h e middle.

When t h e

17 A l a y e r s are imbedded within t h e c r y s t a l l i t e s , t h e calculated x-ray p a t t e r n s

resemble those Reynolds and Hower a t t r i b u t e t o ordered i n t e r l a y e r i n g . The
,
presence of one g l y c o l l a y e r on t h e outer s u r f a c e of t h e c r y s t a l l i t e s produces
t h e same r e s u l t s as t h e presence of a small percentage of 1 0 A layers.

Some

of t h e expanded l a y e r may adsorb only one l a y e r of ethylene glycol (13.5 A)

,
r a t h e r than two (17 A).
As l i t t l e as 1 0 percent one-layer spacings decreases
t h e r e s o l u t i o n i n t h e 7-9'20

region, s h i f t s t h e peak a t 9-10*20 t o lower angles,

'i.

and broadens t h e peak between 15-20'20.

I n t h e i r study of Gulf Coast c l a y s , Perry and Hower (1972) indicated t h a t
4-

l a y e r c o l l a p s e proceeded systematically with depth u n t i l 40 percent expanded

l a y e r s remained.

A t t h i s point, ordered i n t e r s t r a t i f i c a t i o n i s presumed t o

occur, and t h e proportion of expanded l a y e r s abruptly decreases t o 20 percent.

Tettenhorst and Grim (1975 b) suggest t h a t t h e appearance of r e g u l a r i t y i s
caused by t h e presence of a one-glycol l a y e r complex.

The presence of one-

g l y c o l l a y e r complexes would cause t h e amount af 10 A material t o be o v e r e s t i mated.

My own obskrvations are that l a y e r c o l l a p s e i s u s u a l l y r e g u l a r and t h a t

no abrupt rate of c o l l a p s e occurs.

I n any event, t h e estimates of rate and

amount of l a y e r c o l l a p s e are n o t e

i r e l y resolved except i n a g e n e r a l way.

Tettenhorst and G r i m a l s o showed t h a t frayed edges (core and r i n d ) w i l l

produce a secondary x-ray peak i n t h e low-angle region (11 t o 14 A) similar

34
t o t h a t produced as a r e s u l t of r e g u l a r mix-layering;

however, i f a peak i s

a l s o present with a spacing of 8.5 t o 9.8 A ordered i n t e r l a y e r i n g i s indicated.

Exper h e n t a l
Montmorillonite heated under one atmosphere pressure can be dehydrated
I n t h e presence of K and a t r e l a t i v e l y high pressures,

a t from 100" t o 12@C.

some l a y e r s can be contracted t o 1 0 A a t r e l a t i v e l y l o w temperatures, but even

a t 40U'C approximately 25 percent of t h e l a y e r s contain water (Khitarov and
Pugin, 1966).

Lebedev e t al. (1975) heated a montmorillonitic c l a y a t a

pressure of 1000 kg/cm

They noted no appreciable change a t 3000C.

an ordered mixed-layer illite-montmorillonite developed.

A t 4000

Hiltabrand e t al.

(1973) observed no change i n t h e montmorillonite i n Gulf Coast muds heated

a t 200C under a pressure of 53 kg/cm

Hydrothermal s t u d i e s by Warshaw

(1959) showed t h a t i t w a s v i r t u a l l y impossible t o produce a pure 1 0 A mica

phase below 400" t o 5000C when t h e composition of t h e s t a r t i n g material v a r i e d
much from t h a t of i d e a l muscovite.

"Illites" have been produced a t lower

temperatures, but t h e s t a r t i n g compositions were more l i k e t h a t of muscovite

than i l l i t e .
Eberl and Hower (1976) conducted hydrothermal experiments with s y n t h e t i c
b e i d e l l i t e (A12Si3. 66A10. 34010(OH) 2Ko, 34) and Wyoming bentonite (octahedral
Mg present).

When both w e r e s a t u r a t e d with potassium, mixed-layer i l l i t e

smectite w a s formed;

The proportion of i l l i t e l a y e r s increased with increased

temperatures (150 t o 400'C) and increased run time.

k t

a c t i v a t i o n energy

of 19.6h3.5 kcal/mole w a s found f o r conversion of b e i d e l l i t e t o mixed-layer

illite-smectite.

The a c t i v a t i o n energy and rate c o n s t a n t s suggest t h a t t h e

transformation r e q u i r e s t h e breaking of chemical bonds i n t h e 2:l l a y e r s .

35
They attempted t o determine i f t h e r e l a t i o n between temperature and exp a n d a b i l i t y i n t h e n a t u r a l system represented chemical equilibrium o r r e a c t i o n
kinetics.

Their d a t a indicated t h a t i f t h e expandability of buried Gulf Coast

c l a y s is a f u n c t i o n of t h e experimentally determined r e a c t i o n rate, t h e degree

of c o n t r a c t i o n should be much f u r t h e r advanced.

They concluded t h a t expanda-

b i l i t y i s determined by p r e v a i l i n g pressure-temperature conditions r a t h e r than

t h e l e n g t h of time t h e c l a y has had t o react.

The d a t a i n Figure 2 tend t o

support t h i s conclusion.
Further, Eberl and Hower demonstrated t h a t t h e presence of sodium slows
t h e r e a c t i o n rate f o r Wyoming bentonite, though a mixed-layer phase w a s produced a t temperatures as low as 152OC.
duced ( g l a s s + mnectite + mixed-layer

I n t h e i r experiments k a o l i n i t e w a s pro-

+ k a o l i n i t e + quartz).

appear t o happen during b u r i a l diagenesis.

This does not

They concluded that t h e i r k i n e t i c

c_
F

d a t a were c o n s i s t e n t with e i t h e r a n equilibrium o r a k i n e t i c i n t e r p r e t a t i o n

of t h e n a t u r a l reaction.
.+

'f

I n another hydrothermal study of Wyoming montmorillonite, Eberl (1978)

found that t h e rate of collapsed l a y e r formation (rate of increased l a y e r change)

w a s i n v e r s e l y r e l a t e d t o t h e hydration energy of t h e i n t e r l a y e r cation.

He

concluded t h a t t h e g r e a t e r t h e hydration energy of t h e i n t e r l a y e r region,

t h e g r e a t e r t h e charge t h a t must develop on t h e 2 : l l a y e r t o cause dehydration
and, t h e r e f o r e , t h e slower t h e r e a c t i o n rate.

Thus, l a y e r c o l l a p s e i s rela-

t i v e l y r a p i d when C s , Rb, and K are t h e i n t e r l a y e r c a t i o n s and i s retarded

when N a , L i , and v a r i o u s d i v a l e n t c a t i o n s are present.
4-

It i s of i n t e r e s t t o n o t e t h a t t h e Li-treated sample, and perhaps t h e

Ba and Ca, produced c h l o r i t i c l a y e r s (tosudite--regularly

d i o c t a h e d r a l chlorite-smectite).
0

interstratified
/

36

iri

Chemistry
I n order f o r montmorillonite t o be converted t o i l l i t e , K must be added
i n t h e i n t e r l a y e r space and t h e amount of t e t r a h e d r a l A 1 must be increased.
Studies of t h e f i n e , d i a g e n e t i c a l l y formed mixed-layer c l a y by Weaver and
Wampler (1970), Perry (1974), and Aronson and Hower (1976) confirmed t h a t t h e
amount of K increased with depth and temperature as t h e proportion of i l l i t e
l a y e r s increased.

These t h r e e s t u d i e s showed, by K-Ar a n a l y s i s , t h a t t h e K

moved from t h e coarse K-feldspar t o t h e montmorillonite as i l l i t i c l a y e r s

formed (thereby decreasing t h e apparent K-Ar age).
Analyses of t h e <O.lpm mixed-layer f r a c t i o n of a series of samples
from a Gulf Coast w e l l (Hower e t al., 1976) showed t h a t i n a d d i t i o n t o K20,
A1 0

2 3

i n c r e a s e s with increasing proportion of i l l i t e layers.

Si02 decrease with increasing depth.

tite

+ A13+ + K+

= illite

They suggest t h a t t h e r e a c t i o n i s smec-

+ S i4 + c h l o r i t e .

come from K f e l d s p a r and perhaps m i c a .

smectite are believed t o form c h l o r i t e .

The A 1 and K are believed t o

The S i released from t h e smectite

i s believed t o form f i n e grained quartz.

with depth.

The Mg and Fe released from t h e

C h l o r i t e w a s observed t o i n c r e a s e

However, an appreciable p o r t i o n of t h e c h l o r i t e occurs i n t h e

> 2 p m f r a c t i o n (and i n t h e >10 p m f r a c t i o n ) .

The c h l o r i t e / k a o l i n i t e r a t i o

generally increased with increasing p a r t i c l e s i z e .

c h l o r i t e should form such l a r g e p a r t i c l e s .
than 2450 m.

MgO, Fe203 and

It is s u r p r i s i n g that

No c h l o r i t e w a s found shallower

This depth coincided approximately with a major formation

boundary (Anahuac-Frio).

It is p o s s i b l e t h a t , under some conditions, t h e Mg

may be used t o form dolomite and t h e Fe t o form s i d e r i t e o r p y r i t e .

They a l s o found calcite decreasing with depth and believed t h e decrease

w a s due t o d i s s o l u t i o n .

Weaver and Beck (1971) observed t h e same trend.

37

bd
Q

Chemical a n a l y s i s of t h e ~ 0 . 0 8pm f r a c t i o n of mixed-layer c l a y s from

t h e Lower Cretaceous of B r i t i s h Columbia (Foscolos and Kodama, 1974) show
t h e chemical changes t h a t occur with increasing proportion of i l l i t e layers:
47 percent illite layers:

(% .S2Fe3t0.23Ti0.02Mg0.2d)(si3.64N0.36)

09.80(0m2.50%.32Na0.07ca0. 12 (940c)

82 percent illite layers:

(M1 .73Fe3+0.0STi0.02M@.17) (s3.52a0.48)

09.86(0~2.27~.60Nao.05~0.06
(164OC)

Hoffman and Hower (1978) analyzed shallow and deeply buried b e n t o n i t e

beds from t h e Cretaceous of Montana and obtained t h e following average formula f o r t h e 0.2

.5 pm f r a c t i o n :
15 percent illite layers:

(M1 .42Fe3to.22M@.40) (si3.91 MO.Og) 010 ( 0 ~ 2 ~ . o ~ x + 0(<60c)

.28
65 percent illite layers:
.67Fe3+0.18Mb.21) (si3.44%.56) O10(0H)2Ko.45x+'0.1 2

750c)

The montmorillonitic s h a l e s enclosing t h e bentonites have mixed-layer

"i

i l l i t e - m o n t m o r i l l o n i t e r a t i o s similar t o those of t h e bentonite.

Both have

more c h l o r i t e associated with t h e high i l l i t e mixed-layer phase than t h e low

i l l i t e mixed-layer phase.

C h l o r i t e and mixed-layer chlorite-smectite are common

components of t h e Ordovician K-bentonites

but are n o t always present.

(70 t o 80 percent i l l i t e l a y e r s )

The c h l o r i t e generally increased with increasing

depth of b u r i a l , but one bed may contain appreciable c h l o r i t e and another bed

a few f e e t above o r below may have none.

Thus, c h l o r i t e i s not a necessary

by-product of t h e formation of i l l i t i c l a y e r s from smectite (or volcanic g l a s s ) .

The source of t h e K i s believed t o be t h e adjacent shales.

This does

not e x p l a i n t h e source of K when t h e encasing sediments are limestones (Ordov i c i a n K-bentonites).

-W

Rather than A1 being added, it i s more l i k e l y t h a t Si

i s removed from t h e b e n t o n i t e s t o t h e adjacent s h a l e s (Weaver, 1953, and

Slaughter and Early, 1965).

38
Analysis by Weaver and Beck (unpublished) of t h e <0.2 pm f r a c t i o n of
Gulf Coast Pliocene-Miocene c l a y s gives t h e following r e s u l t s :

20-30 percent illite layers:

(N1.24Fe3t0.49Mg0.33)("3.65Ab.35) 010(0~2%.28Na0.1 5&0.01 (500c)
60-70 percent illite layers:
(N1.47Fe0.30M80.27) ("3.53Ab.47) 010(o~2%.43N%.09Ca0.1

3 (l)'ool

Mossbauer and chemical analyses (Weaver and Beck, 1971) of t h e bulk sample
i n d i c a t e t h a t with depth much of t h e Fe3+ is reduced t o Fe

2+

Figure 4 is a graph showing t h e d i s t r i b u t i o n of t h e ions i n t h e above

s t r u c t u r a l formulas as a function of percent i l l i t e l a y e r s .

Figure 5 shows

t h e same chemical d a t a p l o t t e d i n r e l a t i o n t o t h e postulated temperature of

formation.

Considering t h e p o s s i b l e v a r i a t i o n s i n t h e s t a r t i n g material, t h e

r e l a t i o n s are good.

Both t e t r a h e d r a l and octahedral A 1 (and K) i n c r e a s e with

increasing proportion of i l l i t e l a y e r s and temperature.

d r a l M g , Fe, and Mg

+ Fe

decrease.

Conversely, octahe-

Extrapolation of t h e l i m i t e d d a t a i n d i c a t e s

t h a t a c l a y with 100 percent i l l i t e l a y e r s should have t h e following composi-

tion:

(M1.80Fe3+0.1fl@.10) (si3.35N0.65)010(0H)2%.6S%.10

Extrapolation of t h e temperature-structural d a t a i n d i c a t e s t h a t t h i s
composition should be reached a t approximately 190C.

The c a l c u l a t e d formula

contains only about half t h e octahedral Mg and Fe found i n most i l l i t e s (Weaver

and P o l l a r d , 1973).

This could i n d i c a t e t h a t most i l l i t e s d i d not form by

b u r i a l diagenesis and/or do contain some c h l o r i t e o r montmorillonite l a y e r s .

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as t o t a l A 1 i n c r e a s e s t h e amount of t e t r a h e d r a l and octahedral A 1 i n c r e a s e s

a t approximately t h e same rate.

This suggests t h a t r a t h e r than A 1 being added

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bd

t o t h e t e t r a h e d r a l s h e e t Si is removed from t h e sheet along with some Mg

and Fe from t h e octahedral sheet.

Some of these i o n s may combine with t h e

Si and A 1 from t h e K-feldspar (source of K) t o produce a c h l o r i t i c material.

A s t h e proportion 1 0 A l a y e r s increases, t h e amount of i n t e r l a y e r K

increases.

The i n c r e a s e is not linear.

t h e 1 0 A l a y e r s (x-ray),

When a l l of t h e K is assigned t o

t h e amount of K increased l i n e a r l y , from 0.55 per

Olo(OH)2 when only 50 percent of t h e l a y e r s are contracted, t o 0.8 when 100

-

percent of t h e l a y e r s are contracted (Weaver and P o l l a r d , 1973).

This indi-

cates e i t h e r that t h e method of c a l c u l a t i n g t h e proportion of expanded and

nonexpanded l a y e r s is i n e r r o r , o r t h a t t h e d i s t r i b u t i o n of K is not even and
t h a t t h e l a s t l a y e r s contracted contain considerably more K than those t h a t

w e r e contracted i n t h e e a r l y s t a g e s of diagenesis.

The i n t e r l a y e r c a t i o n

s u i t e p r e s e n t during t h e f i n a l s t a g e s of diagenesis is d i f f e r e n t from t h a t

present i n t h e earlier s t a g e s ( t h e C a / N a r a t i o i n c r e a s e s with depth).

Thus,

more charge might be required t o produce exchange and c o n t r a c t i o n i n t h e

later s t a g e s of diagenesis.
Hower (1967) suggest.s t h a t t h e degree of ordering (arrangement of high
and low charged l a y e r s ) w i l l c o n t r o l t h e proportion of l a y e r s t h a t w i l l con-

tract f o r a given amount of K.

H e c a l c u l a t e d t h a t order i n t e r l a y e r i n g pro-

duced more contracted l a y e r s (10 A) per amount of K than did random i n t e r l a y e r ing.

A s ordering i n c r e a s e s with an i n c r e a s e i n t h e proportion of 1 0 A l a y e r s ,

t h e amount of K per 10 A l a y e r should decrease with an increasing number of

10 A layers.

The trend is e x a c t l y t h e opposite.

Another p o s s i b i l i t y is t h a t i n mixed-layer c l a y s with r e l a t i v e l y few

10 A l a y e r s , some v e r m i c u l i t i c l a y e r s and/or exchangeable K is present and

t h e l a y e r s adsorb only one l a y e r of ethylene glycol ( r a t h e r than two).
d

would cause t h e amount of 1 0 A l a y e r s t o be overestimated.

This

42
Hower's graphs i n d i c a t i n g t h a t t h e amount of i n t e r l a y e r K increases as
the number of contracted l a y e r s i n c r e a s e are based on d a t a from samples from a
wide v a r i e t y of formations and may not r e p r e s e n t a d i a g e n e t i c trend.

Data

from individual formations which contain a d i a g e n e t i c sequence (Weaver and

*

Wampler, 1970; Foscolos and Kodama, 1974; and Hower e t al., 1976) do not appear

t o show such a trend.

The K content per l a y e r appears t o be n e a r l y constant

o r may a c t u a l l y decrease as t h e number of 1 0 A l a y e r s increases.

The chemistry of t h e bulk samples shows r e l a t i v e l y l i t t l e change with
depth, i n d i c a t i n g t h a t most of t h e i o n s necessary f o r t h e formation of t h e
i l l i t e l a y e r s are generated i n t e r n a l l y , l a r g e l y from K-feldspar.

Weaver and

Beck (1971) demonstrated t h a t most montmorillonitic s h a l e s do not have s u f f i -

cient K, Mg, and Fe relative t o A 1 t o be converted t o a t y p i c a l Paleozoic

i l l i t e - c h l o r i t e shale.

I f t h e conversion i s t o occur, they b e l i e v e t h a t K,

1

Mg, and Fe must be added t o t h e system by migrating upward from t h e more deeply

buried shales.

Weaver and Beck's (1971) d a t a show t h a t below 3,330 m K, Mg,

and Fe systematically i n c r e a s e relative t o A l .

Dunoyer de Segonzac's (1969)

d a t a f o r t h e Cretaceous of North Africa show a similar trend f o r Mg.

Data i n

Hower e t al. (1976) show a decrease i n Mg and Fe (where does i t go?), and an
increase i n K relative t o A l , w i t h depth.

It is d i f f i c u l t t o e v a l u a t e how

much t h e s e t r e n d s are due t o changes i n t h e composition of t h e d e t r i t a l materia l with depth.

More d a t a are needed.

Release of I n t e r l a y e r Fluids

Water
It is not known f o r c e r t a i n how many l a y e r s of water buried mnectites

contain.

However, t h e experimental s t u d i e s of Van Olphen (1963) and Khitarov

and Pugin (1966) i n d i c a t e t h a t w a t e r l a y e r s i n excess of two are removed

43

f a i r l y easily.

Studies of buried sediments i n d i c a t e t h a t t h e f i n a l one o r

two water l a y e r s are removed'

temperatures and pressures i n t h e range en-

countered i n t h e conversion of montmorillonite l a y e r s t o i l l i t e l a y e r s (500

t o 3OOOC).

Laboratory experiments involve only temperatures and pressure and do not

take i n t o account t h e increase i n l a y e r change-which occurs during b u r i a l
diagenesis.

Vermiculites which have a l a y e r charge l a r g e enough t o allow them

t o c o n t r a c t t o 1 0 A when K is present c o n t a i n two water l a y e r s .

I t seems

l i k e l y t h a t under shallow b u r i a l conditions, as t h e charge i n t h e smectite

l a y e r s increases, t h e smectite contains two l a y e r s of water u n t i l t h e l a y e r s
a c t u a l l y collapse.

Khitarov and Pugin (1966) found t h a t montmorillonite con-

tained two water l a y e r s a t 150C and 5000 atmospheres pressure.

One water

l a y e r w a s p r e s e n t a t 200C and 10,000 atmospheres pressure.

g-

An expanded c l a y with two water l a y e r s contains 20 percent w a t e r by

weight o r approximately 33 percent by volume (10 A c l a y l a y e r , 5 A two water
Y

layers).

The average s h a l e contains approximately 60 percent c l a y minerals.

I f t h e c l a y s u i t e contains 80 percent montmorillonite ( t y p i c a l Gulf Coast

clay) t h e amount of i n t e r l a y e r water l o s t by c o n t r a c t i o n of a l l expanded l a y e r s
would be 9.6 percent.

The t y p i c a l d e t r i t a l montmorillonite contains 20 percent

t o 30 percent contracted l a y e r s and t h e mixed-layer phase s t a b i l i z e s a t 70

percent t o 80 percent contracted l a y e r s a t a temperature of 120'
and p e r s i s t s t o 2OO0C o r higher.

to 16PC

Thus, through t h e i n t e r v a l of maximum dia-

g e n e t i c a l t e r a t i o n 40 percent t o 50 percent of t h e l a y e r s are contracted and

4 percent t o 6 percent of i n t e r l a y e r water (by weight) is t r a n s f e r r e d t o t h e

pores.

t o 1 0 percent.

The volume reduction i n i n t e r l a y e r space would range from 6 percent

An equivalent i n c r e a s e i n pore space and pore water would

presumably be created.

Perry and Hower (1972) state t h a t c o n t r a c t i o n and water l o s s start

abruptly and occur over a r e l a t i v e l y s h o r t depth-temperature i n t e r v a l .

Their

d a t a i n d i c a t e s t h a t t h e c o l l a p s e rate varies as a function of time and/or

temperature.

Unfortunately, t h e two e f f e c t s could not be separated.

I n an

Oligocene w e l l (geothermal g r a d i e n t 1.7C/100 m) t h e c o n t r a c t i o n and w a t e r

release occurred over a depth range of approximately 900 m (40C); i n a Miocene

w e l l (1.4C/100 m) i t occurred over a range of 3,000 m (80C).

The d a t a i n

Figure 2 tend t o confirm t h a t most of t h e w a t e r release due t o l a y e r contract i o n occurs over a r e l a t i v e l y narrow temperature i n t e r v a l ranging from 40to
8OoC.

The depth-temperature range over which l a y e r c o l l a p s e occurs i s i n p a r t

a function of t h e s i z e f r a c t i o n examined.

The d a t a from Hower e t a l . (1976)

i n d i c a t e that t h e f i n e f r a c t i o n of t h e o r i g i n a l d e t r i t a l m o n t m o r i l l o n i t e has

a higher proportion of i l l i t i c l a y e r s than t h e coarser f r a c t i o n .

With in-

creased depth and temperature t h e proportion of i l l i t e l a y e r s i n c r e a s e s i n

both s i z e f r a c t i o n s , but not a t t h e same rate.

The <0.1 urn and t h e 0.5

2 urn

f r a c t i o n s contain 60 percent i l l i t e l a y e r s a t approximately t h e same depth

(3,400 m).

Above t h i s depth t h e proportion of i l l i t e l a y e r s i n c r e a s e s a t a

f a s t e r rate, with depth, i n t h e coarser s i z e f r a c t i o n ; below t h i s depth t h e

s i t u a t i o n i s reversed.

I n t h e eO.1 pm f r a c t i o n t h e proportion of i l l i t e l a y e r s

i n c r e a s e s from 60 percent t o 80 percent over a d i s t a n c e of 500 m and then remains constant f o r t h e remaining 1700 m.

I n t h e 0.5

2 pm f r a c t i o n , t h e

proportion of i l l i t e l a y e r s increases from 60 percent t o only 70 percent over

a d i s t a n c e of 1200 m and then remains constant f o r t h e remaining 800 m.

r e a c t i o n i s apparently s i z e dependent.

The

However, with depth t h e amount of

t o t a l mixed-layer decreases i n t h e f i n e r s i z e f r a c t i o n and i n c r e a s e s i n t h e

coarser s i z e f r a c t i o n .

The d a t a say t h a t as t h e proportion of i l l i t e l a y e r s

i n c r e a s e s i n t h e f i n e s t f r a c t i o n , t h a t p o r t i o n which has t h e fewer i l l i t e

u-

45
l a y e r s becomes coarser and t h e p o r t i o n with t h e most i l l i t e l a y e r s remains
fine.

This perhaps could occur i f i l l i t i z a t i o n proceeds by d i s s o l u t i o n r a t h e r

It i s u n l i k e l y t h e d a t a are r e l i a b l e enough t o make such a

than accretion.
conclusion.

When t h e whole sample i s considered, i n t e r l a y e r water release i s

spread over a much wider depth-pressure i n t e r v a l than indicated by t h e publ i s h e d curves.

For example, a t 17OOC t h e 0.5

2 vm f r a c t i o n (24 percent of

t h e sample) contains 8 percent more expanded l a y e r s (32 percent vs. 24 percent) than t h e less than 0.1 vm f r a c t i o n (9 percent of t h e sample) (Hower

e t a l . , 1976).
Powers (1967), Burst (1969), and Perry and Hower (1972) have constructed
It

water escape curves" which are intended t o show t h e c o n t r i b u t i o n of t h e re-

leased i n t e r l a y e r water t o t h e p o r o s i t y of shales.

curves i s not e n t i r e l y clear.

The meaning of t h e s e

The upper p o r t i o n of t h e curves, shallow

b u r i a l , r e p r e s e n t s t h e rate of l o s s of pore water from t h e mud and t h e lower

p a r t t h e release of i n t e r l a y e r water t o t h e pores.

I n addition, t h e curves

CT.

are not t o scale.

Their curves suggest t h a t t h e released i n t e r l a y e r w a t e r i s

equivalent t o one-third t o one-half

of t h e o r i g i n a l pore w a t e r content.

Cal-

c u l a t i o n s show t h a t t h e t o t a l released i n t e r l a y e r w a t e r , over an i n t e r v a l of

1800 m, should amount t o approximately 5 percent by weight.

Figure 6 contains

a curve showing t h e reduction i n pore water content with depth of a t y p i c a l

Gulf Coast s h a l e section.

Also shown, approximately t o scale, i s t h e con-

t r i b u t i o n of t h e released i n t e r l a y e r water.

Although t h e c o n t r i b u t i o n of t h e

released i n t e r l a y e r water i s not as spectacular as that i n t h e previously publ i s h e d curves, i t i s probably s i g n i f i c a n t .

Weaver (1960) e s t a b l i s h e d t h a t a r e l a t i o n e x i s t e d between o i l production

and t h e occurrence of expanded c l a y s and suggested t h a t t h e i n t e r l a y e r w a t e r

46

H20 BYWEIGHT
20
40

60

/-PORE

iooo

2000

-E
w

-E
3000

4000

5000

Figure 6. Typical s h a l e pore w a t e r curve f o r e a r l y T e r t i a r y Gulf Coast section.

Second curve (diagenetic water), between 1,850 m and 4,000 m shows amount of
water released by conversion of montmorillonite t o i l l i t e . Second curve i s
not cumulative. I f a l l diagenetic water w e r e r e t a i n e d i n t h e s h a l e , t h e amount
of s h a l e pore water below 4,000 m would be increased by 5 percent. T.H.P.
i n d i c a t e s general l o c a t i o n of t h e top of t h e high-pressure zone.

U'

47

u
.*

i n t h e expanded c l a y s provided t h e f l u i d s necessary f o r t h e migration of o i l

a f t e r deep b u r i a l .

Later Burst (1969) constructed a graph showing t h e v e r t i -

cal d i s t a n c e of Gulf Coast productive zones above and below what he c a l l e d

t h e second s t a g e dehydration l e v e l .

Most of t h e production occurs above t h i s

level and i s supposed t o be r e l a t e d t o t h e upward migration of water released

a t t h e second s t a g e dehydration level.

H i s second s t a g e dehydration l e v e l

i s based on t h e depth o r temperature a t which t h e 1 7 A glycolated montmorill o n i t e x-ray peak "disappears".

This disappearance has no p a r t i c u l a r s i g n i f i -

cance, except t h a t i t i s r e l a t i v e l y easy t o observe; however, i t s i d e n t i f i c a t i o n i s highly subjective.

The c o l l a p s e of montmorillonite starts a t a lower temperature and depth
than i s indicated by t h e disappearance of t h e 1 7 A peak.

Depending on t h e

age and geothermal gradient, c o n t r a c t i o n of montmorillonite l a y e r s starts

from 600 m t o 1500 m above and s t o p s ( a t t a i n s a 4:l mixed-layer i l l i t e montmorillonite r a t i o ) from 300 m t o 1500 m below t h e depth s e l e c t e d by Burst

as t h e second s t a g e dehydration level.

When t h e s e limits are p l o t t e d on Burst

curves f o r t h e production-depth d i s t r i b u t i o n (Figure 7), i t can be seen t h a t

v i r t u a l l y a l l production comes from t h e i n t e r v a l between i n i t i a l c o l l a p s e of
montmorillonite l a y e r s and t h e formation of t h e s t a b l e 7:3

4 : l phase.

For

whatever reason, o i l production i s concentrated i n t h e i n t e r v a l i n which t h e

montmorillonite l o s e s 50 percent t o 60 percent of i t s i n t e r l a y e r water (20
percent t o 25 percent of t h e l a y e r s are contracted i n t h e o r i g i n a l montmorill o n i t e , and t h e f i n a l 20 percent t o 30 percent of l a y e r s are not contracted
z

u n t i l temperatures of 200Oto 25OOC).

Thus, s i g n i f i c a n t vertical migration of

t h e released i n t e r l a y e r water i s not required.

.
W

r a t h e r than t h e

Migration need only be l o c a l

r e d s of meters indicated by Burst's mo

Connan (1974) d i s c u s s e s t h e time-temperature dependence of o i l genesis

and notes t h a t t h e threshold of i n t e n s e o i l genesis appears a t much higher

48

PRODUCING ZONES

+3000

+2000

v)

aF=
Z

E
b

w -1000

-2000

500
NUMBER OIL FIELD TOPS

I
1,000

Figure 7 . Relation of i n i t i a l collapse of montmorillonite layers and f i r s t

occurrence of "stable" mixed-layer phase (4:l) to number of producing f i e l d s
i n the Gulf Coast Tertiary. Production data from Burst (1969). Zero l i n e
indicates relative depth a t which 1 7 A x-ray peak can no longer b e observed.

49

LJ

temperatures i n younger sedimentary series than i n o l d ones.

H i s d a t a indi-

cate t h a t t h e temperature f o r t h e threshold of i n t e n s e o i l genesis decreases

from 115" t o 120C f o r s h a l e s 1 2 m.y. old, t o 65" ti, 80C f o r s h a l e s 70 m.y.
ch

old, t o 60'

t o 62C f o r shales 180 t o 359 m.y.

old.

The pseudo-energy of

a c t i v a t i o n i s i n t h e range of 11,000 t o 14,000 cal/mole.

He attributed the

low value t o t h e c a t a l y t i c influence of c l a y minerals and p o s s i b l e organic

matter

Figure 8 shows t h e r e l a t i o n of t h e temperature of t h e threshold of int e n s e o i l generation t o t h e montmorillonite dehydration p a t t e r n .

p a s t 100 m.y.,

i n t e n s e o i l generation has s t a r t e d near t h e c e n t e r of t h e

montmorillonite dehydration zone (1:4-7:3).

are too s p a r s e t o be s i g n i f i c a n t .

For t h e

The d a t a f o r older sediments

The temperature i n t e r v a l over which t h e

montmorillonite i s dehydrated ( 5 a t o 150C) i s similar t o t h e temperature

.2-

i n t e r v a l over which o i l i s generated (Hood e t al., 1975).

To go one s t e p f u r t h e r , i t may w e l l be t h a t l a y e r c o n t r a c t i o n a i d s i n
Ti

t h e generation of hydrocarbons.

When two o r more water l a y e r s are present,

organic material i n t h e i n t e r l a y e r p o s i t i o n may not be i n d i r e c t contact with

t h e c l a y surface.

When l a y e r dehydration starts, t h e organic material i s

brought i n c l o s e r proximity t o t h e s i l i c a t e t r a h e d r a l surface, and t h e necess a r y c a t a l y t i c r e a c t i o n s can occur t o convert t h e organic material t o hydrocarbons.

Another important f a c t o r may be t h a t t h e concentration of i n t e r l a y e r

c a t i o n s i s increased considerably during t h e f i n a l s t a g e s of l a y e r dehydration.

Among o t h e r things, t h e conversion of organic material t o hydrocarbons

r e q u i r e s a decrease i n t h e s i z e of t h e molecules and an i n c r e a s e i n v o l a t i l i t y ,
mobility, and hydrogen content.

Thomas (1949) e s t a b l i s h e d t h a t c a t a l y t i c

cracking by Si-A1 compounds i s caused by t h e presence of hydrogen i o n s i n t h e

+

*LJ

catalysts.

The a c i d i t y , o r exchange capacity, is created by A13+ s u b s t i t u t i n g

f o r Si4+ i n t h e t e t r a h e d r a l oxygen network.

Acidity i n c r e a s e s with i n c r e a s e

a
20

40
60
80

106
0

a:

120

140

5t-

160

180
200
220
240

260

300

325

50

75

100

125

150

Figure 8. Relation of temperature of intense oil generation ( T . I . O . G . )

conversion to mixed-layer illite-smectite. See Figure 2.

MILLION
YEARS

(Connan, 1974) to smectite

51
i n A13+ s u b s t i t u t i o n u n t i l t h e Al/Si r a t i o reaches one.
i

Mortland e t al. (1963),

F r i p i a t e t a l . (1965), and Mortland (1968) showed t h a t t h e a c i d i c p r o p e r t i e s

of i n t e r l a y e r water are considerably g r e a t e r than i n normal w a t e r .

c.

donation i n c r e a s e s with t h e decreasing content of i n t e r l a y e r water.

Proton
The pro-

duction of protons from water molecules i s r e l a t e d t o t h e e l e c t r o n e g a t i v i t y

of t h e cation.

A s t h e e l e c t r o n s are displaced towards t h e metal ion, t h e

proton i s more e a s i l y removed.

A s t h e water content decreases, t h e polariza-

t i o n f o r c e s are less d i l u t e d , and t h e remaining water molecules become more

polarized and b e t t e r proton donors.

The e x t e n t of proton donation by resi-

dual water i n montmorillonite as a function of t h e type of m e t a l i o n increases

as follows: Fe3+ > A13+ > Mg > Ca > Na.

Johns and Shimoyama (1972) noted t h e s e

r e l a t i o n s and suggested t h a t preceding t h e c o n t r a c t i o n of montmorillonite

"r

l a y e r s , adsorbed f a t t y a c i d s undergo progressive decarboxylation and long

chain alkanes are produced.

With increasing temperature, as t h e water con-

t e n t of t h e expanded l a y e r s i s reduced and proton donating c a p a b i l i t i e s are

'c

increased, alkane cracking occurs.

T i s s o t (1969) and T i s s o t e t al. (1974) established t h a t t h e r e w e r e t h r e e
b a s i c groups of organic matter i n sediments.

The t h r e e types were character-

ized by t h e i r p o t e n t i a l t o produce hydrocarbons as b u r i a l depth and temperat u r e increased.

I s h i w a t a r i e t al. (1977) suggested t h a t T i s s o t ' s t h r e e groups

of organic matter w e r e l i p i d , humic a c i d , and kerogen.

Their s t u d i e s support

t h e earlier suggestions of T i s s o t (1969) t h a t t h e pathway f o r hydrocarbon

production from kerogen i s through t h e formation of l i q u i d products which w e r e
I

4.

p r e f e r e n t i a l l y a l t e r e d t o aromatic and a l i p h a t i c hydrocarbons.

This l i q u i d

product would presumably be t h e material t h a t i s adsorbed between t h e l a y e r s

z

of expanded c l a y , as i t i s u n l i k e l y t h a t much of t h e o r i g i n a l organic material

w a s present i n t h e i n t e r l a y e r position.

When humic material i s heated, only

52
a minor amount of l i q u i d product is formed.

It should be noted that t h e water

between t h e montmorillonite l a y e r s is not, f o r each l a y e r , reduced systemat i c a l l y from two l a y e r s t o one l a y e r t o a p a r t i a l l a y e r .

take place, but on a layer-by-layer

basis.

U
T

This sequence may

I n i t i a l l y , l a y e r s with t h e higher

charge c o n t r a c t and l o s e a l l i n t e r l a y e r water; t h e lower charge l a y e r s s t i l l

contain two l a y e r s of water.

Thus, cracking can occur as t h e f i r s t l a y e r s

are contracted (50" t o 80C) and can continue u n t i l t h e f i n a l l a y e r s are contracted.

The i n c r e a s e i n l a y e r charge required f o r t h e l a y e r s t o c o n t r a c t i s

l a r g e l y caused by increasing t h e Si/A1 r a t i o .

The increased charge causes

a n i n c r e a s e i n t h e concentration of i n t e r l a y e r cations.

Both f a c t o r s should

enhance t h e cracking c a p a b i l i t i e s of t h e i n t e r l a y e r region.

Montmorillonite may a i d i n cracking by providing a source of r e a d i l y
a v a i l a b l e H ions.

A r e c i p r o c a l a c t i o n may occur.

It is conceivable t h a t by

removing H i o n s t h e organic material a i d s i n t h e conversion of montmorillonite

to illite.

A number of p o s s i b i l i t i e s exist.

Mortland e t al. (1963) found

i n t h e i r study of t h e i n t e r a c t i o n between ammonia and expanding l a t t i c e s t h a t

t h e r e w a s some exchange between t h e l a t t i c e hydroxyls and t h e adsorbed water.
Thus, i t is p o s s i b l e t h a t as H+ i s complexed by t h e organic material i n t h e
i n t e r l a y e r material, H+ from t h e octahedral OH- moves t o t h e i n t e r l a y e r position.

This would i n c r e a s e t h e l a y e r charge and f a c i l i t a t e contraction.

Es-

s e n t i a l l y , t h e organic material would act as a pump t o remove Ifrom

+ the
montmorillonite layers.
Hydrocarbons can apparently form when expanded c l a y s are n o t present o r

are present i n only minor amounts.

may act as a c a t a l y s t .

The surface o r edge of t h e c l a y p l a t e s

However, when t h e i n t e r l a y e r water is n o t present,

migration should be r e s t r i c t e d .

The a v a i l a b i l i t y of expressed i n t e r l a y e r

water f o r migration may be more important than t h e c a t a l y t i c a c t i v i t y of t h e

u'

53

LJ
&

c l a y i n t h e formation of commercial d e p o s i t s of hydrocarbons.

Hydrocarbons

are p r e s e n t i n many shales, but appear t o be concentrated i n r e s e r v o i r s p r i marily i n those sediments which contain o r contained an appreciable amount of
expandable c l a y (Weaver, 1960).

C o r d e l l (1972) made an e x c e l l e n t review of

t h e f a c t o r s c o n t r o l l i n g t h e o r i g i n and migration of hydrocarbon.

High Pressure
I n some Gulf Coast w e l l s t h e normal decrease i n s h a l e d e n s i t y and p o r o s i t y
w i t h depth is i n t e r r u p t e d by a r e l a t i v e l y abrupt r e v e r s a l of trend.

After a

r e l a t i v e l y s h o r t i n t e r v a l (150 t o 300 m) t h e normal trend continues (Kerr

and Barrington, 1961; Myers and Van Siclen, 1964; Powers, 1967; Weaver and
Beck, 1971; Schmidt, 1973).

Most of t h e s e authors suggest, i n one way o r

another, t h a t t h e released i n t e r l a y e r water i s a f a c t o r i n causing t h e d e n s i t y

reversal and t h e abnormally high pressures associated w i t h t h e reversal.

Powers (1967) and Burst (1976) have suggested t h a t t h e i n t e r l a y e r water h a s a
higher d e n s i t y than pore water and when released t o t h e pores expands, c r e a t i n g
high pressures.

It has n o t been e s t a b l i s h e d t h a t i n t e r l a y e r water has a higher

d e n s i t y than unconfined water.

Changes in w a t e r d e n s i t y are not necessary f o r t h e formation of high

pressures.

Bredehoeft and Hanshaw (1968), F e r t l and Timko (1970 a and b),

Weaver and Beck (1971), Chapman (1972), and o t h e r s have indicated t h a t high
p r e s s u r e s are created by low permeability o r low hydraulic conductivity i n
s e c t i o n s of t h i c k shales.

e
~

Bradley (1975) has reviewed t h e many processes which

could c o n t r i b u t e t o t h e formation of abnormal pressures and concluded t h a t t h e

primary requirement w a s t h e formation of a seal and t h a t temperature w a s t h e
p r i n c i p a l source of pressure.

*W

H e pointed o u t t h a t p o r o s i t y l o s s i s not due t o

overburden stress but i s due t o a group of i n t e r r e l a t e d chemical processes

54
which are dependent on r e a c t i v i t y , temperature, s u r f a c e area, and pressure.
The development of high pressures may be dependent on t h e rate of chemical

ib,
I

changes i n t h e s h a l e s and on t h e timing and e f f e c t i v e n e s s of some forms of

seal.

This seal need not be a pressure seal a t inception.

The p r e s e a l could

restrict water flow and delay chemical process with increases i n density.
Porosity values i n high-pressure zones are s i m i l a r t o those 1500 m t o 2000 m
higher i n t h e s e c t i o n (Weaver and Beck, 1971, and Schmidt, 1973) suggesting
t h e p r e s e a l developed a t these depths.

I n i t i a l l a y e r c o l l a p s e starts i n t h i s

same depth range and may be a f a c t o r i n i t s development.

However, Chapman

(1972) calculated t h a t t h e abnormally high pressures encountered a t 3000 m

t o 3700 m a c q u i r e t h e i r abnormality a t depths of b u r i a l on t h e order of 600 m
t o 800 m.

I n any event, once d i a g e n e t i c r e a c t i o n s are s u f f i c i e n t t o cause l a y e r

collapse, some of t h e released Si and C a can migrate t o t h e b a r r i e r zone, where

c r y s t a l l i z a t i o n of quartz (opal) and calcite w i l l f u r t h e r decrease t h e permeability.
Magara (1975) a l s o concluded that low permeability r a t h e r than d i f f e r e n c e s
i n water d e n s i t y is probably t h e main cause of high pressures.

H e pointed

out t h a t during b u r i a l where a normally compacted s h a l e of r e l a t i v e l y low

p o r o s i t y reached t h e depth-temperature where p o r o s i t y increased (under-compact i o n ) , t h e r e would have t o be a rebound o r volume i n c r e a s e of a t least 6 percent.

The volume increase due t o t h e proposed d i f f e r e n c e i n water d e n s i t y

would be considerably less than t h i s (2 percent).

Weaver and Beck (1971)

c a l c u l a t e d t h a t t h e abrupt change from low p o r o s i t y s h a l e s t o high p o r o s i t y

s h a l e s would r e q u i r e t h e release of six l a y e r s of water.
a b l e v a l u e a t t h i s depth.

This is a n unaccept-

Barker (1972) used t h e pressure-temperature-density

values of water t o show t h a t during b u r i a l t h e heating of entrapped water can

create l a r g e excess pressure (aquathermal pressuring).

id'

55

LiJ

Release of i n t e r l a y e r water t o t h e pores should have no e f f e c t on bulk

d e n s i t y (Magara, 1975), though i t should i n c r e a s e porosity.

It is d i f f i c u l t ,

using heating techniques, t o d i f f e r e n t i a t e between pore water and i n t e r l a y e r

.-

waters.

The major e f f e c t of t h e released i n t e r l a y e r water should be on t h e

chemistry of t h e pore w a t e r ; however, because some of t h e released i o n s and

water are apparently l o s t from t h e pores, a d i r e c t assessment of t h e r o l e of

t h e released water i s d i f f i c u l t .
Hedberg (1978) suggested t h a t methane, generated thermochemically a t
depth, i s t h e major cause of overpressuring i n shales.

Methane i s undoubtedly

a f a c t o r i n t h e formation of many mud d i a p i r s .

As Nagara (1975) has suggested, once t h e seal has formed and abnormal
p o r o s i t i e s are developed (compaction disequilibrium), t h e r e s u l t i n g i n c r e a s e
i n temperature gradient w i l l a c c e l e r a t e t h e i n c r e a s e i n l a y e r c o n t r a c t i o n and
t h e release of t h e i n t e r l a y e r water.

Earlier, L e w i s and Rose (1970) had

noted t h a t as water i s a t h r e e f o l d g r e a t e r i n s u l a t o r than rock, over-pressured

zones should act as i n s u l a t o r s causing an i n c r e a s e i n t h e temperature gradient.
I n a n i n t e r v a l of 1600 m, t h e temperatures can i n c r e a s e by 50 t o 60C more
than what i t would be i n t h e absence of abnormal water content (Timko and
F e r t l , 1972).

The temperature i n c r e a s e is c e r t a i n l y enough t o cause a s i g n i -

f i c a n t i n c r e a s e i n t h e amount of i n t e r l a y e r water released.

Thus, t h e pres-

ence o r absence of high-pressure water can be responsible f o r t h e v a r i a t i o n s

i n t h e depth a t which l a y e r c o l l a p s e starts.

Rather than released i n t e r l a y e r

water causing high pressure, high-pressured water can accelerate t h e release

of i n t e r l a y e r water.
Montmorillonite i s commonly, i f not always, abundant i n high-pressure
shales.

The r o l e of montmorillonite may have l i t t l e o r nothing t o do with its

alteration to illite.

Montmorillonite i s t h e only c l a y t h a t can r e t a i n a high

56
pore water content t o a s u f f i c i e n t depth and temperature t o allow a permeabi-

ii

l i t y seal t o form and t r a p a s i g n i f i c a n t amount of f l u i d .

It is generally assumed t h a t t h e i n t e r l a y e r water completely f i l l s t h e

e n t i r e volume of i n t e r l a y e r space.

This need not be.

Martin (1960) noted

t h a t x-ray p a t t e r n s can i n d i c a t e t h e presence of two water l a y e r s (15 A) when

t h e r e is a c t u a l l y not enough water present t o form one complete w a t e r layer.
Walker (1956) found t h a t vermiculite is f u l l y hydrated ( a l l p o t e n t i a l water
sites occupied) only when immersed i n water o r a t very high r e l a t i v e pressures.

As t h e v e r m i c u l i t e is dehydrated, t h e water i s l o s t molecule-by-molecule

r a t h e r than layer-to-layer,

and during most s t a g e s of dehydration complete

water l a y e r s are not present.

Though i t may w e l l be that when a swelling

c l a y i s buried t h e i n t e r l a y e r space is completely f i l l e d with water, t h i s

s i t u a t i o n need not exist during a l l s t a g e s of b u r i a l .

It is conceivable t h a t

a t some s t a g e water is released from t h e i n t e r l a y e r space t o t h e pores with

no accompanying decrease i n i n t e r l a y e r volume.

I f an expanded c l a y l a y e r
c

containing less than i t s f u l l component of i n t e r l a y e r water is collapsed t o

1 0 A, t h e i n c r e a s e i n void area without a concomitant i n c r e a s e i n pore water
would cause overcompaction.

It is not clear whether t h e s e phenomena are

s i g n i f i c a n t , but they may need t o be considered.

When montmorillonite l a y e r s are converted t o i l l i t e , t h e r e should be

a volume reduction of t h e l a y e r s , exclusive of i n t e r l a y e r volume.

As A13+

i s s u b s t i t u t e d i n t h e octahedral sheet and t h e l a r g e Mg2+ and Fe3+ i o n s are

removed, t h e r e is a decrease i n s i z e in t h e b-axis d i r e c t i o n .

As A 1 s u b s t i -

t u t e s i n t h e t e t r a h e d r a l sheet, i t increases i n s i z e ; however, when t h e l a y e r

charge is l a r g e enough, t h e t e t r a h e d r a l r o t a t e s , decreasing t h e s i z e of t h e
b-axis,

+ into

and locks t h e K

p o s i t i o n (Weaver and Pollard, 1973).

These

'

57

changes should r e s u l t i n a decrease i n l a y e r volume.

*

4+
3+
The released S i , Fe ,

and Mg2+ may r e a c t t o form c h l o r i t e and quartz and compensate f o r t h e reduct i o n i n t h e s i z e of t h e 2 : l layers.

These new minerals would presumably form

some d i s t a n c e from t h e s i t e where t h e ions were taken i n t o solution.

l o c a l i n e q u i t i e s would r e s u l t .
and i n another decreased.

Thus,

I n one area t h e pore volume would be increased

It is u n l i k e l y t h a t a l l of t h e s e ions would migrate

t o t h e zone where t h e seal i s formed, but some evidently do.

Heat generated by high-level r a d i o a c t i v e waste w i l l l i k e l y cause similar
chemical r e a c t i o n s and cause ions t o be mobilized i n t h e high-temperature

zone

and migrate t o lower temperature areas, where they could p r e c i p i t a t e t o form

a permeability b a r r i e r .

Water Chemistry
t

The s a l i n i t y of t h e i n t e r s t i t i a l water i n sandstones normally i n c r e a s e s

with depth (De S i t t e r , 1947; Dickey, 1969, 1972; F e r t l , 1976), reaching values
t e n times t h a t of seawater.

Some i n v e s t i g a t o r s ( T i m and Maricelli, 1953,

and Myers, 1963) found t h a t i n sandstones associated with t h i c k s h a l e s e c t i o n s

t h e waters have lower s a l i n i t i e s than t h a t of seamter.
be due t o t h e i n f l u x of f r e s h e r water from t h e shales.

This is believed t o
Dickey e t a l . (1972)

demonstrated t h a t i n southwestern Louisiana high-pressure formation waters

from sands enclosed i n undercompacted s h a l e s have t h e composition of waters
t h a t normally are 500 m t o 1000 m shallower.
Various s t u d i e s (Sukharev and Krumbul'dt,

1962; Rieke e t al., 1964; F e r t l

and Timko, 1970a; Schmidt, 1973) have shown t h a t t h e s a l i n i t y of i n t e r s t i t i a l

f l u i d s i n s h a l e s is considerably lower than s a l i n i t y i n associated sandstones.
Schmidt found t h a t t h e d i f f e r e n c e was less i n t h e high-pressure zone.

-bj

I n normal-pressured s e c t i o n s , t h e s a l i n i t y of t h e i n t e r s t i t i a l water i n
s h a l e s tends t o i n c r e a s e with increasing depth; however, i n high-pressure zones

58

t h e s a l i n i t y decreases (and p o r o s i t y increases).

The decrease i s commonly

abrupt and can be observed by a decrease i n s h a l e r e s i s t i v i t y .

The decrease

l
i
f

i n r e s i s t i v i t y i s commonly used t o give a forewarning of t h e presence of overpressures.

(For a d e t a i l e d review of t h e phenomenon, see F e r t l , 1976).

Most experimental compactions s t u d i e s of c l a y s and n a t u r a l muds ( f o r

review, see F e r t l , 1976) i n d i c a t e t h a t t h e s o l u t i o n s squeezed o u t a t t h e
beginning of compaction have higher concentrations of ions than t h e i n t e r -

s t i t i a l s o l u t i o n s i n i t i a l l y present and t h a t with increasing p r e s s u r e t h e

e l e c t r o l y t e content i n t h e expressed water decreases.

However, o t h e r s t u d i e s

(Manheim, 1966, and Shishkina, 1968) found no appreciable change i n t h e comp o s i t i o n of extracted water during squeezing.
F e r t l (1976) suggested t h a t t h e laboratory experiments which i n d i c a t e
t h a t t h e s a l i n i t y of squeezed-out s o l u t i o n s progressively decreases with increasing pressure may explain why t h e i c t e r s t i t i a l w a t e r i n shales i s less
than t h a t of water i n associated sandstones.
Aside from t h e f a c t t h a t t h e laboratory r e s u l t s are c o n f l i c t i n g , i t i s

unlikely t h a t t h e r e s u l t s obtained from t h e short-term a p p l i c a t i o n of press u r e can be used as a model f o r long-term b u r i a l .

chemistry and diagenesis go hand-in-hand.

I n t h e n a t u r a l system, water

Diagenetic r e a c t i o n s , which a f f e c t

t h e chemistry of t h e pore w a t e r , cannot be duplicated i n short-term laborat o r y experiments.

Laboratory squeeze s t u d i e s may g i v e an i n d i c a t i o n of w h a t

happens during t h e earliest s t a g e s of b u r i a l .

There i s l i t t l e doubt t h a t t h e

s a l i n i t y of b r i n e s i n sandstones is determined i n p a r t by t h e water i n t h e

enclosing shales.

Some of t h e processes t h a t are believed t o c o n t r o l t h e

migration of s h a l e pore water and i o n s i n t o sand are:

compaction, osmosis,

reverse osmosis, i o n f i l t r a t i o n , d i f f u s i o n , montmorillonite dehydration, and

probably o t h e r s ( f o r review see Rieke and Chilingarian, 1974; Bradley, 1975,
Burst, 1976).

A s Bradley (1975) p o i n t s out, t h e r e i s no c o n s i s t e n t r e l a t i o n

u-

59

bd
*

between s a l i n i t y and depth, s a l i n i t y and pressures, and s h a l e d e n s i t y (porosi t y ) and abnormal pressures.

Thus, i t i s unlikely t h e r e i s a simple answer.

Most of t h e people concerned with t h e problem consider t h a t t h e release

of i n t e r l a y e r water i s a s i g n i f i c a n t f a c t o r i n c o n t r o l l i n g t h e composition of
-=

subsurface waters.

However, they a l l seem t o assume, based on t h e statements

of Powers (1967) and Burst (1969), that t h e released water i s f r e s h .

only p a r t i a l l y c o r r e c t .

is fresh.

This i s

Water released i n excess of t h e f i n a l water l a y e r

Thus, a t shallow depth some f r e s h water i s released.

f i n a l water i s released, some c a t i o n s must be released with it.

When t h e
This release

starts a t b u r i a l temperatures of 50" t o 80C and a t depths of 1500 m t o 2000 m.

The exchangeable i n t e r l a y e r c a t i o n s are l a r g e l y Na, Mg, Ca, and H.

are exchanged f o r K, which i s obtained l a r g e l y from K-feldspar.

These

Thus, t h e

concentration of c a t i o n s i n t h e pore water should i n c r e a s e u n l e s s t h e exc

changed c a t i o n s r e p l a c e t h e K i n t h e f e l d s p a r , which i s unlikely.

ions presumably r e p l a c e t h e K i n t h e feldspar.

Hydrogen

The d a t a of Weaver and Wampler

(1970) show t h a t from t h e beginning of l a y e r c o l l a p s e u n t i l t h e 7:3 mixedl a y e r phase i s reached, approximately 0 . 5 percent K (of d r i e d sample) is moved
from t h e K-feldspar t o t h e montmorillonite.
of Na, Mg, and C a is released.

Presumably a n equivalent amount

I n t h e Gulf Coast T e r t i a r y shales, water

s o l u b l e c a t i o n s ( l a r g e l y i n t e r s t i t i a l ) comprise 0.4 t o 0.5 percent by weight

of t h e d r i e d bulk sample (Weaver and Beck, 1971).

The i n t e r l a y e r c a t i o n s re-

leased from t h e montmorillonite are a s i g n i f i c a n t f a c t o r i n determining t h e

chemistry of subsurface pore waters.
The i n t e r l a y e r water i s r i c h i n cations.

The concentration of c a t i o n s

(half Na, half Mg) i n a t y p i c a l montmorillonite ( c a t i o n exchange capacity

100 meq/100 g) containing two l a y e r s of water is approximately seven times

that i n seawater (assuming 20 percent of c a t i o n s are adsorbed on t h e edges

60
of t h e c l a y f l a k e s ) .

Analyses (Weaver and Beck, 1971) i n d i c a t e t h a t a typi-

c a l shallow buried Gulf Coast T e r t i a r y c l a y contains approximately 60 per-

cent c l a y minerals, of which 80 percent i s montmorillonite containing 80

percent expanded layers.

Approximately 40 percent of t h e s o l i d component

c o n s i s t s of expanded layers.

The amount of i n t e r l a y e r w a t e r present, based

on two water l a y e r s , i s 7 percent by weight of t h e d r y sample.

Interlayer

exchangeable c a t i o n s comprise approximately 0.65 percent of t h e bulk sample.

The amount of c a t i o n s i n t h e i n t e r s t i t i a l water, 20 percent by weight, would
be 0.2 percent, assuming t h e pore water w a s seawater.

Thus, a f t e r t h e muds

are buried a few hundred meters t h e weight of exchangeable c a t i o n s i s about

three times t h a t of t h e c a t i o n s i n t h e i n t e r s t i t i a l water.

I n a t y p i c a l Gulf Coast w e l l t h e proportion of expanded l a y e r s i s reduced from 20 percent t o 70 percent (50 percent of t o t a l expanded l a y e r s )
within a n i n t e r v a l of approximately 1500 m and t h e r e l e a s e d c a t i o n s comprise

0.3 percent by weight of d r i e d sample.

Within t h i s 1500 m i n t e r v a l approxi-

mately 2,040 g of exchange c a t i o n s have t o be released from 150,000 cm

sediment (assuming 20 percent porosity).

of

The t o t a l amount of c a t i o n s i n t h e

i n t e r s t i t i a l water (assuming seawater composition) i n t h i s volume i s 600 g.

Within t h i s i n t e r v a l t h e released i n t e r l a y e r c a t i o n s should dominate t h e pore
w a t e r chemistry.
Weaver and Beck's (1971) d a t a f o r a Gulf Coast w e l l i n d i c a t e t h a t within
t h e interval (approximately 1800 m) where t h e expanded l a y e r s are reduced from
20 t o 70 percent t h e r e is a l o s s of 0.3 percent (1.0 t o 0.70 percent) of exchangeable c a t i o n s , based on dry weight of sample (Figure 9 ) .

The value i s

e s s e n t i a l l y t h e same as t h e c a l c u l a t e d value and i s s l i g h t l y less than t h e

amount of K t h a t is t r a n s f e r r e d from t h e K-feldspar and m i c a t o t h e montmorill o n i t e (Weaver and Wampler, 1970).

Because t h e l a y e r charge must be increased

ti
(c

61

i n order f o r K t o be fixed between t h e l a y e r s , t h e K value should be l a r g e r

than t h e v a l u e f o r exchangeable cations.

Within approximately t h i s same in-

t e r v a l t h e amount of c a t i o n s i n t h e i n t e r s t i t i a l water increases by approximately

0.2 percent by weight (Figure 9).

Most of t h e released i n t e r l a y e r c a t i o n s

appear t o remain i n t h e s h a l e i n t h i s i n t e r v a l .

Though Weaver and Beck's

values f o r t h e various,cation s p e c i e s may not be accurate, t h e t o t a l values

f o r t h e exchange and i n t e r s t i t i a l i o n s should be reasonably correct.
I n normal-pressured muds and shales, as i n t e r l a y e r w a t e r and exchange
c a t i o n s are added t o t h e pore water, compaction pressures f o r c e s much of t h e
pore water, released i n t e r l a y e r water, and some c a t i o n s (and C1) from t h e
shales.

As t h e p o r o s i t y decreases, more and more c a t i o n s are retained i n

t h e pore water, and t h e c a t i o n concentration increases.

When a permeability b a r r i e r develops, a r e l a t i v e l y high proportion of
*

t h e r e l e a s e d i n t e r l a y e r water as w e l l as t h e c a t i o n s are trapped beneath t h e

barrier.
rir

Figure 9 shows t h e r e l a t i o n of l a y e r c o n t r a c t i o n and decrease i n

c a t i o n exchange capacity t o t h e i n c r e a s e i n t h e amount of c a t i o n i n t h e i n t e r s t i t i a l water.

The i n c r e a s e i n i n t e r s t i t i a l c a t i o n concentration coincides

with t h e i n c r e a s e i n l a y e r collapse, suggesting t h a t t h e exchange c a t i o n s are

t h e source of t h e i n t e r s t i t i a l c a t i o n s .

The formation of a permeability bar-

rier t r a p s both t h e released i n t e r l a y e r c a t i o n s and i n t e r l a y e r water causing

a relative i n c r e a s e i n t h e c a t i o n concentration of t h e i n t e r s t i t i a l water.

I n t h e w e l l studied by Schmidt (1973), t h e i n c r e a s e i n c a t i o n concentration
occurs immediately above t h e top of t h e high-pressure i n t e r v a l .

The under-

l y i n g permeability b a r r i e r may i n h i b i t t h e f l u s h i n g of t h e overlying shales.

1

I n t h e w e l l s studied by Weaver and Beck (1971) and Schmidt (1973) t h e

s a l i n i t y maximum i s followed by decrease i n s a l i n i t y with depth; however, t h e

*W

s a l i n i t y values are higher than those above t h e s a l i n i t y maximum and are not

.20

WEIGHT % CATIONS
.40
.60

1.oo

.80

%CONTRACTEDLAYERS
20
40

60

2000

3000

TOP
HIGHPRESSURE

CI

v)

PE
u1

-tiE
3
4000

EXCHANGE
CATIONS

0
)

Figure 9. Percentage (dry weight of sample) of cations i n the i n t e r s t i t i a l

water and exchange cations as related to increase i n percent of contracted
layers. Gulf Coast early Tertiary w e l l . After Weaver and Beck (1971).

63
t r u l y fresh.

w e l l s suggest

The r e l a t i v e l y low s a l i n i t y values i n t h e deeper p o r t i o n s . of t h e

that l a y e r c o n t r a c t i o n occurred i n t h e s e s h a l e s before a per-

meability b a r r i e r formed and many of t h e released i n t e r l a y e r c a t i o n s (and

t

hydrocarbons?) w e r e a b l e t o migrate.
Presumably t h e r e i s no C 1 i n t h e i n t e r l a y e r space, and t h e C 1 d i s t r i b u t i o n should give some i d e a of t h e e f f e c t of l a y e r c o l l a p s e on t h e composition
of i n t e r s t i t i a l water.

The C 1 concentration and weight percent C 1 show a

general decrease with depth (Weaver and Beck, 1971).

As should be expected,

t h e C 1 concentration decreases r a p i d l y through t h e i n t e r v a l where t h e r e i s

a maximum release of i n t e r l a y e r water.

64

ILLITE

Hydrothermal s t u d i e s by Yoder and Eugster (1954) and Velde (1965 a )

established t h a t t h e s t a b l e high temperature muscovite i s t h e 2M polytype.
The one-layer monoclinic disordered (lMd) polytype i s formed a t t h e lowest
temperature and t h e one-layer monoclinic (lM) polytype a t intermediate temperatures.

The sequence with increasing temperature i s lMd + lM

ever, i n nature t h e sequence appears t o be l Md + 2M.

-+

2M; how-

Most hydrothermal ex-

periments have been conducted using compositions similar t o muscovite r a t h e r

than i l l i t e .

Velde (1965 a and b) concluded t h a t lMd and lM polymorphs are

e i t h e r metastable muscovite forms o r are micas with a composition d i f f e r i n g

from muscovite, e.g.

glauconite, celadonite, and i l l i t e .

A r e l a t i v e l y rare

three-layer t r i c l i n i c (3T) polytype a l s o e x i s t s .

Low-temperature i l l i t e s form by t h e weathering of K-feldspar and possibly
by d i r e c t p r e c i p i t a t i o n ; however, most i l l i t e apparently forms by t h e b u r i a l
diagenesis of montmorillonite and volcanic material.
Many i l l i t e s are d e t r i t a l and derived from low-grade metamorphic rocks.
The metamorphic rocks have presumably gone through t h e b u r i a l diagenesis stage.
Whether t h e precursor w a s commonly montmorillonite i s not known.
"Pure i l l i t e " should c o n s i s t e n t i r e l y of contracted 1 0 A l a y e r s ; however,
many i l l i t e s have a r e l a t i v e l y broad 1 0 A r e f l e c t i o n .

The 1 0 A broadens i n

t h e d i r e c t i o n of t h e low angle spacing and t h e 5 A peak i n t h e d i r e c t i o n of

t h e high angle spacing.

Weaver (1965) and Weaver and Beck (1971) have i n t e r -

preted t h i s t o i n d i c a t e t h a t t h e i l l i t e contains some i n t e r l a y e r e d 14 A l a y e r s .

These l a y e r s may be e i t h e r montmorillonite o r c h l o r i t e (possibly dioctahedral).
On t h e b a s i s of chemical d a t a , Raman and Jackson (1966) concluded that many

i l l i t e s contain 20 percent t o 30 percent c h l o r i t e l a y e r s along with varying

65

bd
i

amounts of montmorillonite and vermiculite.

These authors suggest t h a t t h e

" t r u e 1 0 A" l a y e r s i n i l l i t e are c l o s e t o muscovite i n composition and t h a t

t h e high Mg and Fe and low A 1 and-K i s due t o t h e presence of other layers.
Others (Velde, 1965 a; Hower and Mowatt, 1966; Reesman and Keller, 1967)
b e l i e v e i l l i t e i s a single-phase mineral.
between.

The t r u t h is probably somewhere i n

The 1 0 A l a y e r s l i k e l y have a composition d i f f e r e n t from muscovite,

but o t h e r types of l a y e r s are almost c e r t a i n l y present i n many i l l i t e s .

Chemistry
X-ray analyses of i l l i t e samples i n d i c a t e t h a t they commonly contain 10
percent t o 30 percent expanded layers.

Other i l l i t e s , u s u a l l y deeply buried

Paleozoic and Precambrian, have no expanded l a y e r s and appear t o be composed

e n t i r e l y of 1 0 A layers.
r
c

Both "impure" and ''pure"

i l l i t e s commonly contain a n abundance of Fe

and Mg which is assigned t o t h e octahedral sheet.

U

A t y p i c a l i l l i t e would have

t h e following s t r u c t u r a l formula:
(M1 .5OFe3'.2OMg.32) (sj.3.50M.55) 010(0~2K.76Na.01 &.02

There i s a tendency f o r t h e octahedral Fe/Mg r a t i o t o be smaller i n t h e w e l l c r y s t a l l i z e d 2M i l l i t e s .

Phengltes average formula: (d1.37Fe3+,19Fe2+.1 1Mg.38 (si3.33M.67) O10H2 @.8ONa.lOCa.O5)

are mica-like minerals t h a t occur i n t h e low grade metamorphic b l u e s c h i s t and

g r e e n s c h i s t facies (Ernst, 1963).

Their formation i s favored by high pres-

s u r e s and r e l a t i v e l y low temperatures (Velde, 1965 b).

Phengites have a l a y e r

charge of approximately 1.00 (Ernst, 1963; Ernst, 1964; Velde, 1965 b);

illites

have l a y e r charges ranging from 0.60 t o 1.00, with most having a v a l u e less
than 1.00.

LJ

Phengites have a t e t r a h e d r a l charge ranging3rom 0.50 t o 0.95,

with a n average value of 0.65 t o 0.70.

Some i l l i t e s have a charge t h i s high,

66
but most have a lower t e t r a h e d r a l charge (0.45 t o 0.60).

The average octa-

hedral charge f o r phengites (0.36) i s s l i g h t l y l a r g e r than t h e v a l u e f o r

i l l i t e s (0.32).

The average i l l i t e d a t a are misleading, as many of t h e i l l i t e s included

are r e a l l y mixed-layer clays.

The s t r u c t u r a l formula of two of t h e b e t t e r -

c r y s t a l l i z e d i l l i t e s are:
Belt -100 percent 10 A layers (Weaver and Pollard, 1973):
(A1 .51Fe3+.03Fe2+.03w.43) (si3.43A1.57) 0 1 0 ( 0 ~ 2 K . 8 9 N a . 0 2 ~ J 4 ~
Marblehead -95

percent 10 A layers (Gaudette, 1965):

(Ai.51Fe3+.04Fe2+.07w.3d
(si3.54d.46) 010(0~2K.70Na.03G.05

The b e t t e r - c r y s t a l l i z e d i l l i t e s can have a l a y e r charge of 1.0.

They

have less t e t r a h e d r a l and more octahedral charge than t h e t y p i c a l phengite.

Most of t h e s e i l l i t e s have less octahedral Fe than phengites (and less than
well-crystallized

illites).

Figure 1 0 shows t h e d i s t r i b u t i o n of t e t r a h e d r a l and octahedral A 1 relac

tive t o t o t a l Al f o r montmorillonite-beidillites, mixed-layer illite-montmorill o n i t e q , i l l i t e s , and phengites.

Tetrahedral and octahedral Al decreases i n

t h e sequence montmorillonite, mixed-layer clay, i l l i t e , phengite.

This should

be accompanied by an i n c r e a s e i n width of both t h e t e t r a h e d r a l and octahedral

s h e e t s and should cause no s i g n i f i c a n t change i n t h e amount of t e t r a h e d r a l
rotation.

It seems u n l i k e l y t h a t t h i s evolutionary mineral sequence develops

with t h e A 1 content remaining constant.

The same f i g u r e shows t h a t as t o t a l A 1 i n c r e a s e s f o r a given mineral
both t e t r a h e d r a l and octahedral Al increases.

A s t h e t o t a l Al i n c r e a s e s i t i s

equally divided between t h e t e t r a h e d r a l and octahedral l a y e r s , and l a y e r charge

does not show a major i n c r e a s e except f o r t h e mixed-layer c l a y s (slope of

67

TET. OCT.
1.00 2.00

.90

1.90

.80 1.80

.70 1.70

.60 1.60

.M)

1.60

.40 1.40

.30 1.3C

.20

1.2c
MONT.

TETRAHEDRAL
MIXED-LAYER CLAY
MONTMORILLONITE

.10 1.1(

0 1.0(

/
80

1.60

1.70

1.90

2.10

2.30

2.50

TOTAL AL

Figure 10. Aluminum distribution i n dioctahedral 2:l clay minerals. Lines'

indicate range of values. Arrows indicate midpoint of range and indicate
\ amorphim
direction of increased grade of diagenesis-met

2.70

68
octahedral A l graph does not p a r a l l e l t e t r a h e d r a l A l ) .

The width of t h e

t e t r a h e d r a l l a y e r should i n c r e a s e and t h e octahedral l a y e r decrease.

This

favors t h e f i x a t i o n of K.
The maximum t o t a l Al i n c r e a s e s from 2.0 f o r montmorillonite t o 2.30 f o r
mixed-layer c l a y and i l l i t e t o 2.50 f o r phengite.

For values less than t h e

maximum t h e r e i s considerable overlap, but t o t a l A 1 g e n e r a l l y i n c r e a s e s as

t h e temperature a t which t h e minerals formed increases.

The median t e t r a h e d r a l

Al content i n c r e a s e s from 0.16 f o r montmorillonite t o 0.71 f o r phengite.

Octahedral A 1 decreases s l i g h t l y , from 1.50 f o r montmorillonite t o 1.40 f o r
phengite.

The s i z e of t h e t e t r a h e d r a l l a y e r should i n c r e a s e relative t o t h e

octahedral l a y e r favoring t h e development of K-locked micaceous layers.

These

changes i n A 1 content can be caused by adding A 1 t o t h e mineral o r removing

Si.

Laboratory experiments i n d i c a t e t h a t under some conditions S i i s re-

moved from t h e 2 : l layers.

H2

Chemical analyses of muscovites show t h a t they contain approximately 4.5

percent t o 4.7 percent H20.

Phengites commonly contain 4.4 percent t o 4.7

percent H 0, which suggest they do n o t c0ntai.n i n t e r l a y e r s of c h l o r i t e .

2

In

c o n t r a s t i l l i t e s contain from 4.6 percent t o 8.0 percent H 0 with an average

2

of approximately 7 percent.

X-ray p a t t e r n s of i l l i t e have a broader 1 0 A

r e f l e c t i o n than those f o r phengite and muscovite.

The broadening shows as

a less s t e e p s l o p e on t h e low-angle (high A) s i d e of t h e 1 0 A peak.

The

material accounting f o r t h i s change i n slope is presumably t h e material cont a i n i n g t h e excess H 0.

2
Hower and Mowatt (1966) suggested t h a t t h e excess H20 i s present as n e u t r a l
H20 trapped i n nonexpanded layers.

Not only i s t h e 1 0 A peak broadened on t h e

low-angle s i d e , but t h e 5 A peak is broadened on t h e high-angle s i d e .

The

&id'

69

LJ
-c

n a t u r e of t h e 5 A peak i n d i c a t e s t h a t e i t h e r t h e i l l i t e contains some 14 A

i n t e r l a y e r s (which would r e q u i r e two l a y e r s of trapped water) o r t h e c h l o r i t e
contains a l a r g e percentage of 1 0 A l a y e r s .

Raman and Jackson (1966) and

Weaver and Beck (1971) have suggested t h a t t h e broadening of t h e i l l i t e peak,

a
*

and t h e excess H 0 are caused by t h e presence of c h l o r i t e l a y e r s , probably

2
dioctahedral, i n t h e i l l i t e ; however, t h i s does n o t account f o r t h e high S i
content of i l l i t e s .

It seems l i k e l y t h a t some montmorillonite o r v e r m i c u l i t e

l a y e r s are present.
The f a c t that phengites, with no excess H20, have a n octahedral l a y e r
w i t h a s i g n i f i c a n t l y higher R2+ content than muscovites i n d i c a t e s t h a t mical i k e minerals ( i l l i t e ) can exist with t h i s composition; however, phengites
have a l a y e r charge of 1.0 as opposed t o a v a l u e of 0.7 t o 0.8 f o r i l l i t e s .
*

A s Hower and Mowatt (1966) suggested, because a value of 1.0 i s an upper l i m i t

does not mean i t i s a l s o a lower l i m i t .
I n any event many, i f not most, i l l i t e s have not been subjected t o high
enough temperatures and/or pressures f o r a l l of t h e i l l i t e t o form a s i n g l e
phase.

I n most cases t h e second phase i s a n expanded l a y e r .

The base of t h e

1 0 A x-ray peak of "typical" Paleozoic i l l i t e s i s asymetrical, being f l a r e d

s l i g h t l y towards t h e l a r g e r A values.
t o be "pure" i l l i t e s .

These i l l i t e s are commonly considered

When t h e samples are t r e a t e d with ethylene glycol, t h e

low-angle shoulder decreases and t h e r e i s a s l i g h t i n c r e a s e i n t h e sharpness

ratio.

When t h e samples are heated t o 3OO0C t h e r e i s a f u r t h e r i n c r e a s e i n t h e

sharpness r a t i o and a s i g n i f i c a n t i n c r e a s e i n peak height.

.P

Calculations based

on t h e increased peak height a f t e r heating i n d i c a t e i l l i t e s commonly c o n t a i n

1 0 percent t o 30 percent mixed-layer illite-expanded c l a y (probably montmorillonite or beidellite).

td

expanded l a y e r s .

The mixed-layer phase contains 5 percent t o 20 percent

70

It should be noted t h a t f o r t h o s e samples with t h e l a r g e r ,mounts of

calculated mixed-layer c l a y t h e 7 A c h l o r i t e peak decreases when t h e samples

are heated t o 3000C.

It may be t h a t some poorly c r y s t a l l i n e c h l o r i t i c l a y e r s

are present i n t h e mixed-layer phase.

rc

Illit e-P heng it e Relation

P l o t s of d a t a f o r i l l i t e s and mixed-layer illite-montmorillonites v e r s u s

number of contracted l a y e r s (Hower and Mowatt, 1966, and Weaver and P o l l a r d ,
1973) i n d i c a t e t h a t as t h e t o t a l l a y e r charge i n c r e a s e s most of t h e i n c r e a s e
occurs i n t h e t e t r a h e d r a l s h e e t and t h e r e is r e l a t i v e l y l i t t l e change i n t h e
octahedral sheet; however, graphs of chemical changes versus b u r i a l temperat u r e (Figure 4) suggest t h a t with increasing temperature t h e octahedral charge
and octahedral Mg and Fe decrease and octahedral A 1 i n c r e a s e s t o a value of
Phengites commonly contain t h r e e times as much octahedral Mg and Fe.

1.80.

I f t h e r e is a trend f o r t h e Al content of t h e octahedral l a y e r t o i n c r e a s e

with increasing temperature, then t h e phengites must be considered a s e p a r a t e
phase r a t h e r than a p a r t of t h e montmorillonite + T l l i t e + phengite d i a g e n e t i c
Phengites are formed a t high pressures and r e l a t i v e l y low tempera-

sequence.

t u r e s (Velde, 1965 b).

K-feldspar,
and quartz.

Velde has suggested t h a t i l l i t e s (low R

and w a t e r react t o form phengite (high R

A t y p i c a l i l l i t e (high R

2+

2+

2+

), c h l o r i t e ,

), c h l o r i t e (low R

) p l u s K-feldspar

2+

should produce a

phengite and r e q u i r e r e l a t i v e l y l i t t l e r e c r y s t a l l i z a t i o n .
Thus, during diagenesis and metamorphism montmorillonite p l u s K-feldspar
can t a k e two routes.

F i r s t a mixed-layer phase is formed.

I f t h i s phase is

subjected t o high pressures and r e l a t i v e l y low temperatures, t h e o c t a h e d r a l

s h e e t is not "cleaned up" and phengite (low octahedral Al) p l u s quartz is
formed.

I f t h e mixed-layer phase is subjected t o high temperatures and

bi'

71

u
*

r e l a t i v e l y low pressures, t h e octahedral l a y e r i s "cleaned up" and a sericiteo r muscovite-type (high octahedral Al) mineral p l u s c h l o r i t e is formed.

This

dual evolutionary sequence i s a l s o indicated by t h e average MgO values:

montmorillonite 3.6 percent + i l l i t e 2 , 8 percent
muscovite 0.6 percent.
t u r e increases.

s e r i c i t e 1 . 7 percent +

The MgO content decreases as t h e formation tempera-

I n c o n t r a s t , phengites have e s s e n t i a l l y t h e same average

MgO v a l u e ( 3 . 8 percent) as t h e montmorillonites.

Guven (1970) states t h a t i l l i t e s are sometimes subjected t o deep b u r i a l

with t h e r e s u l t i n g g r e a t e r p r e s s u r e i n c r e a s e relative t o temperature; h e concludes t h a t i l l i t e s are t h e r e f o r e environmentally c l o s e r t o phengites than
t o muscovites; however, i n areas l i k e t h e Gulf Coast and other montmorilloniter i c h areas where undercompacted shales exist and where t h e excess w a t e r acts

as a heat s t o r a g e r e s e r v o i r , temperature may be more important than pressure.

*

Hydrothermal Studies
Hydrothermal experiments (300" t o 450C) with n a t u r a l mixed-layer i l l 5 t e Y

montmorillonite (Velde and Bystrom-Brusewitz,

1972) showed that t h e i n i t i a l

transformation i s t h e c r y s t a l l i z a t i o n of quartz and a decrease i n t h e percentage of mixed-layer material and expanded layers.

This i s followed by

t h e exsolution of c h l o r i t e ( k a o l i n i t e , i f Mg and Fe are not present) and t h e

continued decrease i n t h e proportion of expanded l a y e r s .

The mixed-layer

phase becomes ordered when t h e expanded l a y e r s decrease t o 25-30 percent.

I l l i t e may s t a r t t o form a t t h i s time.

The next s t a g e is t h e d e s t r u c t i o n of

t h e mixed-layer phase and formation of a d d i t i o n a l i l l i t e and c h l o r i t e (or

kaolinite).

Eventually t h e i l l i t e breaks down t o form 2M muscovite and chlor-

i t e (greenschist f a c i e s ) .

-bJ

Hydrothermal experiments (Velde, 1977) with a number of n a t u r a l c l a y s

and c l a y mixtures showed that with increasing temperature montmorillonite

72
developed a mixed-layer illite-montmorillonite phase.

The proportion of il-

l i t e l a y e r s increased with increasing temperature; a t t h e same time c o r r e n s i t e

(high R 2+ ) developed.

u
I

With increased temperature, quartz and c h l o r i t e (high R3+)

exsolved (near 300C) from i l l i t e , and t h e i l l i t e gradually developed a b e t t e r

set of 2M r e f l e c t i o n s as more c h l o r i t e w a s exsolved.

C h l o r i t e f i r s t developed

when a n ordered IMII (illite-montmorillonite-illite-illite)-Jhase developed

and p e r s i s t e d as a muscovite-type m i c a developed.
H e a l s o noted t h a t N a , K, and Ca are present i n most n a t u r a l materials
and found t h a t t h e N a and K w i l l e n t e r i n t o mixed l a y e r s and mica phases with
increased temperature, but t h e C a w i l l be released i n t o t h e aqueous s o l u t i o n ,
possibly t o produce calcite where t h e P(C0 ) i s s u f f i c i e n t l y high.
2

The Weaver

and Beck (1971) study of n a t u r a l c l a y s indicated t h a t C a is p r e f e r e n t i a l l y retained i n t h e expanded l a y e r s and that C a i o n s are t h e l a s t i n t e r l a y e r i o n s t o
be released during diagenesis.

This i s compatible with t h e r e s u l t s of Velde.

Polymorphic Forms of I l l i t e
The most common i l l i t e polytypes are t h e 2M and lMd forms.
f o r glauconite and c e l a d o n i t e t h e lM v a r i e t y i s r e l a t i v e l y rare.

Other than
Velde and

Hower (1963) and Maxwell and Hower (1967) proposed peak-height r a t i o s , 2.74 A/
2.58 A and 2.80 A/2.58 A respectively, which can be used t o measure t h e 2M/lMd
ratio.

Experimental curves were constructed using mixtures of 2M muscovite and

lMd i l l i t e .

The physical f o r c e s necessary t o reduce t h e muscovite t o one micron

i n s i z e should d i s r u p t t h e 2M arrangement and lead t o high estimated lMd values.

Their d a t a tend t o confirm t h i s , as they found t h a t t h e 3.74 A12.58 A r a t i o
,
w a s l a r g e r , f o r a given amount of 2Mmica, f o r t h e >1pm f r a c t i o n than f o r
t h e <1vm f r a c t i o n .

These peak-height r a t i o s can be considered t o be only a

rough e s t i m a t e of t h e relative amounts of 2M and lMd forms; however, t r e n d s can

be assumed t o be r e l i a b l e .

73

b,
i

'Most s h a l e s contain both 2M and lMd i l l i t e s .

Velde and Hower (1963)

x-rayed ,various- S i z e f r a c t i o n s of 74' Paleozoic s h a l e samples.

Their a n a l y s i s

indicated t h a t t h e S10 vm f r a c t i o n ' u s u a l l ? containedLon1y 2M i l l i t e .

The

proportion 'of 1Md increases with decreasing g r a i n s i z e , commonly comprising

'U

100 percent of t h e ~0.2um fraction;*however t h e lower l i m i t of d e t e c t i o n f o r

t h e 2M polymorph 3 s believed to be 24 percent (Maxwell and Hower

<1 l
m f r a c t i o n of most samples c o n t a i n less than'50 percent 2M i l l i t e
amount of 2M i l l f t e i n t h e .>1pm f r a c t i o n
no modal c o n c e n t r a t i o

anges from 0 t o 100 percent with

Their data-suggest t h a t t h e

l i t e i n Paleozoic shales

c o n s i s t s of 'an average of apbroximately 30 percent 2M and 70 percent lMd i l l i t e .

A l l e r r o r s would 'cau

an^i n c r e a s e i n t h e 1Md v a l u e

It i s almost c e r t a i n

that t h e 2M polytype is inore abundant than ihdicated by t h e s e data; however,

i t does decrease with decreasing g r a i n s i z e .

T h e g r a i n s i z e of i l l i t e is a

rough measur

f t h e r e l a t i v e amountjof t h e two polytypes

The major problem

i s t o determine how much of t h e 2M i l l i t e is d e t r i t a l and how much has formed

u

during b u r i a l d i a
be d e t r i t a l .

t should a

When lMd i l l i t e is present, many authors assume t h a t i t had an

authigenic o r i g i n .
Several s t u d i e s have demonstrated an i n c r e a s e i n t h e 2M/W r a t i o with
increasing degree of metamorphism (temperature).

Reynolds (1963) found t h a t

i n t h e Precambrian B e l t limestones t h e 2M/lMd r a t i o increased as t h e meta-

&hd

74
b u r i a l increased.

They noted that t h e r e w a s a general trend of increasing

g r a i n s i z e with depth.

I n addition, t h e f a b r i c changes from one showing ex-

c e l l e n t f o l i a t i o n p a r a l l e l t o t h e bedding a t t h e top of t h e s e c t i o n , t o one

showing an increasing d i s o r i e n t a t i o n of t h e l a y e r s i l i c a t e s a t t h e bottom of
t h e section.
than 7/3.

B i o t i t e w a s present i n samples containing 2M/lMd r a t i o s l a r g e r

Thus, i t appears t h a t IMd i l l i t e can p e r s i s t t o r e l a t i v e l y high

temperatures (greenschist f a c i e s ) .
0l8/Ol6

s t u d i e s (Eslinger and Savin, 1973 a and b) of some of t h e s e same

sediments ( ~ 0 . 5p f r a c t i o n ) suggested t h a t b u r i a l temperatures ranged from

225OC f o r a s h a l e having a 2M/lMd r a t i o 1/3 and 310C f o r one with a r a t i o

of 3/2.

Extrapolation indicated that a temperature of 400C would be reThese r e s u l t s w i l l be discussed i n

quired t o o b t a i n 100 percent 2M i l l i t e .

more d e t a i l i n a later section.

Foscolos and Kodama (1974) studied t h e Lower Cretaceous s h a l e s of B r i t i s h

Columbia and established t h e following r e l a t i o n s .
Percent
2M I l l i t e

Crystallinity
Index (mm)

Sharpness
Ratio

Percent I l l i t e
I n ML Phase

Temperature

< 25

77Oc

40-50

94O c

17

1.9

70-80

141" C

15

2.3

80-90

164O C

<25

>20

35

19

50
65

<1.5

These values do not j i b e with t h e d a t a obta,.ied

( M a x w e l l and Hower, 1967; Eslinger and Savin, 1973).

on t h e Precaa,riam B e l t
The B e l t s h a l e s only

have 25 percent 2M i l l i t e a t a temperature of 225OC and only 60 percent a t

18 16
31OoC (0 /O ). I n p a r t , t h e d i f f e r e n c e i s due t o t h e f i n e g r a i n s i z e

(<0.5 lnn) analyzed by Eslinger and Savin (1973) as compared t o t h e less than
2 p f r a c t i o n analyzed by Foscolos and Kodama (1974).

However, Maxwell and

..

75

L4
*

Hower (1967) found similar percent 2Mvalues f o r t h e less than 2 vm f r a c t i o n

of B e l t samples from t h e same section.

Maxwell and Hower r e p o r t t h a t even

t h e most shallow buried i l l i t e s , which contain no d e t e c t a b l e 2M polytype,

are completely collapsed and contain no expanded l a y e r s (though t h e i r x-ray

Q

p a t t e r n s suggest t h i s may not be sa).

The question is whether montmorillonite completely converts t o a nonexpanded lMd i l l i t e before any 2M material i s formed, o r whether t h e 2M polytype s y s t e m a t i c a l l y i n c r e a s e s through t h e mixed-layer s t a g e of diagenesis,

as suggested by Foscolos and Kodama (1974).

A reexamination of t h e ~ 0 . 2pm

f r a c t i o n of Gulf Coast Miocene samples (Weaver and Beck, 1971) i n d i c a t e s t h a t

t h e r e are no 2M r e f l e c t i o n s present i n t h e samples with a mixed-layer r a t i o
ranging from 1 / 4 t o 7/3.

It seems u n l i k e l y that any 2M i l l i t e r e f l e c t i o n s

should develop u n t i l a l l t h e l a y e r s are contracted t o 1 0 A; however, once a

1 0 A phase develops i t should become coarser and may develop a 2M s t r u c t u r e ,
whereas t h e mixed-layer phase would remain i n t h e f i n e f r a c t i o n .
I n t h e J u r a s s i c of t h e Durance basin of France, Dunoyer d e Segonzac (1969)
found t h e 2M/lMd r a t i o systematically increased with depth.
C r y s t a l l i n i t y (Sharpness)

I n a study of low-grade metamorphic shales, Weaver (1961) showed t h a t

t h e "sharpness"'of

t h e 10 A i l l i t e peak increased with increased metamorphism.

Weaver observed t h a t t h e 1 0 A peak became narrower and t h e low-angle shoulder

decreased w i t h increasing degree of metamorphism.

H e proposed that t h e r a t i o

of t h e peak height a t 10.5 A t o t h a t a t 10.0 A (sharpness r a t i o ) could be

used as a measure of degree of metamorphism.

H e demonstrated that i n t h e

s h a l e s f r i n g i n g t h e Ouachita Mountains t h e sharpness r a t i o increased with

*W

increasing degree of metamorphism.

Later, Kubler (1966 a and b) introduced

76
t h e c r y s t a l l i n i t y index (peak width, i n mm, a t half-height).
t h a t t h e peak width i s a measure of c r y s t a l l i n i t y .

Kubler b e l i e v e s

The 10 A peak becomes

narrower as t h e proportion of i n t e r s t r a t i f i e d m o n t m 6 r i ~ ~ o n i t evermiculite,

,
and c h l o r i t e l a y e r s decreases.

Thus, any measure of peak width is a measure

of i l l i t e p u r i f i c a t i o n and does not n e c e s s a r i l y have anything t o do with

crystallinity.

Weaver o r i g i n a l l y r e j e c t e d t h e peak width a t half-height

measure because i t did not include t h e low-angle t a i l i n t h e measurement.

Further, an a b s o l u t e measurement i s dependent upon machine s e t t i n g s .

Lydka

(1974) has suggested a measurement wherein t h e 10 A peak height i s divided

by t h e quartz peak width a t half-height.
Weber (1972) suggested using t h e peak width a t half-height of quartz as
a n i n t e r n a l standard,

H e found t h a t t h e i l l i t e c r y s t a l l i n i t y i n a series of s l a t e s showed r e g i o n a l

v a r i a t i o n s which could be r e l a t e d t o d i f f e r e n t b u r i a l depths and v a r i a b l e

heat flow rates.

H e conducted experiments t h a t showed t h a t t h e peak width

of t h e 10 A peak increased as t h e thickness of t h e c l a y l a y e r on t h e x-ray s l i d e

increased.

This i s because during t h e preparation of s l i d e s t h e f i n e r frac-

t i o n (wider peak) occurs on t h e s u r f a c e of t h e s l i d e s .

H e f u r t h e r noted t h a t

t h e 10 A peak p a t t e r n s from t h e sedimented s l i d e s were wider than those produced from polished s l a b s of t h e s l a t e and t h a t t h e divergence increased as
t h e g r a i n s i z e decreased.

Thus, as expected, g r a i n s i z e must be taken i n t o

account when determining t h e s i g n i f i c a n c e of t h e "degree of c r y s t a l l i n i t y " .

Weber e t al. (1976) proposed
thickness".
size.

easure of " c r y s t a l l i n i t y " c a l l e d "apparent-

It i s based on t h e Scherrer

l a r e l a t i n g peak width t o c r y s t a l

77
Weaver (1965) presented d a t a t o i n d i c a t e - t h a t t h e K content o f i l l i t e s
increased l i n e a r l y as t h e 10-A/5 A r a t i o - d e c r e a s e d . "The K i n c r e a s e a l s o re-

lates t o t h e sharpness r a t i o and peak width a t half-height.

P o l l a r d (1973) showed that t h e r e w a s a

Later, Weaver and

r e l a t i o n between t h e

'r

K20 and Fe203 values of i l l i t e s ,

The Fe 0 content decreases from 1 2 percent

2 3

t o 1 percent as t h e K20 content i n c r e a s e s

5 percent t o 8-11 percent.

Both K and Fe a f f e c t t h e relative i n t e n s i

t h e 10 ,A/5 A r a t i o - but with

An i n c r e a s e i n K causes a decrease i n t h e 10 A / 5 A r a t i o ;

opposite e f f e c t s .

an i n c r e a s e i n Fe causes an i n c r e a s e i n t h e 10 A / 5 A r a t i o
A p l o t of Hpwer and Mowatt's (1966) Fe and K values f o r a number of il
l i t e s and mixed-layer illite-montmorillonites

i n d i c a t e s two-separate trends.

The samples with less than 20 percent expanded Layers and-those with more
-

than 20 percent expanded l a y e r s show s e p a r a t e trends.

n. both cases t h e

, c o n t e n t increases as t h e Fe content decreases.

a decrease i n t h e percentage

B o t h - s e r i e s of samples show a decreas

ri.

of expanded layers.,

here is considerable s c a t t e r ,

Contrary t o t h e general trend (decrease i n Fe with decrease

i n expanded l a y e r s ) , t h e samples withsmore than 20 percent expanded l a y e r s

average less Fe than t h o s e with fewer expanded l a y e r s
of. t h e samples with a high conte

This is because most

of expanded l a y e r s are g-bentonites derived

/

from low-Fe v o l c a n i c - a s h
matergal t h a t had a

The d a t a i n d i c a t e t h a t most llllites developed from

igher Fe content than r h

K l h g e b i e l and Latouche ( 1 9 6 2 ) 3 r e l a t e d t h e . 5
t h e Fe content

AI1

r a t i o of i l l i t e s t

Esquevin (1969), Duyoyer d e Segonzac (1969), a

r e l a t e d t h e (002)j(001) r a t i
a

that the (002) / (001), r a t i o . i n c r e a s e s as "cry

r e l a t e d t h e s e t r e n d s t o :theedegree of metamo
L i d

t i c volcanics.

have suggested

78

epizone).

G i l l e t al. (1977) found t h a t a broad general r e l a t i o n e x i s t e d

f o r i l l i t e s i n sandstones, s i l t s t o n e s , and a r g i l l a c e o u s rocks but n o t f o r

carbonate rocks.

L.
a

Though t h e peak width a t half-height and sharpness r a t i o

do increase with increasing metamorphism, most analyses show only a very general
f

o r no i n c r e a s e i n t h e (002)/(001) r a t i o w i t h increasing metamorphism.

presumably due t o t h e f a c t t h a t K, Mg and Fe a f f e c t t h e r a t i o .

This is

Though an in-

crease i n K u s u a l l y occurs (increasing t h e (002)/(001) r a t i o ) during increased

diagenesis, t h e Mg

+ Fe

content may o r may not (phengite) decrease.

Analyses,

of a series of anchizone samples from t h e Basque mountains (Dunoyer d e Segonzac

and Heddebaut, 1971) showed that t h e r e w a s no r e l a t i o n between t h e Al/Mg

+ Fe

r a t i o of t h e octahedral l a y e r and t h e (002)/(001) r a t i o of t h e i l l i t e peaks.

A p l o t of t h e d a t a used t o o b t a i n t h e r e s u l t s reported by Weaver (1965)
shows t h a t n o t only does t h e 1 0 A/5 A r a t i o decrease as K20 i n c r e a s e s but t h e
sharpness r a t i o increases (Figure 11) and t h e half-width decreases (Figure 12).
Thus, with increasing degree of d i a g n e s i s and metamorphism t h e K content
of i l l i t e s increases, as would be expected.
decreases.

The Mg

+ Fe

content g e n e r a l l y

One question i s whether external K i s added t o t h e i l l i t e o r

whether t h e K remains constant and a n appreciable amount of Mg and Fe are l o s t

from t h e i l l i t e .

Data presented earlier suggest t h a t e x t e r n a l K i s added t o

t h e i l l i t e and t h a t Fey Mg, and S i are l o s t during t h e earlier s t a g e s of diagenesis.

With increasing temperature t h e s e processes appear t o continue; w i t h

increased pressure (phengite) t h e l a t t e r process apparently is modified (Fe

and Mg remain).
Both t h e c r y s t a l l i n i t y index and t h e sharpness r a t i o depend on measureT

ments r e l a t i v e l y high up on t h e 10 A peak and do not f u l l y t a k e i n t o account

t h e low-angle t a i l o f t e n present on 1 0 A peaks.

Another measurement i s pro-

posed that should c o r r e c t t h i s deficiency and g i v e a b e t t e r d e s c r i p t i o n of

I
79

11.(
I

0
0

10s
0

9.0

0
0

0
i

8.0

7.0
0' 0

6.0
0

2.0

1
4.0

6.0
8.0
SHARPNESS RATIO

10.0

12.0

1
14.0

Figure 11. Relation of K20 content of "illites" t o sharpness'ratio of 10 A

x-ray peak.

80

0
0

6.0 I

CRYSTALLINITY INDEX

..

Figure 12. Relation of K20 content o

10 A x-ray .peak.

to crystallinity index of

LJ*

81

u
*

t h e peak.

The measurement i s c a l l e d t h e "asymmetry ratio".

A l i n e i s drawn

from t h e apex of t h e 1 0 A peak perpendicular t o the'lower edge of t h e c h a r t

paper.

From near t h e base of t h e 1 0 A peak, s l i g h t l y above t h e base l i n e

and background noise, t h e d i s t a n c e from t h e c e n t e r l i n e t o each s i d e of t h e

10 A peak is measured.

The width of t h e r i g h t p o r t i o n (low-angle s i d e ) i s

divided by t h e width of t h e l e f t portion.

The width of t h e l e f t p o r t i o n of

t h e base of t h e peak i s r e l a t i v e l y constant.

Thus, t h e r a t i o is l a r g e l y a

measure of t h e flare-out of t h e low-angle p o r t i o n of t h e 1 0 A peak.

Figure 13 shows t h e r e l a t i o n of t h e asymmetry r a t i o t o t h e K 0 content
2
(samples described by Weaver, 1965).

Samples were dispersed with calgon,

a i r d r i e d , and x-rayed without f u r t h e r treatment.

There i s a good l i n e a r

r e l a t i o n , w i t h t h e asymmetry r a t i o decreasing as t h e K 0 content increases.

2
This measurement suggests t h a t peak asymmetry i s r e l a t e d t o t h e K 0 content.
2

The 10 A15 A r a t i o i n c r e a s e s as t h e asymmetry r a t i o i n c r e a s e s i n d i c a t i n g t h a t

whatever is a f f e c t i n g t h e 1 0 A peak i s ' a f f e c t i n g t h e height of t h e 5 A peak
.a-

even more.

This, p l u s t h e r e l a t i o n t o t h e K content, G g g e s t t h a t both r a t i o s

measure t h e amount of non-10 A l a y e r s present.

H e a t treatments suggest that

t h e s e l a y e r s are e i t h e r montmorillonite o r vermiculate (which would have a high

Mg and Fe content).

I t i s d i f f i c u l t t o see how randomly trappe

water molecules (Hower and Mowatt, 1966) can account f o r t h e s e

var

ons
'

The f a c t o r s

are n o t as simple as

.-,

show

he d a t a f o r most formations do n o t

l i n e a r re

Numerous s t u d i e s have shown t h a t t h e sharpness r a t i o and/or c r y s t a l l i n i t y

index v x y as a function of depth of b u r i a l (temperature) and degree of meta-

-W

morphism (Weaver;l960;

Kubler, 1964, 1966 a and b, 1967, 1968; Dunoyer d e

82

% K20

ASYMMETRY RATIO
Figure 13. Relation of K20 content of "illites" t o asymmetry r a t i o of 10 A
x-ray peak.

83

W
.
l
i

Segonzac and Kubler, 1966; Dunoyer d e Segonzac, 1969; Esquevin, 1969; Foscolos

and Kodama, 1974; Dunoyer d e Segonzac and Bernoulli, 1976; Dunoyer d e

Segonzac, 1976; Rowsell and Deswardt, 1976; G i l l e t al., 1977).

Jackson (1977)

determined t h e c r y s t a l l i n i t y index of 24 samples ranging i n age from 0.016 t o

P

3.3 x 1 09 years B.P.

The values show l i t t l e v a r i a t i o n with age except f o r

a n i n c r e a s e i n t h e i n t e r v a l 0.8-1.05
i n c r e a s e is s i g n i f i c a n t .

9
x 1 0 y e a r s B.P.

Jackson b e l i e v e s t h i s

The number of samples seems somewhat limited f o r

such a conclusion.
Various authors (Kubler, 1968; Dunoyer d e Segonzac, 1969; Frey and Hunziker, 1973; and Foscolos and S c o t t , 1975) have assigned s p e c i f i c i l l i t e crys t a l l i n i t y v a l u e s t o t h e boundaries between t h e zone of diagenesis, t h e anchizone, and t h e epizone.

The value assigned t o t h e s e boundaries is not c o n s i s t e n t ,

i n p a r t because of t h e v a r i a t i o n i n t h e x-ray equipment and t h e various sete-

t i n g s used.
on 2.5,

The boundary between t h e anchizone and t h e epizone has been based

4.0, and 7.8 mm peak widths (and t h e development of p y r o p h y l l i t e and

a l l e v a r d i t e ) ; t h e boundary between t h e diagenesis zone and t h e anchizone has

been based on peak widths of 4.0,
based on t h e sharpness r a t i o (S.R.)

7.5, and 12.8 mm.

are 12.1 and 2.3.

The equivalent boundaries

The latter values are

independent of machine s e t t i n g s and can b e t t e r be standardized.

Foscolos and

S c o t t (1975) have proposed separating t h e diagenesis zone i n t o t h r e e subzones

on t h e b a s i s of c r y s t a l l i n i t y index values.

are mixed-layers,

pretreatment and t h e nature of t h e s t a r t i n g material l i m i t

t h e usefulness of t h i s c l a s s i f i c a t i o n .

Because most c l a y s i n t h i s zone

G i l l e t al. (1977) suggested t h a t t h e r e

w a s a t r a n s i t i o n s t a g e between t h e late diagenetsk-zone and t h e anchizone and

t h a t i t be c a l l e d t h e metadiagenetic zone (S.R. 2.0 t o 3.0).

-LJ

Dunoyer d e Segonzac and Abbas (1976) studied a d i a g e n e t i c sequence in t h e

Alps and found that as t h e c r y s t a l l i n i t y index decreased from 7 t o 3 t h e r e w a s

84
an i n c r e a s e i n a l b i t e , c h l o r i t e (5 t o 50 percent) and paragonite.

Chemical

analyses (66) show a l a r g e v a r i a t i o n f o r a given degree of metamorphism.

hj

Average

values i n d i c a t e an increase of t o t a l l a y e r charge from 0.695 i n t h e zone of

diagenesis t o 0.735 i n t h e anchizone t o 0.76 i n t h e epizone.

The d i f f e r e n c e s
a

are s m a l l and, i n view of t h e l a r g e v a r i a t i o n s within zones, of questionable

significance.

The average d a t a f u r t h e r i n d i c a t e t h a t with increasing m e t a -

morphism t h e r e is a s l i g h t i n c r e a s e i n t e t r a h e d r a l A 1 and octahedral Mg and a

decrease i n octahedral Fe.

K increases from 0.66 t o 0.71.

p r i s i n g t h a t t h e chemical d i f f e r e n c e s are so small.

It is s o m e w h a t sur-

There appears t o be an

i n c r e a s e i n t h e octahedral Al/Fei-Mg r a t i o with increasing metamorphism but t h e

d a t a were n o t p l o t t e d and i t i s not clear whether such a trend exists.

Trace element analyses of t h e e2 p f r a c t i o n of t h e s e same samples (Besnus

e t al., 1976) show considerable scatter but, i n general, G a , T i , Co, C r , B a ,
c

Sn, and Pb i n c r e a s e and S i , Fe, and Cu decrease as t h e degree of metamorphism

increases.
Hydrothermal experiments by Smykatz-Kloss and Althaus (1974) confirmed t h a t

" c r y s t a l l i n i t y " increased with increasing temperature; however, they were unable
t o e s t a b l i s h any a b s o l u t e r e l a t i o n between temperature and c r y s t a l l i n i t y and
suggested that t h e c r y s t a l l i n i t y index should be applied very cautiously.

It

should a l s o be mentioned that t h e r e s u l t s of hydrothermal experiments should be

applied w i t h caution.

G i l l et al. (1977) found that c r y s t a l l i n i t y changes were

c o n t r o l l e d t o some e x t e n t by lithology.

Sandstones were t h e most s u s c e p t i b l e

t o change, s i l t s t o n e s less so, and a r g i l l a c e o u s rock t h e least.

Though t h e c r y s t a l l i n i t y index, sharpness r a t i o , assymetry r a t i o , and
E

(002)/(001) r a t i o i n general measure t h e relative temperature t o which t h e 231

c l a y has been exposed, t h e reason f o r t h e peak modifications i s not w e l l understood.

The most s i g n i f i c a n t variable would appear t o be t h e g r a i n s i z e x-rayed

u-

85

bi
IC

and t h e amount andLtype of i n t e r s t r a t i f i c a t i o n .

These v a r i o u s measurements

probably should n o t be applied t o mixed-layer c l a y s containing more than 10

t o 20 percent expandkd layers.

The peak width and shape are s t r o n g l y i n f l u -

enced by t h e r e g u l a r i t y of t h e i n t e r l a y e r i n g and by v a r i a t i o n s i n t h e types of

nonexpanded ( i l l i t e and c h l o r i t e ) and expanded. (montmorillonite and vermiculite)
layers.

A t more advanced s t a g e s of diagenesis t h e s e measurements t o a l a r g e

e x t e n t reflect t h e relative amount of coarse (10 A l a y e r s ) and f i n e (mixedcompletely collapsed

s t r i c t measure

I l l i t e i n Sandstones
Authigenie i l l i t e commonly forms i n porous sandstones during b u r i a l .

In

some i n s t a n c e s i t appears t h a t t h e i l l i t e is probably formed a t temperatures

lower than those a t which i t i s formed i n s h a l e s

These authigenic c l a y min-

erals commonly decrease t h e pOr6Sity and permeability of t h e sandstones.

P

M i l l o t (1970) observed k a o l i n i t e a l t e r i n g ' t o i l l i t e i n t h e Cambrian sands t o n e s of Algeria

I n equivalent age sandstones from t h e same area, Triplehorn

(1967) found authigenic IM i l l i t e at depths of 2,873 t o 3,070 m.

In the shallow

buried,Upper Carboniferbus sandstones of northern Germany (Fiichtbauer, 1967),

t h e d e t r i t a l f e l d s p a r has 'been a l t e r e d t o k a o l i n i t e ; a t depths on t h e order

of 6,000 m t h e f e l d s p a r i s s e r i c i t i z

It i s suggested t h a t a n a c i d environ-

ment i s created by t h e release of CO

humic a c i d s during t h e e a r l y s t a g e s

of c o a l i f i c a t i o n .

During t h e second s t a g e of c o a l i f $ c a t i o n methane i s released,

of

r a l s t o form and r e p l a c e a

86
Wilson and Pittman (1977), i n t h e i r review of t h e l i t e r a t u r e on t h e oc-

C'

currence of authigenic c l a y minerals i n sandstones, show a number of scanning

e l e c t r o n micrographs of authigenic i l l i t e .
f l a k e s with l a t h - l i k e projections.

I l l i t e g e n e r a l l y occurs as i r r e g u l a r

Occasionally-the long l a t h - l i k e p r o j e c t i o n s

are curled and up t o 30 l.un long.

Paragonite
Paragonite i s a common mineral i n highly aluminous p e l i t i c s c h i s t s of lowto-medium grade of metamorphism (Zen and Albee, 1964; Guidotti, 1968).

It i s

most common i n medium grades of metamorphism and i s r e l a t e d t o a relative enrichment i n A1203 and/or NaA102 (Guidotti, 1968).

Winkler (1976) states that

paragonite makes i t s f i r s t appearance a t very-low-grade

(2000 t o 40OOC).

metamorphic conditions

Frey (1970, 1974) described t h e d i s t r i b u t i o n of paragonite

i n anchizone rocks of t h e Alps and suggested t h e following o r i g i n .

illite-montmorillonite
paragonite-phengite

-+

-+

regular mixed-layer mica-montmorillonite

paragonite.

Mixed-layer
-+

mixed-layer

I n t h e lower Paleozoic s h a l e s of t h e southern

Appalachian, I have found paragonite i n anchizone s h a l e s exposed t o high press u r e s ( f a u l t zones), but not i n those exposed t o high temperatures (deep b u r i a l ) .
The (002) spacings of muscovite and paragonite are a f f e c t e d by t h e K/Na
ratio.

Zen and Albee (1964) found t h a t t h e (002) spacing of both minerals

c l o s e l y r e f l e c t s t h e metamorphic grade.

I n rocks from t h e b i o t i t e and c h l o r i t e

zone, paragonite has t h e smallest spacings and muscovite t h e l a r g e s t spacings.

Spacings approach each other as t h e metamorphic grade increases.
Feldspar
z

Weaver and Wampler (1970) found that i n t h e Gulf Coast T e r t i a r y t h e Kf eldspar/Na-f eldspar r a t i o decreased with depth.

Hower e t al. (1976) reported

a decrease i n K-feldspar i n sediments from t h e same general area.

It i s

i,

87

u
3

apparent t h a t t h e K-feldspar

i s being destroyed as t h e K i s used t o convert

montmorillonite l a y e r s t o i l l i t i c layers.
of Na-feldspar increases.

It is not known whether t h e amount

Though secondary o r t h o c l a s e is abundant i n some

sediments (Mzller, 1967; Fairbridge, 1967) much of i t appears t o have formed

'6

from volcanic material a t a r e l a t i v e l y low temperature.

Some s t u d i e s of metamorphosed a r g i l l a c e o u s rocks (Weaver, 1961; Dunoyer
d e Segonzac and Abbas, 1976) have shown that Na-feldspar can be more abundant
than K-feldspar,

and Winkler (1976) notes that p h y l l i t e s may c o n t a i n as much

as 20 percent a l b i t e .
The paragenesis of N a and K f e l d s p a r i n t h e temperature range of 1000 t o
4OO0C is bound t o be complex but t h e general trend appears t o favor a n i n c r e a s e

Na-f eldspar/K-feldspar r a t i o .

88
KAOLINITE

Shales
There i s l i t t l e question that k a o l i n i t e i n s h a l e s . d i s a p p e a r s during deep
E

b u r i a l , but t h e r e i s l i t t l e f i r m information on what happens t o i t

and temperature a t which it disappears vary widely and t h e f a c t o r s which d e t e r mine a t what temperature i t i s destroyed o r transformed are n o t w e l l known.
A review by Dunoyer de Segonzac (1970) i n d i c a t e s t h a t t k a o l i n i t e i n s h a l e s

disappears a t temperatures ranging from 80 t o 190OC.

The p e r s i s t e n c e of b o -

l i n i t e t o a temperature of 180C a t P i e r r e f e u he ascribed t o a very low rock

porosity and t h e r e l a t i v e l y young age (Oligocene) of t h e formation.
Paleozoic of t h e Polignac Basin, k a o l i n i t e p e r s i s t s t o a temperature of a t
least 120OC.

This he believed w a s due t o a high organic content.

The p e r s i s t -

ence of k a o l i n i t e up t o a temperature of 190C i n t h e Salton Trough geothermal

area might a l s o be due t o t h e young age of t h e sediments.

k a o l i n i t e starts t o decrease i n abundance a t 165uC.

I n t h e l a t t e r case

I n t h e Cretaceous Logbaba

s e c t i o n k a o l i n i t e starts t o decrease a t 70C and i s gone by 90C; however t h e

l o s s of k a o l i n i t e coincides with a formation boundary and may never have been
present i n t h e underlying section.
I n t h e Oligocene of t h e Upper Rhine Graben, k a o l i n i t e i s present t o t o t a l
depth i n a w e l l with a bottom h o l e temperature of 169C (Doebl e t al., 1974).
I n Oligocene sediments of t h e Gulf Coast (Hower e t al., 1976), k a o l i n i t e cont e n t decreases abruptly a t 90C and then remains constant t o 174C ( t o t a l depth).

I n a study of Carboniferous Ycaolinite-coal-claystones"

of t h e Ruhr d i s -

t r i c t , Eckhardt (1965) found t h a t t h e b-axis d i s o r d e r of k a o l i n i t e decreased

with a n increasing temperature (increased c o a l rank).

A t temperatures less

89

LJ
4

than 130C t h e r e w a s l i t t l e change i n t h e c r y s t a l l i n i t y of t h e k a o l i n i t e ( i n

claystones).

N o b-axis d i s o r d e r w a s found i n k a o l i n i t e exposed t o temperatures

above 200OC.

I n t h e Low Pennsylvanian-Upper Mississippian Springer shales of

Oklahoma, k a o l i n i t e p e r s i s t s t o a temperature of a t least 2200C (Weaver and

U
'

Beck, 1971, and Hood e t al., 1975).

The k a o l i n i t e content starts t o decrease

a t a temperature of approximately 180C.

Kossovskaya e t al. (1964) reported t h a t only c h l o r i t e and i l l i t e a r e

present i n t h e f l o o r s of semianthracite c o a l seams.
i s lower rank, k a o l i n i t e i s present.

I n areas where t h e c o a l

I n Queensland, A u s t r a l i a , k a o l i n i t e is

present i n Permian t o n s t e i n s associated with medium-volatile bituminous c o a l

(Kisch, 1966 b),

Demaison (1974) has shown t h a t equivalent rank Permian c o a l s

i n A u s t r a l i a have been exposed t o maximum temperatures of 130)C t o 155OC.

Semianthracite c o a l s of equivalent age contain only c h l o r i t e and i l l i t e .

The

temperature f o r t h e formation of c o a l s of t h i s rank c o a l is approximately

2OO0C (Demaison, 1974).

K, Mg, and/or Fe must be present t o convert k a o l i n i t e

t o i l l i t e and c h l o r i t e .

The source of t h e i o n s i s not known.

The presence

of k a o l i n i t e on t h e shallow f l a n k s of a basin does n o t mean i t was once present

i n t h e c e n t r a l , more deeply buried p o r t i o n s of t h e basin.
sylvanian underclays of t h e Mid-Continent-Appalachian

A study of Penn-

area (Schultz, 1958)

e s t a b l i s h e d t h a t t h e r e w a s a r e g i o n a l v a r i a t i o n i n t h e c l a y mineral s u i t e ,
with k a o l i n i t e being more abundant i n t h e s h e l f underclays than i n those i n
t h e geosyncline; however, t h i s p a t t e r n could be due t o v a r i a t i o n s i n b u r i a l
\

depth.
I n a study of r e g i o n a l l y metamorphosed s h a l e s i n t h e Quachita Mountains,

Weaver (1960) found that k a o l i n i t e w a s destroyed before t h e mixed-layer illite-montmorillonite was completely converted t o i l l i t e .

;w

90

LJ

With increased depth and temperature, k a o l i n i t e i n s h a l e s i s commonly

observed t o decrease and c h l o r i t e t o increase.

It i s f r e q u e n t l y suggested

t h a t t h i s p a t t e r n i n d i c a t e s that k a o l i n i t e alters t o c h l o r i t e .
d i r e c t evidence t o i n d i c a t e t h a t t h i s transformation occurs.

There i s no

Weaver and Beck

(1971) suggested that t h e A 1 from t h e k a o l i n i t e may be incorporated i n montm o r i l l o n i t e l a y e r s i n mixed-layer illite-montmorillonite

t o form l a y e r s of

dioctahedral c h l o r i t e .
G r i m (1953) and Weaver (1959) found t h a t k a o l i n i t e w a s less abundant i n

o l d e r shales than i n younger (Cenozoic and Mesozoic) ones.

A similar s i t u -

a t i o n apparently occurs i n Europe (Dunoyer d e Segonzac, 1970, and Stark, 1968)

and i n Russia (Vinogradov and Ronov, 1956; Kossovskaya and Shutov, 1970).
suggested t h a t k a o l i n i t e w a s destroyed during b u r i a l .

Grim

Weaver (1960) suggested

that t h e i n c r e a s e i n k a o l i n i t e w a s due, i n p a r t , t o t h e development of land

p l a n t s and t h e c r e a t i o n of more a c i d conditions i n more r e c e n t times.

Studies i n o t h e r areas i n d i c a t e that k a o l i n i t e i s abundant i n t h e Devonian
of t h e Param Basin of Uraguay (Sanford and Lange, 1960) and i n t h e Cambrian
t o Carboniferous shales of North Africa (Dunoyer d e Segonzac, 1969).

I n Africa

t h e present maximum depth of b u r i a l of t h e Paleozoic sediments i s 3,000 m and

present maximum w e l l

temperatures are less than 120C.

These d a t a suggest

t h a t k a o l i n i t e was probably as abundant i n t h e Paleozoic (but because of contin e n t a l d r i f t i t formed i n d i f f e r e n t areas) as i n younger sediments, and that
i n much of North America, Europe, and Russia many of t h e Paleozoic sediments
have been exposed t o temperatures high enough ( g r e a t e r than 12OoC) t o d e s t r o y
the kaolinite.
T

Sandstones
I n interbedded s h a l e s and sandstones t h e sandstone u n i t s commonly c o n t a i n
more k a o l i n i t e than t h e surrounding shales.

This i s t h e case even when sand

91

W
i

l a y e r s are only 1 mm t h i c k (Weaver, 1967).

Most s t u d i e s i n d i c a t e that t h e

k a o l i n i t e w a s formed during shallow b u r i a l by a c i d waters t h a t formed from

organic material.
linite.

The a c i d a l t e r e d f e l d s p a r o r o t h e r c l a y minerals t o kao-

Bucke and Mankin (1971) reported a similar r e l a t i o n i n Desmoinesian

sand-shale p a i r s .

They noted t h a t i n a d d i t i o n t o organic material (low pH)

and f e l d s p a r as a source of S i and A l , it w a s necessary t o have degraded il-

l i t e t o adsorb potassium released from K-feldspar.

This l a t t e r requirement

is necessary only i f t h e movement of water i s r e s t r i c t e d .

There are many examples of t h e formation of k a o l i n i t e i n sandstones a f t e r
b u r i a l ; some examples from t h e United S t a t e s are described by Glass (1958),

Weaver (1967), and Wilson and Pittman (1977).

I n salt-water-bearing

Cambrian sandstones from t h e Sahara, Kulbicki and

M i l l o t (1961) found that k a o l i n i t e a l t e r e d t o i l l i t e .

i

F k h t b a u e r (1967) found authigenic well-crystallized

J u r a s s i c sandstones of Germany.
increasing c l a y content.
kaolinite.
ment.

kaolinite i n clean

The degree of c r y s t a l l i n i t y decreases with

The enclosing s h a l e s contain poorly c r y s t a l l i z e d

Some of t h e k a o l i n i t e w a s formed from f e l d s p a r i n a n a c i d environ-

The a c i d environment was created by C02 released during t h e e a r l y s t a g e s

of c o a l i f i c a t i o n . With depth, k a o l i n i t e i s believed to be converted t o c h l o r i t e .

Silica i s l i b e r a t e d t o form quartz overgrowths.

I n t h e Cretaceous of Alberta,

Ghent and Miller (1974) found that i n quartz-rich sandstones authigenic kaolin-

i t e formed later than q u a r t z cement.

I n feldspar-rich sandstones i t w a s asso-

c i a t e d with authigen5c c h l o r i t e , a l c i t e , and quartz.

Sarkisyan (1972) reported

that when pore waters are a c i d , regeneration of d e t r i t a l k a o l i n i t e and kaolinia'

z a t i o n of c l a y cements occur a t depths of 1,000 t o 2,000 m.

A t depths of 2,000

t o 3,000 m k a o l i n i t e can form from Si02 ( d i s s o l u t i o n of quartz) and A1203 (dis-

+W

s o l u t i o n of feldspar).

92
Shutov e t a l . (1970) reviewed t h e Russian s t u d i e s and reported that during
t r a n s p o r t a t i o n k a o l i n i t e becomes disordered.

With b u r i a l t h e r e i s a gradual

transformation of k a o l i n i t e t o d i c k i t e through t h e s t a g e of mixed-layer growths.

During deep b u r i a l , v e i n s of d i c k i t e are formed.

Under strong stress condi-

t i o n s , d i c k i t e is transformed t o n a c r i t e .
I n t h e Cretaceous sandstones of t h e Cameroon, d i c k i t e i s
temperature range of 70C t o 90C (Dunoyer de Segonzac, 1969).

formed i n t h e
Though "ele-

vated" o r d i a g e n e t i c temperatures are required t o produce d i c k i t e , t h e tempera t u r e of formation appears t o vary i n response t o varying chemical and physical
conditions.
I n a study of porous Pennsylvanian carbonate rocks of Kansas, Schroeder
and Hayes (1968) found t h a t d i c k i t e had been deposited from w a t e r s heated by
T e r t i a r y i n t r u s i v e igneous rocks.

A t a d i s t a n c e of t e n s of m i l e s from t h e

i n t r u s i o n s , t h e water temperature had cooled s u f f i c i e n t l y t h a t well-crystallized kaolinite precipitated.

The c r y s t a l l i n i t y of both t h e d i c k i t e and kao-

l i n i t e is i n p a r t controlled by t h e p o r o s i t y and permeability of t h e limestone.

Poorly c r y s t a l l i z e d d i c k i t e and disordered k a o l i n i t e occur i n t h e smaller voids
i n t h e less porous rocks.

This i s believed t o i n d i c a t e t h a t t h e w a t e r moving

through t h e r e s t r i c t e d paths cooled more than t h a t i n t h e more porous rocks.

These l a t e r a l changes i n t h e k a o l i n minerals are similar t o those observed
i n t h i c k vertical sections.
Kossovskaya and Shutov (1963) reported t h a t i n quartz-kaolinite sandstones
t h e k a o l i n i t e i s converted t o d i c k i t e when t h e pressure-temperature reaches
t h e s t a g e of deep-seated epigenesis, and t o p y r o p h y l l i t e a t t h e metagenesis
s t a g e (anchizone).

The pH is a c i d t o n e u t r a l .

ences t h e transformation temperature.

They suggest t h a t time i n f l u -

Dickite w a s observed i n lower Paleozoic

rocks a t 1,000-1,500 m and i n Mesozoic rocks a t 2,500 m.

c
1

93

bi

Winkler (1976) reported that in rocks composed largely of kaolinite and

quartz (and containing only minor amounts of K and Mg) the kaolinite can per-

8~

sist to temperatures in the range of 325O to 375OC. At higher temperatures

it can be converted to pyrophyllite.

The temperature of transformation de-

creases as the H 0 pressure decreases. When kaolinite occurs as a minor con2

stituent in shales (less than 30-50 percent of the clay suite), it is usually
destroyed or converted to some mineral other than pyrophyllite at an appreciably lower temperature.
In addition to massive pyrophyllite, solutions can be mobilized and pyrophyllite deposited in fissures produced during dynamometamorphism (Anton, 1975).
Pyrophyllite is abundant in shallow buried (deeper than 1500 m) Devonian
and Silurian sediments of the Sahara where it replaces mica, kaolinite, and
quartz. Associated minerals are calcite, dolomite, halite, and gypsum (Dunoyer
i

de Segonzac, 1969).

The associated mineralogy would appear to be a factor in

the low-temperature formation of pyrophyllite.

Kubler (1966 b) and Kisch (1974) show pyrophyllite to be present in the
anchizone and early metamorphic stages (illite crystallinity 7.5 to 2.0), which
probably indicates a minimum temperature of formation of approximately 2000C.
Frey (1970) found pyrophyllite in sediments which had been exposed to a maximum temperature of about 200C.
Experimental
Henley (1959) established the stability ields of kaolinite, pyrophyllite,

mica, and K-feldspar in terms of temperature and {K }/H 1- If the K concenB

tration and pH are sufficiently high, kaolinite can convert to illite at temperatures encountered at moderate depth.

Such a transformation occurs in porous

rock but does not appear to occur in shales.

lcepi

II
,

94
I n a n i n v e s t i g a t i o n of t h e a l t e r a t i o n of c l a y minerals under hydrothermal
conditions, Frank-Kamenetzky et a l . (1971) found t h a t i n t h e presence of KC1,

t
*

k a o l i n i t e f i r s t i s converted t o montmorillonite and disordered k a o l i n i t e

(~225OC)and then t o a K-hydromica a t 258C.

K-hydromica is t h e only phase

present a t a temperature higher than 400OC.

I n t h e presence of N a C l t h e se-

quence i s similar, except Na-hydromica develops and minor amounts of montmorill o n i t e p e r s i s t t o a temperature of 500OC.
p e r s i s t s t o 375OC.

I n t h e presence of MgC12, k a o l i n i t e

I n t h e absence of quartz and i n t h e presence of K and N a ,

k a o l i n i t e is converted t o micaceous minerals.

Laboratory s t u d i e s by Lagache

e t al. (1963) e s t a b l i s h e d t h a t i l l i t e alters t o k a o l i n i t e a t r e l a t i v e l y low

temperatures (<200"C) i n t h e presence of GO
2'

K a o l i n i t e i n Gulf Coast muds

w a s destroyed a t 100C when the mud w a s heated i n r e a c t o r bombs (Hiltabrand

e t al., 1973).

The sediment-seawater r a t i o w a s 1:5, which does not d u p l i c a t e

n a t u r a l conditions.
I n nature, k a o l i n i t e may be destroyed or modified a t temperatures as low

as 70C o r may p e r s i s t t o 375C.

The temperature a t which it i s destroyed o r

transformed depends on t h e pH, chemistry, and porosity.

The temperature a t

which changes occur appears t o decrease as pH and/or p o r o s i t y increase.

In

porous rocks containing a c i d water t h e c r y s t a l l i n i t y of k a o l i n i t e i n c r e a s e s

with increasing temperature, t h e k a o l i n i t e eventually being transformed t o
dickite.

It i s not clear whether t h e formation of p y r o p h y l l i t e is n e c e s s a r i l y

preceded by t h i s sequence of transformation.

When t h e s o l u t i o n s are a l k a l i n e , t h e k a o l i n i t e is destroyed; i f K i s
abundant, i t can be converted t o i l l i t e .
I n shales, k a o l i n i t e disappears over a wide temperature range, approximately 70" t o more than 20OOC.

The temperature a t which i t i s destroyed i s

95

u
+'

i n p a r t dependent on t h e l e n g t h of time i t is exposed t o t h e s e temperatures.

The chemistry of t h e associated c l a y minerals and organic content (pH) are
also factors.
i n shales.

It is not d e f i n i t e l y e s t a b l i s h e d what happens t o t h e k a o l i n i t e

I n a l l likelihood t h e r e l e a s e d A 1 and S i are reorganized t o form

l a y e r s of d i o c t a h e d r a l c h l o r i t e , o r , where K i s abundant, perhaps i l l i t e .

In

s i t u a t i o n s where k a o l i n i t e i s e s s e n t i a l l y t h e only c l a y mineral present, t h e

amount of b-axis d i s o r d e r decreases i n t h e temperature range of 130 t o 200OC.
It i s n o t known i f a t higher temperatures t h e k a o l i n i t e i s transformed t o dic-

kite.

This appears u n l i k e l y because d i c k i t e is rare i n shales.

Where kaolin-

i t e i s abundant, i t can be a l t e r e d t o p y r o p h y l l i t e a t temperatures as low as

2OO0C (upper p o r t i o n of anchizone).

96
CHLORITE

hojl
f

L e s s i s known about t h e c h l o r i t e minerals i n s h a l e s than about any o t h e r

type of c l a y mineral.
dominant mineral.

C h l o r i t e is present i n most s h a l e s but i s seldom t h e

Thus, i t i s d i f f i c u l t t o o b t a i n d i r e c t chemical analyses or

t o determine t h e polytype.

Most of t h e chemical information i s obtained by

x-ray a n a l y s i s (Brindley, 1961).

However, t h e r e is considerable information

a v a i l a b l e about metamorphic c h l o r i t e s and c h l o r i t e s i n sandstones, limestones,

and evaporites, where c h l o r i t e i s o f t e n t h e dominant c l a y mineral.
Polytypes and Composition
The s t r u c t u r a l v a r i a t i o n s of t h e c h l o r i t e s have been discussed by Brindley
(1961), Brown and Bailey (1962 and 1963), Shirozu and Bailey (1965), L i s t e r
and Bailey (1967), and Eggleston and Bailey (1967).

Taking i n t o account t h e

bonding r e s t r i c t i o n s imposed by t h e superposition of t h e 2 : l l a y e r s and t h e

hydroxide s h e e t s of i d e a l hexagonal geometry, Brown and Bailey (1962) showed
t h a t four d i f f e r e n t arrangements of t h e b r u c i t e sheet relative t o t h e i n i t i a l
2 : l l a y e r w e r e possible.

For each of t h e four c h l o r i t e l a y e r types, t h e hexa-

gonal r i n g s i n t h e repeating 2:l l a y e r may be superimposed i n s i x d i f f e r e n t

orientations.

Six i d e a l systems with semirandom stacking are possible, two

( I b and I I a ) based on an orthorhombic-shaped

c e l l and four (Ia, I b , IIa, I I b )

based on a monoclinic-shaped cell.

Brown and Bailey (1962) examined 300 c h l o r i t e s from d i f f e r e n t l o c a l i t i e s
and found t h a t approximately 80 percent had t h e I I b s t r u c t u r e but found examples
of t h e orthorhombic I b , monoclinic Ib, and Ia s t r u c t u r a l types.

The r e l a t i v e

abundance of t h e polytypes w a s r e l a t e d t o s t r u c t u r a l s t a b i l i t y .

To some ex-

t e n t , composition influences t h e s t a b i l i t y of t h e c h l o r i t e s through i t s e f f e c t

97

u
i

on t h e c a t i o n charge and amount of d i s t o r t i o n of t h e hexagonal network caused

by s i z e adjustments.

Increasing t e t r a h e d r a l A 1 s u b s t i t u t i o n i s accompanied by

a n i n c r e a s e i n octahedral Fe t o maintain a reasonable degree of f i t between t h e

two types of l a y e r s .
'3

There i s considerable overlap i n t h e compositions of t h e various s t r u c t u r a l

polytypes.

The Ia and I b c h l o r i t e s have r e l a t i v e l y d i s t i n c t compositions, both

being low i n t e t r a h e d r a l A l .
The I I b c h l o r i t e i s t h e s t a b l e polytype i n normal chlorite-grade metamorphic rocks and i n medium- and high-temperature o r e deposits.

Brown and Bailey

suggest t h a t when s u f f i c i e n t energy i s a v a i l a b l e t h e most s t a b l e polytype (IIb)

w i l l form.

They found t h a t t h e orthohexagonal and monoclinic I b types were t h e

ones most l i k e l y t o be considered d i a g e n e t i c c h l o r i t e s .

with t h e lowest amount of t e t r a h e d r a l A l .
I

These are t h e c h l o r i t e s

The I b type r e a d i l y converts t o t h e

more s t a b l e I I b type during metamorphism.

Hayes (1970) confirmed t h a t t h e type I c h l o r i t e s are formed by d i a g e n e t i c
processes.

H e proposed t h e following d i a g e n e t i c s t a b i l i t y sequence:

ordered) t o I b (B = 90')

t o IIb.

Ibd (dis-

H e found t h a t t h e type I c h l o r i t e s occurred

l a r g e l y i n sandstone and limestones, where they f i l l e d o r l i n e d voids and replaced such minerals as f e l d s p a r , b i o t i t e , volcanic material, calcite, and
probably montmorillonite.

The s t u d i e s of Brown and Bailey (1962) and Hayes

(1970) i n d i c a t e t h a t t h e r e i s no s i g n i f i c a n t d i f f e r e n c e i n composition between

type I and I I b c h l o r i t e s .

Hayes (1970) found t h a t type I contained from 1.03

t o 1.65 t e t r a h e d r a l A 1 (per f o u r p o s i t i o n s ) .
t o 3.55 (per 6 p o s i t i o n s ) .

The r a t i o Fe

2+

Octahedral Fe2+ ranged from 0.36

/Fe2+

+ Mg

ranged from 0 t o approxi-

p"

mately 0.8 and averaged approximately 0.4.

contain more Mg than Fe.

any d e t a i l .

Thus, most c h l o r i t e s of both types

The source of t h e Mg and Fe was not considered i n

98

LJ

Velde (1977) r e p o r t s that i n rocks containing c h l o r i t e and phengite t h e

c h l o r i t e tends t o be 50 t o 100 percent more Fe-rich ( r e l a t i v e t o Mg) than t h e
phengite.

The higher t h e Fe content of t h e rock, t h e higher t h e Fe content

of t h e c h l o r i t e .
c

Bradley (1955) has suggested t h a t t h e s i l i c a - r i c h t e t r a h e d r a l s h e e t i s

more temperature s e n s i t i v e than t h e octahedral s h e e t and t h a t a t high temperat u r e s t h e t e t r a h e d r a l s h e e t has t h e p o t e n t i a l f o r more lateral extension than
Macrocrystals which have s t r u c t u r a l r e g u l a r i t y are formed

t h e octahedral sheet.
L

a t r e l a t i v e l y high temperatures and have a s t r a i n - f r e e f i t between sheets.

Such

macrocrystals would be put under s t r a i n upon r e v e r s i o n t o ordinary temperatures.

C h l o r i t e s with a r e l a t i v e l y high Fe content have a poor f i t between s h e e t s and
do n o t form c r y s t a l s as l a r g e as those with a more favorable composition.

They

e x h i b i t d i f f r a c t i o n e f f e c t s which could be considered as departures from t h e

ideal chlorite structure.

Bradley b e l i e v e s t h a t i n both cases t h e s t r a i n i s

d i s s i p a t e d by t h e formation of f a u l t s which form by t h e p e r i o d i c reversal of

groups of s i l i c a t e t r a h e d r a similar t o t h a t which occurs i n t h e palygorskite
structures.

This i r r e g u l a r d i s t r i b u t i o n of f a u l t s would tend t o d i f f u s e t h e

odd order x-ray r e f l e c t i o n s which a l t e r n a t e with t h e sharper even order reflections.

Foster (1962) calculated t h e s t r u c t u r a l formulas f o r 150 s e l e c t e d trioctahedral c h l o r i t e s .

These formulas i n d i c a t e t h a t t h e S i content ranges from

2.34 t o 3.45 per four t e t r a h e d r a l p o s i t i o n s , t h e d i s t r i b u t i o n being highly

skewed toward t h e higher S i values.

Most c h l o r i t e s tend t o have a much higher

t e t r a h e d r a l A 1 content than t h e 2:l clays.

5.46 t o 6.05.

Octahedral occupancy ranges from

R3+ octahedral occupancy ranges from approximately 10 t o 47

percent of t h e f i l l e d p o s i t i o n s with most of t h e values ranging from 15 t o

35 percent.

bi

99

6)
5

A c l a s s i f i c a t i o n of t h e c h l o r i t e s w a s devised by Foster (1962) based on

i o n i c replacement of A 1 by S i i n t h e t e t r a h e d r a l s h e e t and Mg by Fe2+ i n t h e

octahedral sheet.

The dividing l i n e s are a r b i t r a r y and imply no g e n e t i c sig-

n i f i c a n c e ; i n fact, they probably have some.

Y

Experimental hydrothermal s t u d i e s i n a p o r t i o n of t h e system MgO

Si02

- H20

- A1203 -

(Nelson and Roy, 1958) showed that a complete sequence of 14 A chlor-

i t e s could be synthesized ranging i n composition from amesite ( Q 4 A 1 2 )

(Si2A12)

A c e r t a i n minimum
amount of R3+ s u b s t i t u t i o n is necessary i n order t o provide s u f f i c i e n t l a y e r
charge t o bind t h e v a r i o u s l a y e r s .

The c h l o r i t e s t r u c t u r e i s not s t a b l e with

more than one-third of t h e octahedral p o s i t i o n s f i l l e d with A l ; if more 41 i s

present, a three-phase assemblage i s produced, containing a c h l o r i t e of t h e

amesit e composition.
E

The same compositions, but a t lower temperatures (below 400-5OO0C), produce a 7 A s t r u c t u r e of t h e k a o l i n type.
z

materials s e p t e c h l o r i t e s .

Nelson and Roy (1958) c a l l e d t h e s e

It w a s not established whether t h e 7 A phase w a s

metastable o r not.
R e l a t i v e l y few d i o c t a h e d r a l c h l o r i t e s have been described but they may
I n order t o maintain electrical

be more abundant than p a s t s t u d i e s i n d i c a t e .

n e u t r a l i t y , t h e octahedral s h e e t s must contain more than 4 A 1 per Olo(OH)s.

1

The excess o c t a h e d r a l charge should equal t h e amount of negative t e t r a h e d r a l

charge i f no exchange c a t i o n s are present.
from 0.60 to 1.30.
f

Reported t e t r a h e d r a l charges range

These charges are f u l l y s a t i s f i e d by excess octahedral

occupation i n hydrothermal samples but not i n t h e sedimentary samples.

The

sedimentary specimens have a much higher t e t r a h e d r a l A 1 content (1.20 and 1.30)

than t h e hydrothermal clay, which would suggest t h a t t h e b a s i c 2:l l a y e r s were

+w

100
not o r i g i n a l l y s t r i p p e d i l l i t e o r montmorillonite.

It may be t h a t t h e s t a r t i n g

material w a s s t r i p p e d b i o t i t e o r c h l o r i t e from which much of t h e octahedral Mg

b.l
*

and Fe w a s removed and, i n p a r t , replaced by A 1 (Weaver and P o l l a r d , 1973).

Mode of Formation

C h l o r i t e forms under a wide v a r i e t y of conditions and temperatures.

Present

d a t a i n d i c a t e l i t t l e r e l a t i o n between composition and temperatures, but some

r e l a t i o n between composition and t h e environmental conditions i n which authigenic c h l o r i t e forms.
Soils
C h l o r i t e s weather e a s i l y and are rare i n s o i l s except i n r e l a t i v e l y cold
climates.

B a l l (1966) has described a c h l o r i t e - r i c h s o i l from t h e mountainous

region of North Wales.

The c h l o r i t e ( I I b , Hayes, 1970) i s r e s i d u a l and con-

centrated by t h e weathering of c h l o r i t i c t u f f s .
1.0 t o 1.7.

The Fe2+/Fe2+

+ Mg

Tetrahedral A l ranges from

r a t i o ranges fromb.17 t o 0.53, with 20 of

t h e 26 samples having value less than 0.34.

These "volcanic" c h l o r i t e s have

a higher Mg content than most of those found i n sedimentary rocks.

I n s o i l s , smectites and v e r m i c u l i t e are frequently p a r t i a l l y "chloritized"
by t h e p r e c i p i t a t i o n of hydroxy-Al,
( f o r review see Rich, 1968).

Fe, o r Mg between t h e expanded l a y e r s

"Chloritization"

hydroxy material occurs as i s l a n d s .

i s seldom complete and t h e

The o r i g i n a l c l a y i s most o f t e n diocta-

hedral and hydroxy-AI. i s t h e most common i n t e r l a y e r material.

AI. and Fe hy-

droxides are p r e c i p i t a t e d under a c i d conditions and Mg hydroxide under b a s i c

conditions.

Weaver and Beck (1977) have observed Fe-rich c h l o r i t e forming

from k a o l i n i t e and Fe oxides i n t h e s o i l s of t h e southeast U.S.

101

Marine
Under marine conditions some hydroxy-Mg p r e c i p i t a t e s between montmoril-

r'

l o n i t e l a y e r s causing p a r t i a l c h l o r i t i z a t i o n (Grim and Johns, 1954).

Rex

(1967) d e s c r i b e s hydroxy-Fe p r e c i p i t a t i n g between montmorillonite l a y e r s i n

P a c i f i c Ocean clays.
B o n a t t i and Arrhenius (1965) found Fe c h l o r i t e (Ibd, Hayes, 1970) forming
i n t h e P a c i f i c Ocean from Fe-A1 oxide hydrate coatings ( d e s e r t varnish) on
s i l t g r a i n s , and Swindale and Fan (1967) described c h l o r i t e forming from sandand s i l t - s i z e g i b b g i t e g r a i n s off t h e c o a s t of H a w a i i .

Conversely, Berry and

Johns (1966) and Heath (1969) found t h a t d e t r i t a l c h l o r i t e w a s being degraded

i n t h e bottom muds of t h e A t l a n t i c . a n d P a c i f i c Oceans.

Studies of sediments

from t h e Mid-Atlantic r i d g e (Siever and Kastner, 1967, and Copeland e t al., 1971)
i n d i c a t e t h a t Fe c h l o r i t e s from t h e outcropping greenstones are slowly changed,
P

through contact with seawater, t o Mg c h l o r i t e .

It appears t h a t e i t h e r Fe o r

Mg c h l o r i t e s can form i n t h e marine environment.

Evaporites
Authigenic c h l o r i t e is commonly present i n s a l t y c l a y s associated with
s a l t d e p o s i t s (Fgchtbauer and Goldschmidt, 1959; Braitsch, 1971; Nelson, 1973),

but is r e l a t i v e l y rare i n t h e dolomites associated with t h e s e deposits.

c h l o r i t e s are reported t o be Mg-rich,

less than 0.1.

t y p i c a l l y having a Fe2+/Fe

+ Mg

These

ratio

Microprobe a n a l y s i s (80) of authigenic c h l o r i t e from t h e Si-

l u r i a n s a l t s of New York (Bodine and Standaert, 1977) shows they are a l s o &rich:
2

mQ.51 Fe2+0.23All,211 (Al.06si2.91) 010(om8

.
C h l o r i t e tends t o be predominant i n t h e s t r a n d l i n e d e p o s i t s of t h e Ger-

*u

man Zechstein d e p o s i t s (Braitsch, 1971).

I n a survey of e v a p o r i t e d e p o s i t s

102
of North America, Droste (1963) found t h a t c h l o r i t e and c o r r e n s i t e w e r e commonly present, though i l l i t e w a s t h e predominant c l a y i n most deposits.
l i t e i s present i n most evaporite deposits.

11-

Corrensite o r various forms of

mixed-layer chlorite-vermiculite and chlorite-montmorillonite is a common component of e v a p o r i t i c s a l t and s u l f a t e beds (Kubler, 1973).
Carbonates
C h l o r i t e and mixed-layer chlorite-montmorillonite are r e l a t i v e l y abundant
i n Paleozoic and Mesozoic carbonate rocks (Weaver and Beck, 1977).

These two

minerals are t h e most abundant c l a y minerals i n Lower Ordovician and Upper

Mississippian carbonate rocks extending over thousands of square kilometers
i n t h e e a s t e r n United S t a t e s .

Limited d a t a suggest t h e s e are mostly t i d a l

d e p o s i t s and t h e c h l o r i t i c material has a high Mg/Fe r a t i o (Weaver, 1961, and

Peterson, 1961).

Ephemeral hypersaline conditions are believed t o have existed

i n t h e t i d a l f l a t environments i n which t h e s e c l a y s formed (Weaver, 1961).

The d a t a from t h e e v a p o r i t e and carbonate rocks s t r o n g l y suggest that
Mg-rich c h l o r i t e s form under hypersaline conditions; however, i t is not known
whether a l l of t h e s e c h l o r i t i c c l a y s are authigenic o r whether some are formed

after b u r i a l .

C h l o r i t e s of similar composition are a l s o common i n metamorphic

rocks.
Ironstones
Fe-rich c l a y s are abundant i n many sedimentary i r o n d e p o s i t s (Berg, 1944;
Chilingar, 1956; Schoen, 1964; Hunter, 1970).

Most of t h e c l a y minerals are

t h e 7 A v a r i e t y (chamosite, s e p t e c h l o r i t e , g r e e n a l i t e , and c r o n s t e d t i t e ) , but

c h l o r i t e is a l s o present.

Schoen (1964) calculated from x-ray d a t a t h a t t h e

c h l o r i t e i n t h e Clinton ironstones had t h e following composition:

103

crs
3

The 2 : l l a y e r had more Fe than t h e hydroxide sheet.

Coexisting, primary 7 A

chamosite from which much of t h e c h l o r i t e formed has a similar composition.

Schoen f u r t h e r concluded t h a t t h e Fe/Mg r a t i o of t h e c h l o r i t e had increased

H e believed t h i s w a s caused by an i n c r e a s e i n Fe/Mg acti-

during diagenesis.

v i t y r a t i o i n t h e s o l u t i o n r a t h e r than by temperatures.

Sandstones
Nondetrital c h l o r i t e commonly occurs as pore f i l l i n g s and g r a i n c o a t i n g s
i n sandstones.

As most of t h i s c h l o r i t e appears t o have formed a f t e r b u r i a l ,

i t w i l l be discussed i n d e t a i l i n another section.

Shales
3-

There are few, i f any, chemical analyses of c h l o r i t e s i n shales.

X-ray

analyses by Weaver (Weaver and -Pollard, 1973) and Hayes (1970) i n d i c a t e that
t h e c h l o r i t e s i n Paleozoic s h a l e s t y p i c a l l y contain 1.0 t o 1.6 t e t r a h e d r a l A 1
and have an Fe

2+

/F

2+

+Mg r a t i o ranging from 0.25 t o 0.67.

The range of compo-

s i t i o n i s similar t o t h a t f o r metamorphic c h l o r i t e s except f o r those with e i t h e r

a very high Fe o r Mg content (Brown and Bailey, 1963).

It is l i k e l y t h a t most

of t h e c h l o r i t e s i n s h a l e s are d e t r i t a l metamorphic c h l o r i t e s .

This i s by no

means c e r t a i n , as i t is l i k e l y t h a t appreciable c h l o r i t e i s formed during t h e

transformation of montmorillonite to i l l i t e .

Diagenesis
Diagenetic c h l o r i t e forms i n n e a r l y a l l , i f not a l l , t h e major rock types
<

*W

during b u r i a l .

The composition i s q u i t e v a r i a b l e and appears t o be more depen-

dent on t h e composition of t h e s o l i d phase and t h e s o l u t i o n than on temperature.

104
Sandstone
The presence of d i a g e n e t i c c h l o r i t e i n sandstones has been described by
numerous people (reviewed by Weaver, 1967; Hayes, 1970; and Wilson and Pittman,
1977).

There has been some controversy as t o whether t h e c h l o r i t e - r i c h m a t r i x

1

i n graywacke w a s primary o r diagenetic.

Recent s t u d i e s (Lovell, 1972; Reimer,

1972; and Galloway, 1974) i n d i c a t e t h a t much of t h e matrix is formed by t h e

d i a g e n e t i c decomposition of unstable components.
The development of c h l o r i t e i n sandstones during diagenesis and metamorphism has been described by Kossovskaya and Shutov (1958 and 1963).

They p o i n t

out that t h e s t a b l e mineral assemblages formed during diagenesis and low-grade

metamorphism are dependent on t h e bulk composition of t h e o r i g i n a l rock.
minerals are necessary f o r the formation of c h l o r i t e .
f i r s t develops as a cement.

Femic

The c h l o r i t e (and i l l i t e )

With increasing depth, temperature, and lateral

stress, c h l o r i t e aggregates form.

A t t h e slate s t a g e of metamorphism, c h l o r i t e

has a perpendicular o r i e n t a t i o n and p e n e t r a t e s i n t o regenerated quartz and

f e l d s p a r grains.

I n slate, c h l o r i t e l e p i d o b l a s t s develop.

Segregation t a k e s

place both on t h e s u r f a c e bedding and along cleavage planes.

I n a study of T e r t i a r y sedimentary arc-related basins along t h e P a c i f i c
c o n t i n e n t a l margin, Galloway (1974) found t h a t a t depths g r e a t e r than 300 m
authigenic c h l o r i t e and montmorillonite formed as coatings around d e t r i t a l
grains.

With increasing depth (900 t o 3,000 m) and temperature, open pore

spaces are f i l l e d with authigenic z e o l i t e , c h l o r i t e , o r montmorillonite.

Vol-

canic rock fragments, plagioclase feldspar, and mafic heavy minerals were t h e
source material f o r t h e c l a y s and z e o l i t e s .

I n advanced s t a g e s of b u r i a l , re-

placement of f e l d s p a r and rock fragments by c h l o r i t e and o t h e r minerals occur,

and t h e matrix i s r e c r y s t a l l i z e d and p a r t i a l l y replaced by c h e r t and micas.

4.

105

W
i

Karpova (1969) found I b c h l o r i t e cement formed from volcanic fragments

i n c o n t i n e n t a l and d e l t a i c sandstones
of t h e Russian Platform.

from t h e Upper and Middle Carboniferous

With depth I I b c h l o r i t e becomes predominant.

more abundant i n I I b than i n t h e I b c h l o r i t e .

Mg i s

Sarkisyan (1972.) r e p o r t s t h a t

below a depth of 3,500 m c h l o r i t e cement forms i n sandstones, s i l t s t o n e s , and

s i l t y shales.
s i l t increases.

The c h l o r i t e content increases as t h e proportion of sand and

I n a Permian basin i n Russia, c o r r e n s i t e and Mg c h l o r i t e ( i n

lagoonal sediments.) and Fe-Mg c h l o r i t e ( i n marine sediments) are believed t o

have formed a f t e r b u r i a l i n both s h a l e s and sandstones (Kossovskaya, 1969).
Almon e t al. (1976) described t h e occurrence of authigenic c o r r e n s i t e i n
Upper Cretaceous v o l c a n i c l a s t i c d e l t a i c sands.
occurred i n t h e associated marine sands.

Authigenic montmorillonite

They suggested t h a t t h e c o r r e n s i t e

formed i n a hyposaline r a t h e r than a hypemaline environment.

I t i s of i n t e r e s t

6'

t o note t h a t t h e i r c o r r e n s i t e contains more Fe than Mg, whereas c o r r e n s i t e

associated with e v a p o r i t e d e p o s i t s i s Mg-rich.

The limited chemical d a t a indi-

cate t h a t c o r r e n s i t e s have a range of compositions and t h a t t h e composition

appears t o be a t least p a r t i a l l y r e l a t e d t o s a l i n i t y .
I n t h e Eocene sandstones of southwest Texas t h e disappearance of k a o l i n i t e

a t 150-200C is accompanied by an i n c r e a s e i n c h l o r i t e .
replaced by a n k e r i t e a t about 117-120C.

Calcite cement i s

K-feldspar i s destroyed a t a tempera-

t u r e i n t e r v a l of qetween 199"and 120C (Boles and Franks, 1979).

i.

From x-ray analyses of d i a g e n e t i c c h l o r i t e s , l a r g e l y from sandstones,

Hayes (1970) found t h a t I I b c h l o r i t e s ( d e t r i t a l ) tend t o have more Mg and Si

than type I c h l o r i t e s , which d e f i n i t e l y have higher Fe and A 1 contents.
t

However,

he concluded t h a t composition alone is unimportant i n determining t h e s t a b i l i t y

ranges of t h e d i f f x e n t polytypes.

Chemical composition is influenced by t h e

106
bulk composition of r e a c t a n t s i n t h e d i a g e n e t i c environments.

Hayes suggests

t h a t 150OC may be about t h e temperature a t which I b converts t o I I b c h l o r i t e .

Id
c

Wilson and Pittman (1977) noted t h a t t h e concentration of Fe i n secondary

c h l o r i t e s v a r i e d with morphology.

The r e l a t i v e concentrations of Fe were p l a t e s

and r o s e t t e s > honeycomb > cabbagehead.

I n t h e Cretaceous a r e n i t e s and . c a l c a r e n i t e s of northeastern Algeria, globu l a r 14 A c h l o r i t e s occur as s h e l l f i l l i n g s .

I t is believed that t h e s e p e l l e t s

o r i g i n a l l y formed as 7 A c h l o r i t e s and were converted t o 14 A c h l o r i t e when

exposed t o b u r i a l temperatures of 25C t o somewhat above 100C (Velde et al.,
1974).
Shales
Hower et al. (1976) observed i n a Gulf Coast T e r t i a r y w e l l t h a t an i n c r e a s e
i n c h l o r i t e coincided with an i n c r e a s e i n t h e i l l i t e l a y e r s i n t h e mixed-layer
illite-montmorillonite.

They b e l i e v e t h e c h l o r i t e i s a by-product of t h e trans-

formation of montmorillonite t o i l l i t e .
temperature of 700C.

C h l o r i t e i s f i r s t observed a t a w e l l

It increases t o a depth where t h e temperature i s l o P C ,

then remains constant t o t o t a l depth (174C).

A reexamination of t h e d a t a obtained by Weaver and Beck (1971) from a

study of a Gulf Coast Miocene s e c t i o n i n d i c a t e s t h a t a t a temperature of 8 0 3 C

t h e ~0.2pm f r a c t i o n contained a mixed-layer
Below t h i s depth-temperature,

crete c h l o r i t e .

illite-chlorite-montmorillonite.

t h e r e is a s l i g h t i n c r e a s e i n t h e amount of d i s -

I n t h e Pennsylvania Springer s h a l e s of Oklahoma, h e a t treat-

ments i n d i c a t e t h a t t h e c r y s t a l l i n i t y of c h l o r i t e i n c r e a s e s w i t h depth and t h a t

t h e amount of expanded l a y e r s (mixed-layer chlorite-vermiculite)

decreases with

depth (Weaver, 1958).

Fschtbauer and Goldschmidt (1963), Dunoyer d e Segonzac (1969), and o t h e r s
have observed t h a t i n thick sedimentary s e c t i o n s k a o l i n i t e decreases and

107

bd
mi

t r i o c t a h e d r a l c h l o r i t e i n c r e a s e s with depth and temperature, and they suggest

that k a o l i n i t e alters t o c h l o r i t e .

I n t h e J u r a s s i c s h a l e s of Lower Saxony,

Ffichtbauer (1967) found t h a t c h l o r i t e increased a t t h e expense of k a o l i n i t e

and suggested that S i w a s l i b e r a t e d t o form quartz cement i n sandstones.

In

t h e Upper Carboniferous sandstones b i o t i t e f l a k e s are c h l o r i t i z e d below 3400 m.

Weaver and Beck (1971) showed t h a t as k a o l i n i t e decreased with depth i n t h e

Springer s h a l e s a d i o c t a h e d r a l c h l o r i t e developed.

Minor amounts of k a o l i n i t e

p e r s i s t t o depths where t h e present temperature is near 220OC.

A t 22OOC only

d i o c t a h e d r a l c h l o r i t e i s present.
Sarkisyan (1972) reported t h a t i n t h e Caucasus c o r r e n s i t e (50 percent expanded l a y e r s ) c o e x i s t s with mixed-layer illite-montmorillonite
t o 30 percent expanded layers.

containing 25

This suggests t h a t t h e temperature t o which t h e

rocks were exposed w a s a t least 120'C.

I n t h e Lower and Middle Ordovician

shales and shaley limestones of Newfoundland, c o r r e n s i t e i s believed t o have

formed d i a g e n e t i c a l l y from volcanic d e t r i t u s (Suchecki e t al., 1977).
a s s o c i a t e d mixed-layer illite-montmorillonite
expanded l a y e r s .

The

contains only 1 0 t o 15 percent

T h i s suggests t h a t t h e temperature t o which t h e s e sediments

have been exposed i s i n t h e range of 170'to 220'C.

I n metamorphosed Alpine rocks c o r r e n s i t e is present i n rocks containing
well-crystallized

i l l i t e (Kubler, 1968).

The thermal s t a b i l i t y range of c o r r e n s i t e exceeds t h a t of illite-montmorill o n i t e and appears t o range from approximately 90C t o temperatures i n excess

of 2OO0C, perhaps as high as 300OC.

Suchecki e t al. (1977) suggest t h a t t h i s

i s due t o t h e t r i o c t a h e d r a l character of t h e chlorite-montmorillonite.

The

hydrogen bonds of t h e octahedral OH i o n s are oriented perpendicular t o t h e c l a y

l a y e r , allowing f o r g r e a t e r e l e c t r o s t a t i c repulsion between i n t e r l a y e r c a t i o n s

%id

and t h e layer.
4

,)

108

LJ

On t h e southwestern border of t h e Russian Platform (Karpova, 1969), I b

c h l o r i t e s occur i n t h e Upper and Middle Carboniferous sandstones.

Deeper i n

t h e s e c t i o n t h e I I b polytype i s present and contains more Mg than t h e I b type.

It i s not known whether t h e I I b polytype w a s formed from t h e I b polytype by

Mg-metasomatism o r a f t e r t h e I b polytype w a s dissolved.

I n f e l s i c t u f f s i n t h e Neogene of Japan ( I i j i m a and Utada, 1971, montm o r i l l o n i t e changes t o c o r r e n s i t e a t approximately 100C (analcime zone) which
i n t u r n a l t e r s t o c h l o r i t e a t approximately 120C ( a l b i t e zone).
Kossovskaya e t al. (1964) r e p o r t t h a t d i a g e n e t i c c h l o r i t e and i l l i t e are
abundant i n t h e f l o o r of semianthracite c o a l seams i n t h e Petchora Basin.

In

A u s t r a l i a , Kisch (1966b) reported t h e presence of abundant Fe- and Al-rich

diagenetic c h l o r i t e (along with mixed-layer illite-montmorillonite-chlorite)
i n t o n s t e i n s associated with c o a l of semianthracite rank (90-91.5 percent carbon).
The c h l o r i t e is believed t o form from k a o l i n i t e when Mg and Fe are present.

The

Fe is believed t o come from s i d e r i t e which through t h e loss of Fe i s converted

t o a n k e r i t e (Kisch, 1968 a).

When Mg and Fe are n o t present, t h e k a o l i n i t e

becomes b e t t e r c r y s t a l l i z e d o r converts t o d i c k i t e .

Semianthracite c o a l i s

believed t o have been subjected t o temperatures on t h e order of 20PC (Demaison,

1974).

A minor amount of c h l o r i t e i s present i n t o n s t e i n s associated with c o a l s

having 89 percent carbon (~150OC).

The presence of mixed-layer illite-mont-

m o r i l l o n i t e with (001) spacings ranging from 10.2 t o 12 A confirms t h a t t h e

rocks w e r e probably not exposed t o temperatures much g r e a t e r than 2O(PC, and
f u r t h e r demonstrates t h a t d i a g e n e t i c c h l o r i t e s form a t lower temperatures than
pure i l l i t e (100 percent 10 A l a y e r s ) .
Dunoyer d e Segonzac and Bernoulli (1976) observed t h a t i n t h e Upper T r i assic of t h e Southern Alps c h l o r i t e and c o r r e n s i t e are present i n t h e deeply

109

u
8
'

buried Generoso Basin but not i n t h e shallow buried sediments i n t h e Lugarro

Swell.

Only i l l i t e and c h l o r i t e are present i n t h e Austro-alpine maps.

Analysis of c h l o r i t e from metamorphic and igneous rocks (Albee, 1962)

shows t h a t t h e i r composition depends on t h e t o t a l composition of t h e rock and
minerals associated with it.

Thus, c h l o r i t e s with a high A 1 content are

u s u a l l y associated with high-A1 minerals (muscovite, margarite, s p i n e l , etc.).

C h l o r i t e s may have any proportion of Fe t o Mg.

The proportion depends on t h e

Fe/Mg r a t i o of t h e bulk rock and t h e n a t u r e of t h e other minerals among which

t h e Fe and Mg are p a r t i t i o n e d .
grades of metamorphic rocks.

I n general, c h l o r i t e s are more Mg-rich i n higher

This has been demonstrated by t h e experimental

s t u d i e s of Nelson and Roy (1958) which showed t h e maximum s t a b i l i t y temperature

of Mg-chlorite t o be higher than t h a t of Fe-chlorite.
The composition of c h l o r i t e formed from montmorillonite and i l l i t e during
diagenesis would presumably be determined by Fe and Mg content of t h e octahedral
s h e e t of t h e s e two clays.
rn

However, i t cannot be assumed t h a t t h e Fe and Mg

are released on t h e same proportion i n which they occur i n t h e octahedral sheet.

Data compiled by Weaver and Pollard (1973) showed that t h e r e is a negative
r e l a t i o n between K20 and Fe203 f o r both i l l i t e and mixed-layer illite-montmorill o n i t e ; MgO is not r e l a t e d t o K20.
h e d r a l s h e e t more e a s i l y than Mg.

t o be reduced t o Fe2+.

During diagenesis, octahedral Fe3+ tends

The d i o c t a h e d r a l c l a y s can accommodate only a r e l a t i v e l y

s m a l l amount (0.20 per OloOH2)

structure.

This suggests t h a t Fe may leave t h e octa-

of t h e l a r g e f e r r o u s ion and i t must leave t h e

Actually i t may help d i s r u p t t h e s t r u c t u r e and f a c i l i t a t e t h e dia-

genetic reactions.

Thus, c h l o r i t e s formed during diagenesis should have a l a r g e r

Fe/Mg r a t i o than t h e mixed-layer c l a y o r i l l i t e from which they were derived.

In t h e Karroo s h a l e s of South Africa c h l o r i t e is f i r s t encountered c l o s e

*u

t o t h e boundary between anchi- and epimetamorphism a t a suggested temperature

,'
.

I10
of 28OOC (Rowsell and Deswardt (1976).

The Fe and Mg were believed to have

been derived from illite during recrystallization. Some of the chlorite occurs as porphyroblasts, as veinlets, and intergrown with muscovite.

Crystal-

linity values range from 2.7 to 3.3.

Dunoyer de Segonzac and Abbas (1976) found that in a dolomite series in
the Alps the thermal stability of chlorite increased with increasing degree
of diagenesis and metamorphism. Thermal stability was measured with the following ratio:
I

Intensity 7 A, unheated
R - Intensity 7 A, heated

Chlorite can be formed in shales, sandstones and limestones at relatively

low temperatures.

Conversely, in the laboratory, many chlorites formed at low

temperatures can be destroyed at temperatures as low as 3000C when they are

heated in the absence of water.
K-Bentonites
A study of the K-bentonite beds of Sweden (Bystrom, 1957) indicates that
the content of chloritic material increases as the tectonic deformation of the
beds increases.

In the Appalachian region, K-bentonites commonly contain chlo-

rite or mixed-layer chlorite-montmorillonite. At least some of the chlorite

is dioctahedral (Weaver, 1959).

Chloritic material has not been reported in

the equivalent age K-bentonite beds from the mid-content. These data suggest
that the formation of chlorite is related to the depth of burial or temperatures.
However, in the Appalachians chlorite may be present in one K-bentonite bed
and not in another a few feet away in the same outcrop (Weaver, 1953).

Somec

thing other than temperature must be involved. A chemical analysis of one of

the chlorites from the Appalachian region indicates that it contains less than
2 percent Fe20g.

111

b+
i'

Hydrothermal

In the Salton Sea hydrothermal area, Muffler and White (1969) observed
that Mg-rich chlorite starts t o form at temperatures of 130" to 165C.

In

the Wairakei thermal area (Steiner, 1967), Fe-chlorite starts forming from
'*

montmorillonite at temperatures of less than 100C.

Eslinger and Savin (1973)

found that the chlorite stage was preceded by a corrensite stage. Corrensite
was observed at 112C (shallowest sample examined) and chlorite at 140C.
Chlorite and mixed-layer chlorite-montmorillonite are commonly formed in wall
rock altered by hydrothermal fluids or intrusions (Bundy and Murray, 1959;
Naboko and Berkhin, 1970; Sudo et al., 1957; Chen, 1972; Harvey and Beck,

1960; Blatter et al., 1973).

The chlorite is generally at the outer (cooler)

rim of the alteration halo.

In the low-grade metamorphic portion of the Oua-

chita System, thin veins of pure-Mg-rich chlorite are abundant (Weaver, 1961).
Kubler (1973) concluded that under normal diagenetic conditions corrensite
forms at temperatures of approximately 90" to 100C and persists to at least

150"C.

Hydrothermally altered pillow basalts from the Mid-Atlantic Ridge consist predominantly of chlorite-rich greenstones (Humphris and Thompson, 1978).
The chlorite MgO/FeO ratio is approximately one. Much of the Mg is obtained
-

Temperatures range from ambient bottom water temperatures to

from seawater.

a few hundred degrees centigrade.

Corrensite and swelling chlorite are present in the basaltic rocks of
the geothermal area on Reykjanes, Iceland, at temperatures ranging from 1500
z

to 280C.

At lower temperatures, only montmorillonite is present.

Normal

chlorite was found in one well in the temperature range of 22OOC to 29OOC.
Mixed-layer chlorite-smectite dominates at 200"to 23OOC (Thomasson and Kris-

LJ

'tannsdottir, 19j2).

112
ORGANIC MATERIAL
6

The s c i e n t i s t s studying c o a l have e s t a b l i s h e d a r e l a t i o n between c o a l

rank and temperature.

Following t h e s e e a r l y s t u d i e s , t h e petroleum s c i e n t i s t s

have established that t h e organic material i n s h a l e s w a s temperature sensit i v e and t h a t t h e type of hydrocarbon generated w a s dependent on temperature.
Recent s t u d i e s have demonstrated that time i s as ,important as temperature.
The book "Stach's Textbook of Coal Petrology" (Stach e t al., 1975) prov i d e s a n up-to-date

review of c o a l i f i c a t i o n .

Much of t h e f i r s t p a r t of t h i s

discussion i s taken from t h e i r review.

C o a l i f i c a t i o n Process
The development from peat through l i g n i t e , subbiwminous coals, and bituminous c o a l s t o a n t h r a c i t e s and meta-antracites is termed c o a l i f i c a t i o n .

The

chemical and physical changes t h a t t a k e p l a c e during c o a l i f i c a t i o n i n d i c a t e

t h a t only t h e processes t h a t operate up through t h e s t a g e of l i g n i t e ( s o f t
brown coal) can be classed as diagenetic.

The a l t e r a t i o n s t h a t occur from

t h e beginning of t h e subbituminous (hard brown coal) s t a g e are so severe t h a t

they are regarded as metamorphism.
Coals r e a c t so much more s e n s i t i v e l y t o temperature than do minerals
that t h e temperature, time, and pressure necessary f o r t h e formation of bitu-

minous c o a l s cause only minor d i a g e n e t i c changes i n associated sediments.

Thus, t h e degree of c o a l i f i c a t i o n i s perhaps t h e b e s t method of determining
t h e temperatures t h a t existed during t h e e a r l y s t a g e s of sediment diagenesis.

I b e l i e v e t h e c l a y minerals are as sensitive t o temperature as are coals.

The c l a y minerals have t h e advantage of being present i n n e a r l y a l l sediments.

113

bi

Both chemical and physico-structural

changes occur during c o a l i f i c a t i o n .

Decreases i n porosity, moisture content, and o p t i c a l anisotropy p a r a l l e l t o

t h e bedding planes occur during t h e e a r l y s t a g e s of diagenesis (peats and
brown c o a l s ) .

More advanced s t a g e s of diagenesis and metamorphism cause

changes predominantly i n chemical p r o p e r t i e s and o p t i c a l p r o p e r t i e s (dependent

on chemical composition).

As t h e moisture content decreases, t h e c a l o r i f i c value of t h e c o a l increases.

The loss of moisture depends on a decrease i n porosity and on t h e

decomposition of hydrophylic f u n c t i o n a l groups, p a r t i c u l a r l y OH-groups.

Also,

carboxyl, methoxyl, and carbonyl groups are s p l i t o f f , increasing t h e carbon

content.

During t h e l i g n i t e t o subbituminous s t a g e t h e l a s t remnants of

l i g n i n and c e l l u l o s e are transformed i n t o humic materials.

The humic a c i d s

condense t o l a r g e r molecules, losing t h e i r a c i d character t o form alkali-ins o l u b l e "humins".

The most s t r i k i n g changes a t t h i s s t a g e are petrographic.

Geochemical g e l i f i c a t i o n ( v i t r i n i t i z a t i o n ) of t h e humic substances occur and

gr

t h e c o a l becomes black and l u s t r o u s .

During t h e bituminous s t a g e t h e v o l a t i l e matter (V.M.)
decreases and r e f l e c t i v i t y rises.

systematically

About equal amounts of CH4 and CO

released ( J h c g e n and Karweil, 1966).

are

The a n t h r a c i t e s t a g e is characterized

by a r a p i d f a i l of hydrogen content and of atomic H/C r a t i o , and a strong

increase i n r

and o p t i c a l anisotropy.

only are rele

Large q u a n t i t i e s of methane

g r a p h i t i z a t i o n occurs, e s p e c i a l l y during t h e
changes are summarized i n Table 1.

The c o a l f i c a t i o n process i s controlled primarily by temperature and time.

1

Pressure r e t a , d s chemical r e a c t i o n during c o a l i f i c a t i o n by i n h i b i t i n g t h e

t

release of gas.

"b

Chemical rank normally increases with depth.

The rate of

114

Table 1. The different stages of coalification and their distinction on the

basis of different physical and chemical rank parameters. After Stach et al.
(1975). D.A.F. = Dry Ash Free.
:al. Valut

Rank

German

Btullb

USA

%
-0.2

- 68

[kcallkg:

Vitrite

---

- 64
Weich-

.0.3
Lignite

.x

Matt-

SubBit.

_ C6_

.0.4

0.5

Flamm-

- 5 -.
rn

1.0

=
x

0.8

x
m

Medium
Volatile

._ Bituminous

-u

EssMager-

vJ

1.4

- 44

1.6

Volatile
Bituminous
SemiAnthracite

1.8

2.0

c
Anthracite
Meta-A.

.ca. 35

- ca. 71

-ca. 17

ca. 25

ca. 8-1

1200
140001

. 9900
155001

12600

I70001

- 40
-

- 36
- 32

- 28
-

. ca. 87

15500
l0650l

ca. 91

ifim

- 24
-

low

Anthrarit

Jleta-Anthr.

- 56
- 52
- 48

1.2

5:

Fett-

-ca. 75

- 60
-

Y)
3

.I

asflamm-

Gas-

0.6

- ca. 60

3.0
4.0

- 20
-

16

12

- 8

186501

115
rank i n c r e a s e i s dependent on t h e geothermal gradient and on t h e heat conduct i v i t y of t h e rocks.

Studies i n folded regions i n d i c a t e t h a t pressure has

l i t t l e e f f e c t on c o a l i f i c a t i o h .

I n most instances t h e c o a l i f i c a t i o n rank w a s

obtained during b u r i a l and before folding.

Adjacent t o f a u l t s along which

movement has been rapid, t h e c o a l rank may be increased due t o t h e c r e a t i o n

of f r i c t i o n a l heat.

Generally, movement i s so slow t h a t f r i c t i o n a l heat i s

--?

l o s t before i t a f f e c t s t h e coal.
Temperatures on t h e order of

loOD-

150C w i l l normally produce a bitumi-

nous c o a l and temperatures on t h e order of 3OOOC (20OOC i s a more common value)

w i l l produce a n t h r a c i t e .

Numerous examples i n d i c a t e t h a t f o r samples buried

t o s i m i l a r depths those that have been buried f o r a longer time w i l l have a

more advanced degree of c o a l i f i c a t i o n .

The influence of time i s g r e a t e r t h e

higher t h e temperature.
Demaison (1974) has compiled d a t a showing t h e r e l a t i o n of m a x i m u m paleotemperature t o c o a l rank (Table 2).
C

Presumably much of t h e v a r i a t i o n is due

t o t h e influence of l e n g t h of exposure t o heat.

i n f l u e n c e of time i s minor p a s t about 200 m.y.

Demaison believes t h a t t h e
of exposure t o maximum h e a t

effects.
Calculations have been made showing how c o a l rank i s r e l a t e d t o temperat u r e and time (Huck and K a r w e i l , 1955; K a r w e i l , 1956; Lopatin, 1971; Lopatin
and Bostick, 1973).

Lopatin (1971) notes t h a t i t i s necessary t o sum t h e time

a c o a l w a s i n t h e v a r i o u s thermal zones i n order t o properly e v a l u a t e t h e timetemperature

ects (sum of t h e adjusted d u r a t i o n s of t h e process).

Bostick (1973) reviewed some examples.
e f f e c t r e g a r d l e s s of time.

Temperatures below

Lower Carboniferous c o a l s of t h e

not been subjected t o temperatures higher than 2 Y C and

116

Table 2. Relation of coal rank to burial temperature. D.A.F.

After Demaison (1974). For references see original paper.

I
FRANCE

GERMANY

PARIS

= Dry Ash Free.

1
U.S.S.R

USA

US.SR

U.S.A

GRABEN

BlTUM

BlTUM

1.51 90

DARK

DROWN

1.92 91

TO
BLACK

KARTSEV
IASSOEVICH
ETAL

BOSTICK

STARIN
ElAL

OEMWXN
ITHIS P A E R

1969

1970

1971

I971

1973

1913

80"

60"
80"

75"

100"

115"

115"

90"

115"

60"
90"

'O

55"

co

100"

135"
150"

65"

34c=

130"

c0

120"

170"

BITUh!.

PPiTHRACITE.

60"

140"

1NTHRAr

2.50

)PAQUE

TEICHMULLEI

'I,
MEDIUM
VOL
BlTUM

13.5

CORREIA

200"

155'

117

6.
e

remain l i g n i t e s .

I n c o n t r a s t , a temperature of 100C has produced a n t h r a c i t e

i n t h e Upper Carboniferous, Oklahoma (270 m.y.);

about 175C w a s required t o

convert coaly material t o a n t h r a c i t e i n J u r a s s i c (160 m.y.);

and i n t h e Salton

Geothermal Field (Late Pliocene-Early Pleistocene), temperatures of 2900 t o

300C were required t o produce a n t h r a c i t e coal.

Diagenetic changes of c l a y

minerals are much less time dependent (Figure 8).

Damberger (1974) determined t h e c o a l i f i c a t i o n p a t t e r n s of t h e Pennsylvan i a n c o a l basins of t h e e a s t e r n United S t a t e s and noted t h a t though they genera l l y r e f l e c t t h e depth of b u r i a l during later Pennsylvanian and Permian times
t h e r e i s a superimposed p a t t e r n due t o r e g i o n a l thermal disturbances.

From

Permian t o r e c e n t t i m e s high h e a t flow apparently e x i s t e d i n t h e Rhode I s l a n d

Meta-anthracite region, i n t h e Pennsylvania a n t h r a c i t e region extending w e s t ward i n t o t h e low- and medium-volatile bituminous c o a l s of Pennsylvania and
i

West Virginia, and i n t h e high-rank bituminous c o a l s i n southern West Virginia.

Shales
Finely divided coaly p a r t i c l e s are present i n most s h a l e s and s i l t s t o n e s .
Bostick (1974) coined t h e term phytoclasts f o r d e t r i t a l p l a n t material i n

sediments which has a composition similar t o c o a l (others use t h e term kerogen).

H e concluded t h a t 90 t o 95 percent of t h e organic matter i n sediments i s phy-

t o c l a s t s r a t h e r than compounds s o l u b l e i n organic solvents.

Most of t h e phy-

t o c l a s t s consi$t of p l a n t spores and pollen, l e a f c u t i c l e s , and fragments t h a t

have bordered
i

i t s , r i b s , f i b e r s , o r cellular s t r u c t u r e .

Some c o n s i s t of in-

s o l u b l e humate and f l o c c u l a n t masses t h a t may be of a l g a l o r i g i n .

rements can be made with t h e microscope on t h e s e organic par-

titles.

*bid

Untre ted rock samples are more s a t i s f a c t o r y than concentrates prepared

118
by chemical o r physical methods.

However, s e p a r a t i o n i s o f t e n necessary

because many rocks have an extremely low content of organic material.

One of t h e simplest methods of determining t h e degree of thermal altera t i o n is through t h e use of a color index (Staplin, 1969; Hood e t al., 1975;
Epstein e t al., 1976).

The color of kerogen generally changes from yellow t o

brownish yellow t o v a r i o u s shades of brown and f i n a l l y t o black as the degree

of a l t e r a t i o n increases.

A yellow color i n d i c a t e s t h a t t h e kerogen has been

subjected t o temperatures of less than 6OOC; yellow t o brown, temperatures

60' t o 125OC; and black, temperatures g r e a t e r than 125OC.

More q u a n t i t a t i v e

measurements include v i t r i n i t e r e f l e c t a n c e (deVries e t al., 1968, and Bostick,

1974), carbon content, and e l e c t r o n s p i n resonance.
Casta'iio

and Sparks (1974) found l i t t l e d i f f e r e n c e i n v i t r i n i t e r e f l e c t a n c e

of coal-shale p a i r s except when t h e s h a l e s contained small amounts of v i t r i nite.

Palynomorphs i n limestones have s i g n i f i c a n t l y lower r e f l e c t a n c e values

than associated c o a l s (Epstein e t al., 1976).

i n sandstones is less than t h a t i n mudsmnes

The r e f l e c t a n c e of v i t r i n i t e
(Chichua, 1964).

Hydrocarbons and Temperature

C o a l i f i c a t i o n and bituminization are d i a g e n e t i c processes during which
mobile products (gas o r crude o i l ) are evolved and aromatization and condenstion

of t h e s o l i d r e s i d u a l products (coal o r kerogen of petroleum source

rocks) take place.

I n general, t h e parent substance and t h e i n i t i a l decompo-

s i t i o n soon a f t e r deposition w i l l determine whether c o a l o r petroleum forms.

Coals are formed primarily from l i g n i n and c e l l u l o s e from higher p l a n t s , and
petroleum from lower organisms (algae, animal plankton, and b a c t e r i a ) .

These

l a t t e r organisms decompose anaerobically t o produce l i p i d s , t h e most important

progenitors of hydrocarbons.

During t h e geochemical bituminization process,

t h e l i p i d s become incorporated i n t o kerogen.

119
Thermal degradation of organic matter i s required t o produce petroleum

bd

( P h i l i p p i , 1965).

Degradation forms smaller molecules of increasing v o l a t i l i t y ,

mobility, and hydrogen content (with methane as t h e end product).

The car-

bonaceous r e s i d u e (condensation) l o s e s hydrogen, with g r a p h i t i c carbon being

t

t h e end product (Dobryansky, 1963).

The r e s u l t s of s t u d i e s r e l a t i n g hydrocarbon occurrence t o rank of assoc i a t e d coaly matter i n various o i l pr'ovinces w e r e tabulated by Bostvick and
Danberger (1971).

O i l and associated gas occurs mainly i n rocks i n which t h e

coaly material has reached subbituminous t o high-volatile bituminous rank.

Dry g a s (methane) i s formed during t h e medium-volatile bituminous c o a l through
t h e a n t h r a c i t e stage.

The base of t h e o i l zone a l s o coincides with 65 t o

70 percent fixed carbon and v i t r i n i t e r e f l e c t a n c e values of 0.8-1.1.

A com-

parison of Table 1 with Table 2 (coal rank t o temperature r e l a t i o n s ) indi-

cates t h a t t h e base of t h e o i l zone occurs a t 10Oo-14OOC.

The e f f e c t s of time on hydrocarbon generation were demonstrated by Lap l a n t e (1972).
'

I n t h e Gulf Coast T e r t i a r y he found t h e l e v e l of carboniza-

t i o n necessary f o r hydrocarbon generation increased from 8OoC f o r Oligocene

sediments t o 86 C f o r lower Miocene and 97C f o r Upper Miocene.
Pusey (1973 b) introduced the concept of a l i q u i d window.

H e noted that

thermal "cracking" of kerogen and hydrocarbon generation starts a t 65W, and

t h a t l i q u i d hydrocarbon d e s t r u c t i o n becomes dominant a t temperatures g r e a t e r
than 150C.

This temperature i n t e r v a l he termed l i q u i d window.

Of t h e 266

known g i a n t o 1 f i e l d s , 262 occur i n t h i s temperature range.

73) used e l e c t r o n s p i n resonance (ESR) d a t a as a geothermometer.

The number of f r e e r a d i c a l s i n c r e a s e s as kerogen i s subjected t o increasing
temperature.
e-

ESR provides a measure of t h e number of f r e e e l e c t r o n s per gram

120
The maximum paleotemperature determined by ESR w a s only 205C.
no c o r r e c t i o n f o r e f f e c t i v e heating t i m e .

Pusey made

Earlier Binder (1965), C r e l l i n g

LwJ
I

and Dutcher (1968), and Retcofsky and F r i e d e l (1968) used ESR t o rank coals.
The various coal-ranking p r o p e r t i e s ( c a l o r i f i c value, moisture content,
v o l a t i l e content, hydrogen content, and v i t r i n i t e r e f l e c t a n c e ) are not applicable over a wide temperature range.

Hood e t a l . (1975) suggested a scale

which i s continuous over t h e temperature range of approximately 50C t o 300.C

and which can be c o r r e l a t e d with coal-rank parameters.

Though temperature i s

t h e major defining f a c t o r i n t h e process of organic metamorphism, t h e e f f e c t

of time is important enough t h a t a temperature scale cannot be used as a
general measure of organic metamorphism.
They c a l l t h e i r scale "Level of Organic Metamorphism" or "LOW'.

scale i s a l i n e a r subdivision of a type-section

The

(Tertiary-Cretaceous of New

Zealand) o r organic-rich sediments which w a s buried a t e s s e n t i a l l y a constant

rate and a constant temperature.

Their s c a l e i s a r b i t r a r y and they note that

t h e c o a l rank of a Carboniferous relative-depth column compiled by Bostick

and Danberger (1971) does not coincide with t h e one they chose t o use.
Lopatin (1971) and o t h e r s concluded t h a t doubling t h e r e a c t i o n rate with
each increase i n temperature of l o O C provided a model of t h e relative e f f e c t s
of temperature and time i n subsurface organic metamorphism.
combined maximum temperature (T

max

Hood e t a l . (1975)

) with a n e f f e c t i v e heating time ( t e f f ) t o

develop a s i m p l i f i e d method of p r e d i c t i n g LOM f o r petroleum source rocks.

Using a v a r i e t y of b u r i a l h i s t o r i e s and a wide range of a c t i v a t i o n energies
(8.4 t o 55 kcal/mole), they concluded t h a t t h e e f f e c t i v e heating time during
which a rock has been within 15C of i t s maximum temperature r e p r e s e n t s a
s u i t a b l e d e f i n i t i o n of e f f e c t i v e heating time.

Thus, i f a sediment deposited

u-

121

SI

150 m.y.

ago required 100 m.y.

t h e remaining 50 m.y.

W'

t o reach a temperature of 120C, and i f during

reached a maximum temperature of 135OC and d i d not drop

below 120C, t h e l a s t 50 m i l l i o n years i s counted as t h e e f f e c t i v e heating

tbe.

Figure 14 shows t h e suggested r e l a t i o n of LOM and other parameters t o

t h e p r i n c i p a l s t a g e of petroleum generation.
i n t h e lowest LOM stages.

Diagenetic methane i s formed

This i s followed, with increasing LOM, by t h e

generation of o i l , condensate p l u s w e t gas, and high-temperature katagenetic

methane

LOM values obtained from s h a l e from two w e l l s i n d i c a t e that t h e values

are not l i n e a r with depth.

Shallower samples have higher LOM values than

those defined by l i n e a r r e l a t i o n s of LOM t o depth.

They b e l i e v e t h i s i s mainly

a r e s u l t of an i n c r e a s e i n apparent a c t i v a t i o n energy with increasing LOM.

4'

The lower a c t i v a t i o n energies, a t low LOM values, i n d i c a t e a g r e a t e r importante

of t i m e with r e s p e c t t o temperature.

Thus, f o r low LOM values t h e devia-

t i o n from l i n e a r i t y i s l a r g e r f o r Paleozoic than Mesozoic and Cenozoic rocks.

The published d a t a (Hood e t al., 1975, and Pusey, 1973 a) i n d i c a t e t h a t ,
_-

r e g a r d l e s s of age, t h e depth-temperature r e l a t i o n s are l i n e a r a t temperatures

higher than approximately 15Oo-16O0C.

LOM and ESR parameters are l i n e a r l y

r e l a t e d t o both a t t h e s e higher temperatures.

Between 75O and 150-160C

t h e same r e l a t i o n s are n e a r l y l i n e a r , but t h e LOM and ESR parameters i n c r e a s e

a t a slower r a t e as a f u n c t i o n of increased temperature.

I n t h e T e r t i a r y sediments of t h e Upper Rhine Graben (Doebl e t al., 1974),

r e f l e c t a n c e of h u m i n i t e s / v i t r i n i t e s i n c r e a s e s from 0.20 (40'C)

t o 0.86 (169OC)

i n t h e w e l l with t h e higher geothermal g r a d i e n t and from 0.20 (4OoC) t o 0.73

(130'C)
I

&'Ci

i n a w e l l with a lower g r a d i e n t and containing a t h i c k e r section.

~-~

122

~~

PRINCIPAL STAGES OF
PETROLEUM GENERATION
RSSOYEVICH LlM.Il97l

UAlUI111

EARLY
METHANE

IMMATURE

01L

ZONE OF
INITIAL MATURITY
'OIL GENERATION)

CONDENSATE
6 WET GAS

MATURE

-U
-9

- 10
L 11

'-HiGH;
VOL
Elf
10-

- 12

- 13
.

-14

- - -15
61'
12
LV
Ell
-1

MV

14

- SEMI- ANTH

16-

18-

6
POST-MATURE

HIGHTEMPERATURE
METHANE

ANTH

Figure 14. Organic metamorphic stages of petroleum generation. LOM = Level

of Organic Metamorphism; VM = Volatile matter. After Hood, et al. (1975).

123

(1
t

The t r a n s i t i o n from l i g n i t e t o hard coal, corresponding t o a r e f l e c t a n c e

High v o l a t i l e bituminous c o a l w a s found only

value of 0.6, occurs a t 130C.

i n t h e deepest sample, 169OC.

These temperatures are considerably higher

than those reported f o r equivalent r e f l e c t a n c e values f o r c o a l (Demaison,

1974).

The r e l a t i v e l y low r e f l e c t a n c e values f o r t h e measured temperatures

may be due t o t h e young age of' t h e sediments,

l a r g e l y Oligocene and Miocene,

and a r e c e n t i n c r e a s e i n t h e geothermal gradient.

I n t h e w e l l with t h e higher geothermal g r a d i e n t (7.7OC/lOO m) t h e f i r s t
formation of petroleum hydrocarbons w a s observed a t a depth of 700 m (65C);
i n t h e w e l l with t h e lower g r a d i e n t (7.2OC/lOO m) they were f i r s t observed
a t 2600 m (118OC).

This study f u r t h e r emphasizes t h e r o l e of time and t e m -

p o r a l v a r i a t i o n s i n t h e geothermal g r a d i e n t i n determining t h e e x t e n t of min-

eral and organic transformation.

Conodonts
I n a r e c e n t study, Epstein e t al. (1976) r e l a t e d t h e color a l t e r a t i o n
of conodonts t o a n index of organic metamorphism.

Conodonts are t h e hard

p a r t s , 0.1 t o 1 m m i n s i z e , of a n unknown organic group and are composed

l a r g e l y of carbonate apatite.

They established a color a l t e r a t i o n index

(CAI) by heating conodonts a t v a r i o u s temperatures till they obtained a s t a b l e

c o l o r (Table 3).

124
Table 3.

Munsell s o i l c o l o r s of conodont color a l t e r a t i o n indexes

(Epstein e t al., 1976)

Munsell S o i l Color

CAI
-

P a l e yellow (2.5YR7/4 t o 8/4)

14

Very p a l e brown (10YR7/3 t o 10YR8/4)

Brown t o dark brown (10YR4/2 t o 7.5YR3/2)

Very dark grayish brown (10YR4/2) t o dark reddish

brown (5YR2.5/2), t o black (10YR2.5/1)

Black (5YR2.5/1)

Black (7.5YR2.5/0)

t o black (10YR2.5/1)
t o black (2.5YR2.5/0)

An Arrhenius p l o t of t h e d a t a from conodont open-air heating runs w a s

made t o allow f o r t h e e f f e c t s of time.

The maximum heating time w a s 1000

8
hours and t r e n d s w e r e extended t o 5 x 10 years.

Confined pressure during

heating had no e f f e c t on carbonization; however, pressure i n t h e presence of

water retarded carbonization.

Using t h e Arrhenius p l o t s , they concluded t h a t

time had r e l a t i v e l y l i t t l e e f f e c t on t h e CAI beyond d u r a t i o n s of about 50

m i l l i o n years.

They p o i n t out t h a t v a r i o u s s t u d i e s , including t h e i r s , have

shown t h a t c o a l i f i c a t i o n i s a function of depth of b u r i a l , and tectonism influences i t only where i t increases depth of b u r i a l .
The CAI and temperature d a t a (from Arrhenius p l o t ) were compared with
t h e translucency index and with v i t r i n i t e r e f l e c t a n c e (Table 4).

E
rocks in

N.J.

2.3

localities.
1M) MILES

100 KILOMETRES

126
Table 4.

Organic metamorphism i n d i c e s (Epstein e t al., 1976)

Conodonts
CAI

Temperature "C

1
1%
2
3
4
5

Palynomorphs
Weight Percent
Translucency
Carbon i n
Index (Amoco)
Kerogen

1-5
5-up. 5
5-6
UP. 5-6
6
UP. 6-7

<50-80
50-90
60-140
110-200
190-300
300-400

<82
81-84
81-87
83-89
84-90
+90

Vitr i n i t e
Reflectance

Percent
Fixed
Carbon

<O. 8
0.7-0.85
0.85-1.3
1.4-1.95
1.95-3.6
+3.6

<60
60-65
65-73
74-84
84-95
+95

The translucency index is most s e n s i t i v e a t lower temperatures ( l e s s than

16OoC), and C A I and v i t r i n i t e r e f l e c t a n c e a t higher temperatures.

a considerable temperature range f o r each CAI value.

and t h e CAI show s i m i l a r trends.

There i s

The r e f l e c t a n c e d a t a

Comparison with published d a t a (Demaison,

1974) i n d i c a t e s t h a t temperature values are i n reasonably good accord, though

f o r a given measurement t h e r e is considerable spread f o r both sets of temperat u r e values.
Epstein e t a l . (1976) determined t h e CAI of conodonts from 705 limestone
samples from t h e Appalachian Basin.

They constructed CAI isograd maps f o r

t h e Ordovician, mainly Middle Ordovician, S i l u r i a n through Middle Devonian,

and Upper Devonian through Pennsylvania.
grads f o r t h e Ordovician.

Figure 15 is a map showing CAI iso-

An isopach map of Middle Ordovician through Permian

rocks w a s constructed t o determine i f t h e CAI values were r e l a t e d t o t h e maximum depth of b u r i a l .

Unloading is believed t o have begun i n t h e Triassic.

Throughout most of t h e basin, CAI isograd and isopach t r e n d s are conformable.

The CAI values g e n e r a l l y decrease from east t o w e s t .

CAI = 1.5 begins

a t 1,220 m of overburden and p e r s i s t t o 2,440 m; CAI = 2 p e r s i s t s from 2,440

u
.

127

L4

t o 3,660 m of overburden; CAI = 3 p e r s i s t s from 3,660 t o 5,490 m of over-

*'

burden; CAI = 4 p e r s i s t s from 5,490 t o 7,625 m of overburden; C A I = 5 begins

a t about 7,625 t o 9,150 m of overburden.

geothermal g r a d i e n t ( 3 . 3 O

By assuming that t h e present-day

per 100 m) p e r s i s t e d throughout post-Ordovician

time, they c a l c u l a t e d t h e temperature range f o r t h e v a r i o u s overburden depth

intervals.

The c a l c u l a t e d values compared w e l l with t h e experimental (heated

conodonts) values.

-,

I n some areas CAI values are anomalously low.

that occur as windows i n t h r u s t sheets.

These values are f o r rocks

Anomalously high values are found f o r

conodonts i n rocks near Cenozoic i n t r u s i o n s .

The CAI isograd p a t t e r n s of t h e

younger sediments show similar r e l a t i o n s , though t h e CAI values are g e n e r a l l y

lower.

The o i l f i e l d s are w e s t of t h e 2 isograd.

t o a v i t r i n i t e r e f l e c t a n c e range of 0.85-1.3.

A CAI of 2 i s equivalent

G a s production extends i n t o

areas where s u r f a c e rocks have CAI values as high as 4 (equivalent v i t r i n i t e

r e f l e c t a n c e range i s 1.95-3.6).
Figure 16 i s a map of a p o r t i o n of t h e e a s t e r n United S t a t e s showing t h e
r e l a t i o n of o i l and g a s occurrence t o t h e 70 percent fixed carbon l i n e (1000
14OOC) i n Upper Paleozoic strata.

Equivalent strata t o t h e east of t h i s l i n e

were exposed t o higher temperatures (Bostick and Danberger, 1971).

Relation of Mineral Diagenesis t o Organic Metamorphism

Coal p e t r o l o g i s t s u s e t h e term "metamorphism" t o t e f e r t o changes that
occur i n t h e temperature range which includes both t h e zones of "diagenesis"
'
I

and "metamorphism".

I n t h e following s e c t i o n t h e l i t e r a t u r e i s reviewed which

shows t h e r e l a t i o n of mineral diagenesis

-C-i

morphism.

and metamorphism t o organic meta-

128

Figure 16. Regional r e l a t i o n of o i l and gas occurrence to coal rank i n Upper

Paleozoic strata of the eastern United States. After Bostick and Danberger
(1971).

129
Clay Minerals

I$

Kisch (1968 a and 1974) reviewed the relation between coal rank and burial
L

metamorphic mineral facies. He notes that minerals formed during burial are
commonly metastable and that mineral composition, C02, H20, pore salinity,
&

and pressure have an effect on progressive coalification.

Figure 17 summarizes Kisch's (1974) conclusions. He compared the data
of the Russian authors to those of the French and Swiss and concluded that
the zone of diagenesis is equivalent to the epigenesis zone; the anchimetamorphic zone is equivalent to the early metagenesis zone; and the epizone is
equivalent to the stage of late metagenesis.

The diagenesis-anchizone boundary

coincides with the change from lean coal to anthracite (V.M. 8 percent, V.R.
2.5).

This change in coal rank occurs at a temperature of approximately 2OOOC

(Demaison, 1974, and Hood et al., 1975).

c

The boundaries of the anchizone are

based on crystallinity values for illite, upper 7.5

- lower 4.0.

Dunoyer de

Segonzac (1970) uses values of 4.0 and 2.5 for these boundaries.
Coal rank-mineral data on the Carboniferous of the Karaganda Basin and

the Permian of thespetchora-Vorkuta Basin are given by Kossovskaya et al.

I

(1964); Botscharnikowa (1965); Kossovskaya and Shutov (1970).

tabulated in Table 5.

I have estimated the temperatures, using the values

74) and Hood et al. (1975).

Their data are

I-L

w
r

ANTHRACITE

"ANCHI METAMORPHIC
ZONE"("STAGE OF
EARLY METAGENESIS7
Illite cryrtalllnitie, 7.5-4.0

(Kubier 1969) Pyrophylllte,

allevordite, paraqonite, phcngite

42VM

-2.5%~

Low-wnk

-Q72H META -ANTHRACITE

Hlqh- rank:
(h kl)XR D reflections

E:

E PIZON .GREEN5CHiS T
FACIES.(in.cl."STAGE OF
U T E METAGENE5 I5")

Figure 17. Schematic relation of diagenetic-metamorphic stages to coal rank.

After Kisch (1974). For references see original publication.

131
\

LJ

Table 5.

Relation of c o a l rank t o s h a l e mineralogy and temperature i n some

r u s s i a n Paleozoic sediments (Kossovskaya e t a l . , 1964)

Possible
Temp., O C

Rank

V.M.%

High v o l a t i l e bituminous

35-30

Montmorillonite (probably
containing <50% i l l i t e
layers)

Medium and low v o l a t i l e

bituminous

30-18

Mixed-layer, 20-50%
expanded l a y e r s

100-170

Low v o l a t i l e bituminous
and semi-anthracite

18-10

I M i l l i t e (lMD?)

150-180

Anthracite

<6%

Clay Minerals

2M i l l i t e , c h l o r i t e

90-115

>200

I n a d e t a i l e d study of t h e T e r t i a r y c l a y s of t h e Upper Rhine Graben,

Doebl e t al. (1974) r e l a t e d t h e transformation of organic matter and c l a y
minerals t o v a r i o u s geothermal gradients.
w

They e s t a b l i s h e d from a study of

numerous w e l l s t h a t smectite p e r s i s t s t o temperatures i n t h e range of 68O t o

76OC, though i n young, r a p i d l y buried sediments i t p e r s i s t s t o temperatures

as high as 1 1 5 O C .

The absence of smectite presumably r e f e r s t o t h e absence

of a 17 A r e f l e c t i o n and t h e formation of a mixed-layer illite-smectite w i t h

less than 40percent expanded l a y e r s .

The maximum temperature they reported was 169OC' (2063 m).

Though void

r a t i o and pore r a d i i decrease with increasing temperature, and r e f l e c t a n c e of

huminites and vitrinites increase, t h e r e i s no major change i n t h e c l a y mineral
*

s u i t e (smectite, mixed-layer illite-smectite,

i l l i t e , k a o l i n i t e , and c h l o r i t e ) ,

o t h e r than t h e conversion of smectite t o mixed-layer c l a y , with depth and

temperature.

-U

There i s some suggestion that i n t h e temperature range of 130

t o 169OC k a o l i n i t e decreases and c h l o r i t e increases.

Approximately 20 percent

132
/

calcite i s present and does not decrease with increased depth and temperature.

K a o l i n i t e disappears from sandstones a t a depth of 3000 m i n t h e Upper Namur

C.

The associated c o a l i s a n a n t h r a c i t e (7 percent V.M.).

Kisch (1974) has compiled t h e d a t a on t h e c o a l ranks associated with

anchizone minerals ( i l l i t e c r y s t a l l i n i t y 7.5 t o 4, a l l e v a r d i t e , paragonite

pyrophyllite).

H e p o i n t s out t h e problem of measuring i l l i t e c r y s t a l l i n i t y

when p y r o p h y l l i t e (9.2 A) o r paragonite (9.7 A) are present.

The c o a l s asso-

c i a t e d w i t h t h e anchizone minerals l i s t e d above are a n t h r a c i t e s (8 t o 4 perc e n t V.M.).

The upper l i m i t of t h e anchizone i s t h e lower l i m i t of t h e exis-

tence of l i q u i d hydrocarbons.

K a o l i n i t e and mixed-layer i l l i t e - m o n t m o r i l l o n i t e

are presumed not t o be present i n anchizone sediments; however, t h e compiled

d a t a i n d i c a t e t h a t k a o l i n i t e , commonly along with pyrophyllite, is present i n
t h e underclays associated with t h e a n t h r a c i t e c o a l s of t h e northeastern United
S t a t e s , along with pyrophyllite, i l l i t e , and c h l o r i t e .

Mixed-layer paragonite-

muscovite has been reported i n some Alpine anchizone d e p o s i t s (Hoefs and Frey,
1976).

The temperature range i s estimated t o be from 2 0 8 t o 358C.

Para-

g o n i t e i s a common component of anchizone and higher grade p e l i t i c and marly

rocks of t h e Alps (Frey, 1974).

Earlier Frey and Niggli (1971) considered

t h a t t h e upper anchizone boundary (7.5 c r y s t a l l i n i t y index) coincided with

c o a l s containing 35 t o 19 percent V.M.

8 percent V.M.).

(compared with Kisch's boundary a t

The lower boundary i s s i m i l a r t o t h a t proposed by Kisch.

Quinn and Glass (1958) found a n t h r a c i t e and low-rank meta-anthracite of t h e

Narragansett basin, Rhode I s l a n d , associated with rocks of t h e muscovitec h l o r i t e subfacies of t h e greenschist f a c i e s , and a higher-rank meta-anthracite
with rocks of t h e b i o t i t e - c h l o r i t e subfacies.
Albrecht and Ourisson (1969) studied a w e l l penetrating t h e Cretaceous
Douala s h a l e s of t h e Cameroun and established that extra s t a b l e heavy s a t u r a t e d

b'

133

LJ
JL

hydrocarbons were most abundant i n t h e depth range of 1300 to 2200 m.

day w e l l temperature over t h i s i n t e r v a l i n c r e a s e from 60" t o 105OC.

Present
My i n t e r -

p r e t a t i o n of Dunoyer d e Segonzac (1970) x-ray d a t a i n d i c a t e s that through t h i s

i n t e r v a l t h e proportion of i l l i t e l a y e r s i n t h e montmorillonite i n c r e a s e s
c

from approximately 10 percent t o 70 percent.

The i l l i t e l a y e r s i n c r e a s e t o

approximately 90 percent a t a bottom h o l e depth of 418.5 rn and temperature

of 155OC.

Pusey (1973 b) e s t a b l i s h e d a c o r r e l a t i o n between ESR-kerogen d a t a and

t h e "first-collapse"

of montmorillonite i n t h e Cretaceous of South Texas.

O i l is produced above t h e " f i r s t collapse" of montmorillonite (1200 C) but

g i v e s way t o dry gas below t h e " f i r s t collapse".

Foscolos and Kodama (1974) and Foscolos e t a l . (1976) have studied t h e
c l a y minerals and organic material i n a series of Lower Cretaceous s h a l e s from
*

n o r t h e a s t e r n B r i t i s h Columbia and have e s t a b l i s h e d d i a g e n e t i c r e l a t i o n s .

They

found t h a t t h e amount of 2M i l l i t e , i t s c r y s t a l l i n i t y index, and i t s sharpness

e

r a t i o i n c r e a s e s with depth.

The proportion of i l l i t e l a y e r s i n mixed-layer

i l l i t e - m o n t m o r i l l o n i t e i n c r e a s e s from approximately 50 percent t o 85 percent

with depth (maximum depth 3078 m).
with depth; Si02

+ Fe203 + MgO/A1203

I n t h e ~0.08pm f r a c t i o n , K 2 0 i n c r e a s e s
and C.E.C.

decrease.

V i t r i n i t e . r e f l e c t a n c e values show considerable v a r i a t i o n i n t h e s h a l e s

where d i a g e n e t i c r e a c t i o n s .have been minor, but i n c r e a s e s y s t e m a t i c a l l y as
mineral d i a g e n e s i s increases.

The i n t e r v a l of maximum y i e l d of e x t r a c t and

hydrocarbons '(mg/g organic C) coincides with t h e i n t e r v a l where t h e proportion

of i l l i t e i n t h e mixed-layer i l l i t e - m o n t m o r i l l o n i t e i n c r e a s e s from 25 percent

t o 75 percent.

The r e l a t i o n , p a r t i c u l a r l y t h e upper boundary, i s not good.

I n p a r t , t h i s is because t h e assumption i s made t h a t t h e s t a r t i n g material

~

134
contained a f u l l y expanded montmorillonite.

The d a t a suggest that t h e o r i g i -

bi

n a l ( d e t r i t a l ) expanded c l a y contained approximately 50 percent i l l i t e l a y e r s ,

r a t h e r than f u l l y expanded montmorillonite.

I n Figure 18, I have p l o t t e d t h e v i t r i n i t e r e f l e c t a n c e values vs. t h e

percent i l l i t e l a y e r s i n t h e mixed-layer c l a y f o r t h e Lower Cretaceous shales
and or t h e l i t e r a t u r e d a t a as i n t e r p r e t e d by Foscolos e t al. (1976).

Also

included are temperature ranges f o r t h e v a r i o u s v i t r i n i t e r e f l e c t a n c e values.

Temperature d a t a are from Demaison (1974).

On t h e upper boundary of t h e graph

are p l o t t e d t h e paleotemperatures calculated by Foscolos and Kodama (1974)

or t h e Lower Cretaceous shales, assuming a geothermal g r a d i e n t of 3.6"C/100 m.
The l i t e r a t u r e d a t a are reasonable, but some of t h e v i t r i n i t e r e f l e c t a n c e
values f o r t h e Lower Cretaceous s h a l e s are higher than those observed i n other

areas.
G i l l e t a l . (1977) s t u d i e d t h e c l a y s i n t h e sediments associated with

c o a l s i n t h e South Wales c o a l f i e l d and e s t a b l i s h e d a r e l a t i o n between c o a l

rank and mineral diagenesis-metamorphism.

They d e s c r i b e a d i a g e n e t i c zone

f o r terrigenous rocks i n which t h e i l l i t e s have a sharpness r a t i o (S.R.)

2.0-3.0;

of

t h e carbonate rocks i n t h i s zone have a S.R. of 2.1 t o 2.5 and t h e

mixed-layer c l a y s 35 t o 40 percent expanded l a y e r s .

range from 65 t o 80 percent.

The fixed carbon values

I n t h e metadiagenetic zone ( l a t e s t a g e diagene-

sis), t h e r e s p e c t i v e S.R. values are 3.0 t o 4.0 and 2.5 t o 3.2 and t h e mixedl a y e r c l a y s i n t h e carbonate rocks contain 20 t o 35 percent expanded l a y e r s .
Fixed carbon values range from 80 t o 90 percent.

I n t h e anchizone, anthra-

cites w i t h fixed carbon g r e a t e r than 90 percent, t h e S.R.

values are 4.0 t o

6.0 f o r terrigenous rocks and 3.2 t o 4.0 f o r carbonates.

The carbonates con-

t a i n mixed-layer c l a y s with 0 t o 20 percent expanded l a y e r s p l u s new vermicular

k a o l i n i t e and d i c k i t e .

The terrigenous rocks contain a l l e v a r d i t e and pyrophyllite.

&*

135

TEMPERATURE "C

164
rEMPERATURE
"C

VlTRlNlTE
REFLECTANCE

200

2.50

- 210

2.00
165

1.50

120

- 170

100

- 130

1.oo

.50

55-

0
0

10

20

30

40

50

60

70

80

90

65

100

% ILLITE LAYERS IN MIXED-LAYER CLAY

Figure 18. Relation of percent i l l i t e l a y e r s i n mixed-layer illite-montmorill o n i t e t o v i t r i n i t e r e f l e c t a n c e and temperature. Dots and temperature values
a t top of graph are based on d a t a from Foscolos, e t a l . (1976). Squares outl i n e range of v a l u e s from l i t e r a t u r e . Temperature scale on r i g h t axis i s based
on d a t a from Demaison (1974) and relates t o V.R. values.

136
Van de Kamp (1977) attempted to relate LOM values to clay mineral changes.
He states that the montmorillonite zone occurs in the interval LOM 0 to 7;

mixed-layer illite-montmorillonite, LOM 7 to 9-10; illite zone, LOM 9-10 to

14; greenschist facies, LOM greater than 14. These associations are incom-

patible with other data. A more realistic relation would be: montmorillonite,
LOM 0 to 9-10; mixed-layer illite-montmorillonite, LOM 9-10 to 18-20; illite,
LOM 16+. An LOM value of 20 is considered to be equivalent to 2 percent V.M.
(meta-anthracite) and the greenschist facies; however, the data does not support this. Hood et al. (1975) report that the organic matter in the Carboniferous shales from the Shell Rumberger 5 (Oklahoma) should have an LOM value
of 20 at approximately 7500 m, which should be in the greenschist facies.
My x-ray analysis of a shale core from 7318 m (Total Depth) from the

same

well

showed that it is composed of illite and chlorite (dioctahedral) and 25 percent mixed-layer illite-montmorillonite.

The sharpness ratio is 2.9, the cry-

stallinity index 10.0, and the bottom hole temperature approximately 22OoC.
The deeper samples in this particular well illustrated some of the prob-

lems involved in establishing the diagenetic-metamorphic grade of rocks with

a high content of sheet silicate minerals.

The LOM and vitrinite reflectance

values indicate that the organic matter in the shales has been altered to the
level of the greenschist facies (meta-anthracite); but the clay suite, sharpness ratio, and crystallinity index indicate that the clays have been exposed
only to diagenetic conditions.

The temperature value is intermediate, but

fits the clay interpretation better than the organic interpretation. It has

been assumed that the beginning of the anchizone (crystallinity 7.5, S.R. 2.3-

4.0) and the formation of anthracite coincide with the loss of mixed-layer
illite-montmorillonite and the formation of pure illite. In many instances,
if not all, this is not correct. Expanded layers persist in "illites" to much
higher temperatures and crystallinity and sharpness ratio values than those

L"

W
5

-selected

,437

fine,--tbe, appe

h a t time %s not ,a

s f g n i f i e a n t actbra?-imthe i l l i t c z a t l o n of.montmor

ite is,illustraged.b

the: ipresence f of miired-layer ,511&te-mcmtmorillonlr

th :20 t o 39*percent

expanded dayers, and even d i s c r e t e rnontmor$il6nite i n Precambrian rocks 1.7

I n d e t a i l t h e LOM scale and t h e other o r g a n i c s c a l e s do8not:correLate.

The organic material i s s i g n i t i : __ .
f i c a n t l y a f f e c t e d by t i m e as w e l l as temperature, whereas t h e c l a y minerals

w e l l with t h e changes i n t h e c l a y minerals.

>

I_
I

changes occur, with time, u n t i l t h e r e is a major i n c r e a s e i n temperature.

ai

of humification of polar organic matter vary i n a complex and apparently

:.

138
systematic way through geologic time.

H e suggests t h a t t h e o r i g i n a l s t r u c t u r e

and composition of t h e organic matter influenced postdepositional changes i n

t h e c r y s t a l l o g r a p h i c p r o p e r t i e s of sedimentary c l a y minerals.
too few t o be convincing.

The d a t a are

Further, i t seems l i k e l y t h a t t h e p a t t e r n i s due

t o v a r i a t i o n s i n t h e depth of b u r i a l (temperature) r a t h e r than any organic

c o n t r o l of i l l i t e diagenesis.
Carbonates
C u r t i s (1978) has reviewed t h e d a t a on carbonate cementation during diagenesis.

H e p o i n t s out t h a t t h e activities of chemical s p e c i e s i n s o l u t i o n

w i l l be controlled by t h e composition and amounts of t h e s o l i d s present r a t h e r

than t h e o t h e r way round.

It i s u n l i k e l y t h a t Eh and pW c o n t r o l t h e precipi-

tapion of d i a g e n e t i c minerals.
H e suggests t h a t t h e d i a g e n e t i c carbonate cements i n mudstones tend t o

r e p l a c e pore w a t e r .

Therefore, t h e cement/elastic component volume r a t i o s

should be i n d i c a t i v e of t h e depth of b u r i a l .
goes t o completion a t a given depth.

This i s t r u e only i f cementation

Carbon i s o t o p e d a t a demonstrate that t h e

source of t h e carbonate o f t e n l i e s i n organic matter degradation r e a c t i o n s .

Carbonate types vary with b u r i a l depth and C u r t i s relates them t o t h e establfshed organic d i a g e n e t i c zones and temperatures.

Calcite and p y r i t e preci-

p i t a t e i n t h e shallow b a c t e r i a l sulphate reduction zone.

Ferroan calcite,

f e r r o a n dolomite, o r s i d e r i t e p r e c i p i t a t e i n t h e zones of b a c t e r i a l fermentat i o n and decarboxylation.

The rate of bicarbonate generation and i r o n reduc-

t i o n i n c r e a s e s with depth and temperature u n t i l t h e r e a c t a n t materials become

exhausted.

The temperature a t t h e base of t h e lower zone i s given as 75OC

above s u r f a c e temperature.

I n t h e deeper zones where l i q u i d hydrocarbons and

139

u
t

methane are generated, carbonate formation is not strongly influenced by bicarbonate derived from organic matter; instead the main processes are dissolution, re-precipitation, or replacement reactions involving unstable primary
carbonates and early diagenetic carbonates. In these higher temperature zones

.e

any carbonate mineral may form.

1

Zeolites
Zeolites will be discussed briefly. Most of the information comes from
a comprehensive review by Kisch (1974).
A study of the Tertiary coals of Japan by Shimoyama and Iijima (1976)

showed that clinoptilolite and mordenite (largely in tuffs) occur with lignite and subbituminous coals. The base of this zone occurs at approximately
85-9OoC. The bituminous coals belong exclusively to the analcime zone.

In

the upper half of the analcime zone, alkali clinoptilolite is replaced by

heulandite and locally by calcium clinoptilolite.

In the lower half, laumontite

substitutes for heulandite, for calcium clinoptilolite and, in place, for mordanite.

In New South Wales, analcime is associated with coals having a carbon

content below about 85 percent (high volatile bituminous) and laumontite with
coals having a higher carbon content (Kisch, 1966 a).

In a number of areas kaolinite, montmorillonite, and mixed-layer illitemontmorillonite are found in laumontite-bearing sequences. The evidence from
the associated coal rank indicates that the laumontite zone correlates with
lower grades of metamorphism than the anchizqne (Figure 17).

Limited data

suggest that the beginning of the prehnite-pumpellyite facies corresponds to

i

a slightly lower coal rank (15 percent V.M.)

zone ( 8 percent V.M.).

than the beginning of the anchi-

The coals associated with anchizone glaucophane-

lawsonite-schi-8
"fh

a c i b are largely anthracites and 'ow-rhnk mera-anthracites.

s assodated'wLth glaucophanit$c'$reenschist-facies are-prcsmabl

meta-anthracites
Zen"and Thompso
associations.

the anchizone.

1974) have sugg&stedkslightlg different coal rankdzealite

The main difference is the extension of -the-laumontS-te

zone into

. . ."

- -

u
mpleteness ,:?eFp+er;Lmental:and $heow

me

hase ,equilibrium

?the more Lpert;inent experimenta

e rstability;-rreAa$
!$

zsyqtem :a:aye ;relatively w

&emperattares

,.Inmost instances

t h e s e s t a b i l i t y r e l a t i o n s are e s t a b l i s h e d by heating g l a s s e s of variousrcom-,

p o s i t i o n under hydrothermal: coaditions.

iThe phases produced are -primarily

cal r e a c t i o n s occur i n water and t h a t t h e minerals ar

water.

Thus, i t i s necess

n d ' t h e aqueous s o l u t i o n

$.he ;c;qmpQsiti??n
of
2

t i v e l y i n s o l u b l e and i s assumed .!zpbe.;an

I

*LJ

The s t a b l e a h e r a l s s s

&n$ktr*
component.

ga-~r
Sa cgiven&et-.!of physical axid r,chemida

conditions i s t h a t with t h e lowest f r e e energy under those conditions.

An

142

equation is written for an equilibrium reaction between two minerals conserving A1 in the solids. For a given pressure and temperature, these reactions are defined by equilibrium constants. The equilibrium constant (K) is
equal to the product of the activities of the products raised to the power of
their numerical coefficients divided by the product of the activities of the
reactants raised to the power of their numerical coefficients. The log of
the equilibrium constant is taken, and the activities are arranged into terms
of log Na+/H+, log K+/H+, etc. and log Si02. These units are used to characterize the aqueous environment in the system and are used to describe the phase
equilibria.
A typical example is the K- mica
2KA13Si3010(OH)2

4- 2H+

log K

- kaolinite reaction.

+ 3H20 =

3H4A12Si209

+ 2K+

log K+2

H+2

It is then necessary to relate the free-energy changes of the reactions

to their equilibrium constants and to define the free-energy content of the

various types of substances. It is necessary to obtain the free energy of
the reaction to form one mole of the substances in their standard states from
the stable elements under standard conditions. The standard free-energy change
of a reaction is the sum of the free energies of formation of the products in
their standard states, minus the free energies of formation of the reactants
in their standard states

AFz

products

cAFi
reactants.

The standard free-energy of reaction is related

to

the equilibrium constant by

AF; = -RT !2n K.

Equilibrium is obtained only when the free-energy of a reaction is zero. If

LJ
c

143

sd

t h e AF;

i s negative, t h e products are s t a b l e relative t o t h e r e a c t a n t s ; i f

A F O is p o s i t i v e , t h e r e a c t a n t s are s t a b l e .

The amount of silica i n s o l u t i o n i s primarily l i m i t e d by amorphous s i l i c a

saturation.

A t 25OC t h e s o l u b i l i t y of amorphous s i l i c a ranges from 100 t o

160 ppm a t pH c 9.

S o l u b i l i t y i n c r e a s e s t o approximately 800 ppm a t 200C.

The accuracy of t h e c a l c u l a t e d s t a b i l i t y r e l a t i o n s depends on t h e accuracy of t h e thermodynamic d a t a used and i n knowing t h e composition of t h e

phases involved.

Many of t h e values f o r t h e standard f r e e energies of forma-

t i o n of compounds, dissolved species, and elements a t various temperatures

are s u b j e c t t o l a r g e u n c e r t a i n t i e s .
d i c t e d phase r e l a t i o n s .

This l i m i t s t h e r e l i a b i l i t y of t h e pre-

Tardy and Garrels (1974) have developed a method of

estimating t h e standard f r e e energies of formation of l a y e r silicates.

It i s

based on t h e assumption t h a t t h e oxides and hydroxide components of t h e s e sili-

cates have fixed Gibbs e n e r g i e s of formation within t h e silicates.

A l l of

t h e s e c a l c u l a t i o n s are based on assumed chemical compositions of t h e mineral

3F

phases.

Because t h e chemical composition of most c l a y minerals v a r i e s over

a wide range, no s i n g l e diagram can a c c u r a t e l y represent t h e phase r e l a t i o n s .

Figures 1 9 and 20 are examples of a c o l l e c t i o n of a c t i v i t y diagrams calculated by Helgeson e t al. (1969).

Though t h e aqueous phase i s not shown,

i t i s a coexisting phase i n a l l s t a b i l i t y f i e l d s and i s s a t u r a t e d with t h e

minerals shown i n t h e diagrams.

of u n i t a c t i v i t y of t h e *lids

The diagrams are based on a standard state

and u n i t a c t i v i t y of t h e aqueous s p e c i e s i n a

hypothetical one molar l i q u i d s o l u t i o n a t one atmosphere and t h e temperature

of interest.

Increasing pressure has only a s l i g h t e f f e c t on equilibrium con-

s t a n t s a t temperatures below 300OC.

The thermodynamic c a l c u l a t i o n s do not t a k e I n t o account t h e k i n e t i c fac-

;Cd

tors.

Some r e c t i o n s i n silicates are rapid but many are sluggish and occur

MICROCLINE

2 .aon

KPUL I N~ T E

-3.52 = quartz saturation.

After Helgeson-9

ki

146
over long periods of time. Factors affecting the rates of reaction of materials include their structural state, textural character, and the influence of
nonreacting substances.

Some minerals have an inherent resistance to change

that allow them to persist "metastably" at new physical conditions.

Thus, the

validity of the predicted activities depends on high temperature experiments

and even more

so

on the changes that can be observed in the natural system

where the contribution of time is a major factor. Nevertheless the thermodynamic calculations "affords an insight into the chemical environment in which
geochemical processes occur and facilitates prediction of mass transfer in
geologic systems" (Helgeson et al., 1969).

However, these insights apply

best to water-saturated surface systems and hydrothermal environments.

A more empirical approach to constructing phase diagrams is based on

obtaining experimental information and interpreting it on the basis of obser-

vations of natural mineral associations. The accuracy of much of the experimental data is affected by the same kinetic problems discussed previously.
The major problem is that as conditions change, previously formed crystalline
phases may persist (metastability).

A few examples will be given to show

the uncertainties in these types of data.

Figure 21 is a diagram illustrating the experimentally derived stability
relations in the Na20

- A1203 -

Si02

H20 system (Henley et al., 1961).

Ex-

perimental decomposition temperatures rather than true stability limits are

shown by broken lines for the sodium montmorillonite and kaolinite. The decomposition pr0duc.t of the montmorillonite obtained in the experimental work
is a mixed-layer sodium montmorillonite-mica. Mixtures of paragonite and
mixed-layer phase show a slow conversion to mica, and results are generally
inconclusive. However, they conclude that paragonite is probably the thermo>

dynamically stable phase over much or all the field of formation of the mixedlayer material.

Ld-

147

: 148

Velde (1977) has reviewed much of the experimental data and, using his
knowledge of natural associations, constructed a number of phase diagrams.
One of these diagrams for the experimental system muscovite-pyrophyllite is
shown in Figure 22.

Though Fe and Mg are not present he considers that the

-

_r

--

solid solution i n muscovite is indicative of an Al-rich illite. Farther from

the muscovite end member, a mixed-layer phase is formed consisting of Alillite and montmorillonite.

The

to be stable to

400OC; however, kberl and Hower (1977),

1 kinetic experi-

based on hydro

ments, concludedtthat this is likely an2unstable phase

reacting towards

i i

forming illite. The

has pyrop

e appearing as a

reaction product,atabout 3OO0C, whereas under the sam

not find it in runs below 345OC.

Velde admits a certa

ement of personal

bias is involved in the interpretation.

Eberl et al. (1978) establi
octahedral smectite can be incre
of hydration energy greater than K.

hydrothermal stability of disaturation with interlayer cations

They noted that it is not clear whether

revat

omemon.

Figure 23 is Velde's summary of the experimental results of the,effects

sure and temperature

sen

chlorite composition. The temperature scale is more likely to be established

from a study of the natural system than from experimental data or thermodynamic
calculations. At the lowest temperatures, disordered interlayer minerals are
present. With increasing temperature the proportion of expanded layers decrease and the layers become more ordered.

Because most shales contain several

clay minerals, the phase relations they reflect are those towards the center
of the diagram.

150

Ld

Muscovite+ Chl

Figure 23.

K-mica

P o s s i b l e general phase r e l a t i o n s f o r i l l i t e and associated phyl-

l o s i l i c a t e s as a function of varying P-T conditions.

I11 = i l l i t e , e i t h e r

predominantly lMd o r 2M i n polymorph; I = i l l i t e , 2M mica; Io = 4 l a y e r or= mixed layered 3 o r 2 l a y e r ordering giving

ss
a s u p e r s t r u c t u r e r e f l e c t i o n ; ML = mixed layered, ordered s t r u c t u r e with no

dered mixed layered phase; ML

superstructure; MLr = mixed layered non-ordered;

Mo = f u l l y expandable mont-

m o r i l l o n i t e ; Chl = c h l o r i t e ; Kaol = k a o l i n i t e ; Exp = expanding c h l o r i t e and/or

corrensite.

After Velde, 1977.

The illite field decreases in width with increasing temperature. This

indicates that the illite has become more Al-rich (more muscovite-like).
Velde suggests that in the natural system a similar trend is indicated by an
,

increase in the sharpness ratio and decrease in the crystallinity index with
c

increasing depth of burial.

A t low temperatures, compositions with a high R2+R3+ content montmoril-

lonite coexist with chlorite and kaolinite. At higher temperatures, Velde

believes that the stable phases are a regular mixed-layer illite-montmorillonite and chlorite-montmorillonite, plus chlorite.
Velde points out that PH

will play a role in determining the mineral

<

assemblage in a rock. Permeable sandstones would be likely to have PH

2

whereas impermeable shales should normally have PH =

lithostatic
lithos tatic
2
Sandstones should behave as system open to certain mobile components. The
4

shales would normally be closed to externally controlled chemical potentials

of elements in the fluid phase.
c

This brief review of theoretically and experimentally determined phase

relations illustrates some of the limitations and uncertainties of the techniques.

The kinetic problems are such that the information can only suggest

the nature of the phase changes to be expected with changing pressure-temperature.

At present, equilibrium phase relations in shales can best be es-

tablished by studying the natural system.

152
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esis of the

.
AOYAGI, K., N. KOBAYASHI, and T. KAZAMA.

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rived soils in Snowdonia, North Wales.

BARKER, C.

1972.

Aquathermal pressuring-role of temperature in development

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BERG, G.

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Verglaichende petrographic colithischen Eisenerze. Arch.

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153
BERRY, R. W. and W. D. JOHNS.

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n

BINDER, C. R.

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Clays Clay Miner.,

BODINE, M. W.,

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Regularly i n t e r -

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became a j o u r n a l , and has been published by several d i f f e r e n t

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some keyed t o volume number a d o t h e r s keyed t o p u b l i c a t i o n number or t o

c

t h e number of t h e conference (e.g.,

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COLORADO SCHOOL OF MINES

S S GOLDICH

BREAZEALE REACTOR
SAMUEL H LEVINE

COLUMBIA UNIVERSITY
WALLACE BROECKER

BRICHAM YOUNG UNIVERSITY

DEPARTMENT OF ARCHAEOLOGY
KIMBALL T HARPER
ROBERT L LAYTON
GLEN T NELSON
MORRIS S PETERSON
STANLEY L WELSH

COMMONWEALTH ASSOCIATES INC

YOSSEF BALAS

BROOKHAVENNATIONAL
LABORATORY
A J FRANCIS
P W LEVY
DONALD SCHWEITZER
BROWN UNIVERSITY
B GILETTI
BURNS AND ROE
JOHNPIRRO
CALIFORNIA DEPARTMENT OF
CONSERVATION
JAMES F DAVIS
CALIFORNIA ENERGY COMMISSION
A J SOINSKI

CONNECTICUT STATE GEOLOGIST

HUGO F THOMAS
CONTROL DATA CORPORATION
R F KUECHENBERG

CORNELL UNIVERSITY
JOHN BIRD
ARTHUR L BLOOM
K B CADY
CYNTHIA DYBALLA
JACK OLIVER
ROBERT POHL
CORTLAND COUNTY (NY) HEALTH
DEPARTMENT
J V FEUSS

DAMES AND MOORE

A E AIKENS JR
SUE FINGERMAN
TODD M GATES
LIBRARIAN

CALIFORNIA ENERGY RESOURCES

G SIMON

DAPPPOLONIA CONSULllNG
ENGINEERS INCORPORATED
R D ELLISON

CAPITAL AREA (LA)GROUNDWATER

CONSERVATION COMMISSION
A N TURCAN

DARTMOUTH COLLEGE
J 6 LYONS

CATHOLIC UNIVERSITY OF AMERICA

D D EBERT
PAUL E THIESS
CAYUGA COUNTY (NY) PLANNING
BOARD
ROBERT BROWER
CENTRAL NEW REGIONAL PLANNING
AND DEVELOPMENT BOARD
WALKER BENNINC

DATA-DESIGN LABORATORIES
PROGRAM DEVELOPMENT
DAWCON
DAVID A WEBSTER
DELAWARE STATE GEOLOGIST
ROBERT R jORDAN
DENVER POST
BILL RlTZ

D-2
EARTH SCIENCE LABORATORY
LIBRARIAN
EG&G IDAHO INCORPORATED
T H SMITH
ELSAM (DENMARK)
ARNE PEDERSEN
FALCON RESEARCH AND DEVELOPMENT
WILLIAM J GALYEAN
FLORIDA DEPARTMENT OF NATURAL
RESOURCES
CHARLES W HENDRY JR
FLORIDA POWER AND LIGHT COMPANY
JAMESR TOMONTO
FMC CORPORATION
MIKE WALLIS
FORD BACON AND DAVIS ENGINEERS
CONSTRUCTORS
DARRELL H CARD
BURTON J THAMER
FOSTER MILLER ASSOCIATES
INCORPORATED
GREY L RILEY
FOUNDATION SCIENCES
INCORPORATED
LOU BATTAMS
FREDERICF MELLEN GEOLOGICAL
ASSOCIATES
F F MELLEN
FSU ENVIRONMENTALTASK FORCE
SUC GENESSEO
FUGRO INCORPORATED
I CARL STEPP
GENERAL ATOMIC COMPANY
G W HANNAMAN
JAMESN SILTANEN
R F TUPNER
GEOLOGICALSOCIETY OF AMERICA
INCORPORATED
JOHNC FRYE

GESELLSCHAFT FUR KERNFORSCHUNG

MBH
HELMUT KRAUSE
HARVARD UNIVERSITY
R SIEVER
HAWAII DEPARTMENTOF LAND AND
NATURAL RESOURCES
ROBERT T CHUCK
HOWARD UNIVERSITY
GEORGE FERGUSON
IAEA (AUSTRIA)
ROBERT CATTLIN
IDAHO BUREAU OF MINES AND
GEOLOGY
MAYNARD M MILLER
IDAHO STATE UNIVERSITY
V HARRY CHARYULU
ILLINOISSTATE GEOLOGICALSURVEY
JACK A SIMON
INDIANA STATE GEOLOGIST
JOHNB PATTON
INSTITUTEOF GEOPHYSICALSCIENCES
(UK)
DAVID A GRAY
INTERNATIONALENGINEERING
COMPANY INCORPORATED
JOHNCOCAN
HEADQUARTERS OFFICE
INTERNATIONALRESEARCH AND
EVALUATION
R DANFORD
INTERNATIONALSALT COMPANY
R L FRIANT
IOWA STATE GEOLOGIST
STANLEY C GRANT
IOWA STATE UNIVERSITY
RICHARD DANOFSKY
IRT CORPdRATION
W E SELPH

GEOLOGICALSOCIETY OF CANADA
J GALE
B SANFORD
J S SCOTT

I l l RESEARCH INSTITUTE

GEOLOGICALSURVEY OF SWEDEN
OTTO BROTZEN

IAMES F MACLARENLIMITED
(CANADA)
VALERIE CASSADAY

GEORGIA DEPARTMENTOF NATURAL

RESOURCES
JOHNR GEORGE

JOHNSHOPKINS UNIVERSITY
JAREDCOHON

GEORGIA INSTITUTEOF TECHNOLOGY

GEOFFREY EICHHOLZ
LAWRENCE W FRY
J W POSTON
JOHN RUSSELL
CHARLES E WEAVER

E R BANGS

KAISER ENGINEERS INCORPORATED

W J DODSON
J S RlTCHlE
KAMAN SCIENCES CORPORATION
PAUL A ELLIS

KANSAS STATE GEOLOGICALSURVEY

WILLIAM W HAMBLETON
KBS (SWEDEN)
TONIS PAPP

KENT STATE UNIVERSITY

JIMCOWDEN
RONALD W MANUS
KENTUCKY GEOLOGICALSURVEY
DONALD C HANEY

LAW ENGINEERINGTESTING COMPANY

J G LA BASTIE
LAWRENCE BERKELEY LABORATORY
JOHNA APPS
LEWIS COHEN
PAUL A WITHERSPOON
LAWRENCE LIVERMORE LABORATORY
L B BALLOU
R J BORG
A DUBA
H C HEARD
ALFRED HOLZER JR
DANA ISHERWOOD
CAMILLE MINICHINO
L D RAMSPOlT
DONALD TOWSE
LOS ALAMOS SCIENTIFIC LABORATORY
KEAPT
J R BRIDWELL
G A COWAN
BRUCE R ERDAL
D C HOFFMAN
W C LUTH
KURT WOLFSBERG

LOS ALAMOS TECHNICAL ASSOCIATES

INCORPORATED
S E LOGAN
LOUISIANA DEPARTMENT OF
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R T SUTTON
LOUISIANA GEOLOGICALSURVEY
CHARLES S GROAT
LEO W LOUGH
LOUISIANA STATE UNIVERSITY
JEFFERY S HANOR
E B JERNICAN
JOHNLOOS
J D MARTINEZ
ROBERT L THOMS
STEVEN WHIPPLE
LOZlER
WAYNE P ACKART
MAINE STATE GEOLOGIST
ROBERT G DOYLE
MARYLAND GEOLOGICALSURVEY
KENNETH N WEAVER
MASSACHUSETTSSTATE GEOLOGIST
JOSEPH A SINNOTT

D-3

*
1

MEMBERS OF THE GENERAL PUBLIC

LINDSAY AUDIN
RANDY BREWER
HALBRODIE
A L BROKAW
IRENE DICKENSON
BILL DUESING
SHIRLEY M GIFFORD
EDWIN D GOEBEL
S GONZALES
CHARLES KILLGORE
SCOTT KRAMER
K K LANDES
NEIL MELDGIN
LOUIS MIRON
J B MUCKERHEIDE
ZORAN MUSlCKl
JOHNNESBITT
A M PIPER
M A SABET
WARREN SCHADT
KEN STOFFLET
L S TOBIAS
CHARLES TRAUTMANN
R F WALTERS
MICHIGAN STATE GEOLOGIST
ARTHUR E SLAUGHTER
MILLSAPS COLLEGE
CHARLES SALLIS
ERIK YENSON

6.

MINNESOTA GEOLOGICAL SURVEY

MATT S WALTON

MISSISSIPPI FUEL AND ENERGY

MANAGEMENT COMMISSION
P T BANKSTON
PETER J WALLEY

MISSISSIPPI GEOLOGICAL ECONOMIC

AND TOPOGRAPHICAL SURVEY
ALVIN R BICKER JR
WILLIAM H MOORE

NORTH CAROLINA DEPARTMENT OF

NATURAL RESOURCES AND
COMMUNITY DEVELOPMENT
STEPHEN G CONRAD
GEOLOGICAL SURVEY SECTION

NASA LEWIS RESEARCH CENTER

JACK B ESGAR
NATIONAL ACADEMY OF SCIENCES
JOHNPOMEROY
NATIONAL ATOMIC MUSEUM
GWEN SCHREINER
NATIONAL AUDUBON SOCIETY
DEDE ARMENTROUT
NATIONAL SCIENCE FOUNDATION
ROYAL E ROSTENBACH
NATURAL RESOURCES DEFENSE
COUNCIL
T R LASH
NEBRASKA CONSERVATION A N D
SURVEY DIVISION
VINCENT H DREESZEN

NETHERLAND SEWELL AND ASSOCIATES

CLARENCE M NETHERLAND
NEVADA BUREAU OF MINES AND
GEOLOGY
JOHN H SCHILLING
NEW HAMPSHIRE STATE GEOLOGIST
GLENN W STEWARD
NEW JERSEY STATE GEOLOGIST
KEMBLE WIDMER
NEW JERSEY INSTITUTEOF TECHNOLOGY
BEN STEVENSON
NEW MEXICO BUREAU OF MINES AND
MINERAL RESOURCES
FRANK E KOTTLOWSKI

MISSISSIPPISTATE UNlVERSlTJ
BOB T CHAPIN
RICHARD A MARSHALL
ROGER S REYNOLDS
VICTOR L ZlTTA

NEW MEXICO DEPARTMENT OF ENERGY

AND MINERALS
ERNEST CORIZ

MISSISSIPPIWATER RESOURCE DIVISION

C A SPIERS

MORGANTOWN (WV) ENERCY

RESEARCH CENTER
WILLIAM K OVERBEY

MISSISSIPPIMUSEUM OF NATURAL
SCIENCE
NATURAL HERITAGE PROGAM

NEWYORK STATEJOINT LEGISLATIVE

COMMISSION ON ENERGY SYSTEMS
ANGEL0 GRAZIO

NEFCO
JAMES T KING

MISSISSIPPIAIR AND WATER POLLUTION

CONTROL COMMISSION
CHARLES T BRANCH

MONTANA BUREAU OF MINES AND

GEOLOGY
S L GROFF

MISSOURI GEOLOGICAL SURVEY

WALLACE B HOWE

MlTSUBlSHl METAL CORP RATION

JOAN C ABENA
MONSANTO RESEARCH CORPORATION
I
K V GILBERT

NEW YORK STATE ELECTRIC AND GAS

CORPORATION
F S DOOLITTLE
PAUL ROMAR
LEWIS L STALEY
NEW YORK STATE ENERGY OFFICE
T K DE BOER
NEW YORK STATE GEOLOGICAL SURVEY
RICHARD DANCE
JAMES F DAVIS
ROBERT H FAKUNDINY
ROBERT H FlCKlES

NORTH DAKOTA STATE GEOLOGIST

LEE C GERHARD
NORTHEAST LOUISIANA UNIVERSITY
JAN FULLERTON
JOHN LEWIS
B E PRINCE
NUCLEAR ASSURANCE CORPORATION
CLAUDIA DRUM
CAROL THORPU
NUCLEAR ENERGY AGENCY (FRANCE)
F CERA
NUCLEAR FUEL CYCLE SECCION
(W GERMANY)
M HAGAN
NUCLEAR SAFETY ASSOCIATES
J A LIEBERMAN
NUCLEAR SERVICES CORPORATION
FRANCIS J KENESHEA
NUCLEAR SYSTEMS ASSOCIATES
INCORPORATED
NUCLEAR WASTE WATCHERS
HELEN LETARTE
NUS CORPORATION
W G BELTER
R J DAVIS
J DI NUNNO
M I GOLDMAN
BRUCE D GUILBEAULT
SUSAN MUTHA
BARRY N NAFT
L A STINNETT
OAK RIDGE ASSOCIATED UNIVERSITIES
H G MACPHERSON
A M WEINBERG
OAK RIDGE NATIONAL LABORATORY
A G GROFF
T F LOMENICK
W C MCCLAIN
E G ST CLAIR

OHIO DEPARTMENT OF ENERGY

ROBERT RYAN

OHIO DEPARTMENT OF NATURAL

RESOURCES
HORACE R COLLINS

OHIO EPA
JOHN NOYES
OHIO SITING COMMISSION
H KOHN

D-4

OHIO STATE UNIVERSITY

R N CHRISTENSEN
F A KULACKI
WAYNE PETTYJOHN
F UPHAM
OHIO UNIVERSITY RESEARCH INSTITUTE
GIRARD E KREBS
ADAM MARSH
OKLAHOMA GEOLOGICAL SURVEY
CHARLES J MANKIN
ONTARIO COMPANY
ROBERT BARROWS
ONTARIO HYDRO
C F LEE
OREGON DEPARTMENT OF ENERGY
J TAPPAN
OREGON STATE GEOLOGIST
DONALD A HULL
OREGON STATE UNIVERSITY
BRIAD DODD
PACIFIC GAS AND ELECTRIC COMPANY
GENE BLANC
PACIFIC NORTHWEST LABORATORIES
DON J BRADLEY '
A BRANDSTETTER
L L BURGER
J B BURNHAM
M KRIETER
A M PLATT
J R RAYMOND
R JEFF SERNE
R WALTER
E C WATSON
R D WlDRlG
L D WILLIAMS
PENNSYLVANIA DEPARTMENT OF
ENVIRONMENTAL RESOURCES
ARTHUR A SOCOLOW
PENNSYLVANIA STATE UNIVERSITY
WILLIAM A JESTER
D M ROY
WILLIAM B WHITE
MICHAEL ZOLENSKY
PORTLAND GENERAL ELECTRIC
J W LENTSCH
POTOMAC ALLIANCE
FRED MILLAR
PRINCETON UNIVERSITY
HARTMUTT KRUGMANN
G E PINDER
PROJECT REACH INCORPORATED
ROBERT BATES
PURDUE UNIVERSITY
R H JOHNSON
RAILROAD COMMISSION OF TEXAS
J H MORROW

RALPH M PARSONS COMPANY

ALVIN E SMITH
RENSSELAER POLYTECHNIC INSTITUTE
BIMAL MALAVIYA

JOHN E MOSIER
RICHARD W STAROSTECKI
M J SZULINSKI
ROBERT WILEMS

RE/SPEC INCORPORATED
PAUL F GNIRK

SENECA COUNTY (NY) DEPARTMENT OF

HEALTH
BRIAN DOMBROWSKI

RIDIHALGH EGGERS AND ASSOCIATES

J RIDIHALGH

SHAFER EXPLORATION COMPANY

WILLIAM E SHAFER

ROCHESTER GAS AND ELECTRIC

CORPORATION
L L PHILLIPS
RICHARD 1 WATTS
ROCKWELL HANFORD OPERATIONS
H BABAD
G S BARNEY
R A DEJU
B DIETZ
GEORGE C EVANS
W J KURZEKA
C W MANRY
R A SEXTON
DAVE A TURNER
D D WODRICH
D E WOOD
P A YBARRA
ROCKWEU INTERNATIONAL
R H KARLSSON
R J MERLIN1
LAWRENCE J SMITH
R E SMITH
SANDIA LABORATORIES
E H BECKNER
J F CUDERMAN
DEPARTMENT 4510
R G DOSCH
JERRY M FREEDMAN
LESLIE R HILL
THOMAS E HlNKEBElN
0 E JONES
R D KLEll
R LINCOLN
R W LYNCH
G F RUDOLF0
A R SATTLER
L w SCULLY
A E STEPHENSON
DANIEL M TALBERT
L D TYLER
W D WEART
WlPP CENTRAL FILES
SAVANNAH RIVER LABORATORY
J L CRANDALL
R G GARVIN
H J GROH
C H ICE
F D KING
IW MARINE
W C RElNlG
SCIENCE APPLICATIONS
INCORPORATED
SOPHIE CARMAN
C W CRAYEN
RONALD HOFFMANN
DAVID H LESTER

SIERRA CLUB MISSISSIPPICHAPTER

id
3

S M STOLLER CORPORATION
W KUPP
SOLUTION MINING RESEARCH
INSTITUTE
H DIAMOND
SOUTH CAROLINA STATE GEOLOGIST
NORMAN K OLSON
SOUTH DAKOTA SCHOOL OF MINES
AND TECHNOLOGY
W GRAMS
SOUTH DAKOTA STATE GEOLOGIST
DUNCAN J MCGRECOR
SOUTHERN TIER CENTRAL REGIONAL
PLANNING AND DEVELOPMENT BOARD
KEVIN BYRNE
2

SOUTH PLAINS ASSOCIATION

COMMUNITY DEVELOPMENT
PLANNER
SRI INTERNATIONAL
R K WHITE

STANFORD UNIVERSITY
KONRAD B KRAUSKOFF
P KRUGER
IRWIN RENISON
STATE UNIVERSITY COLLEGE
(CORTLAND)
DANIEL J BRENNAN
STATE UNIVERSITY COLLEGE (BUFFALO)
IRVING H TESMER
STATE UNIVERSITY OF NEW YORK
(ALBANY)
KEVIN BURKE
STATE UNIVERSITY OF NEW YORK
(BINGHAMTON)
ALBERT A DEKIN JR
T W DONNELLY
STATE UNIVERSITY OF NEW YORK
(SYRACUSE)
DONALD F BEHREND
PETER BLACK
ARTHUR R ESCHNER
NORMAN RICHARDS

D-5

STEARNS-ROGER ENGINEERING
COMPANY
J H JONES

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STEPHEN F AUSTIN UNIVERSITY

JAMES E CORBIN
ELRAY NIXON
STONE AND WEBSTER ENGINEERING
CORPORATION
CRAIG F GROCHMAL

3
SUL ROSS STATE UNIVERSITY
BATON H WARNOCK
SYRACUSE UNIVERSITY
LEE HARRINGTON
ERNEST H MULLER
SYSTEMS SCIENCE AND SOFNYARE
PETER LAGUS
TENNESSEE STATE GEOLOGIST
ROBERT E HERSHEY

+'

TEXAS A&M UNIVERSITY

J HANDIN
ROY W HANN JR
D K PARRISH
STEPHEN RITER
J RUSSELL
JOSEPHL SCHUSTER
JIMSMATHERS
JAMES G TEER
TEXAS CHRISTIAN UNIVERSITY
JACK L WALPER
TEXAS DEPARTMENT OF HEALTH
JOENANUS
TEXAS ENERGY ADVISORY COUNCIL
ALVIN ASKEW
TEXAS TECHNICAL UNIVERSITY
JOHNS MECHAM
BILL MEYER-OAKES
TRW SYSTEMS AND ENERGY
E R CHRISTIE
F MEYERS
HERBERT N ROSENBERG

TULANE UNIVERSITY
CHARLES CARTER
WALTER MASON
TUSKEGEE I N S T I M E
IRA C DILLON

LJ

UNIVERSITY OF AKRON
R G CORBETT
UNIVERSITY OF ARIZONA
JAAK DAEMEN
STANLEY N DAVIS

CHARLES LYON
JAMES C McCRAY
R G POST
ROBERT L SEALE
DAVID L SOUTH
UNIVERSITY OF CALIFORNIA (BERKELEV)

UNIVER~TY OFCALIF
ANGELES)
D OKRENT
UNIVERSITY OF FLORIDA
WILLIAM H ELLIS
M J OHANIAN
UNIVERSITY OF GEORGIA
J D SPAULDING
DAVID B WENNER

UNIVERSITY OF MISSOURI
(KANSAS CI)
TRUMAN STAUFFER
UNIVERSITY OF MISSOURI (COLUMBJA)
W D KELLER
WALTER MEYER
DARROL H TIMMONS
UNIVERSITY OF MISSOURI (ROLLA)
NICK TSOULFANIDIS
UNIVERSITY OF NEW MEXICO
E LOGAN
D M WOODALL
UNIVERSITY OF NORTH CAROLINA
(CHAPEL HILL)
JAMES H CRAWFORD

UNIVERSITY OF HAWAII AT M A N O A
MURLl H MAUGHNANI

UNIVERSITY OF NOTRE DAME

JOHN LUCEY
K T YANG

UNIVERSITY OF HOUSTON
JOHN R HOWELL

UNIVERSITY OF OKLAHOMA
KENNETH S JOHNSON

UNIVERSITY OF ILLINOIS
FRED A DONATH
GLENN GERDIN

UNIVERSITY OF PENNSYLVANIA
SAT1 SADHAL

UNIVERSITY OF INDIANA
J B DROSTE
HAYDN H MURRAY
CHARLES J VlTALlANO
UNIVERSITY OF KANSAS
LOUIS F DELWIG
UNIVERSITY OF LOWELL
WILLIAM FILLIPONE
JOSEMARTIN
JAMES R SHEFF
UNIVERSITY OF MARYLAND
KAZGS ALMENAS
DICK DUFFEY
FRANK M U N N O
UNIVERSITY OF MICHIGAN
JOHNS KING
UNIVERSITY OF MINNESOTA
S L CROUCH
E N LINDMER
D H YARDLEY
UNIVERSITY OF MISSISSIPPI
CLYDE E COOK
FREDERICK MANLEY
ED MEEK
VELON MINSHEW
MARLIN PURDIE

UNIVERSITY OF PITTSBURGH
B L COHEN
UNIVERSITY OF RHODE ISLAND
EDWARD P LAlNE
ROBERT L McMASTER
UNIVERSITY OF SOUTHERN MISSISSIPPI
CHARLES R BRENT
RALPH D CROSS
GEORGE PASSONEY
OSCAR L PAULSON JR
JAMESW PINSON
JOHN N SKATES
UNIVERSITY OF TENNESSEE
J B FUSSELL
UNlVERSlTY OF TEXAS AT ARLINGTON
CHARLES I SMITH
UNIVERSITY OF TEXAS AT AUSTIN
RICHARD ASHLEY
L F BROWN
E LlNN DRAPER JR
WILLIAM L FISHER
EARNEST F GLOYNA
JOHN B GORDON
CLARK HUBBS
E C JONAS
DALE KLEIN
JOED LEDBETTER
G WERMUND

D-6
UNIVERSITY OF UTAH
JOHNS ALLEN
DUNCAN FOLEY
FRANK C HACKMAN
S K KAO
ROBERT C PENDLETON
HOWARD P ROSS
GARY M SANDQUIST
EDWARD B SISSON
UNIVERSIlY OF VIRGINIA
T G WILLIAMSON

US DEPARTMENT OF ENERGY (OAK

RIDGE)
T ENSMINGER
DEWEY E LARGE
TECHNICAL INFORMATION CENTER

US DEPARTMENT OF ENERGY
(RICHLAND)
T A BAUMAN
R B GORANSON
D J SQUIRES
F R STANDERFER

UNIVERSITY OF WISCONSIN
CHARLES W MAYNARD
JOHNB HElL

US DEPARTMENT OF ENERGY
(RICHLAND-COLUMBUS)

U S DEPARTMENT OF COMMERCE
L H CEVANTMAN

US DEPARTMENT OF ENERGY
(SAN FRANCISCO)
C D JACKSON
JOHNMUHLESTEIN

US DEPARTMENT OF ENERGY
(ALBUQUERQUE)
D DAVIS
DORNEST SCHUELER
WlPP PROJECT

US DEPARTMENTOF ENERGY (CHICAGO)

R NACK
US DEPARTMENT OF ENERGY (DENVER)
JACK 0 BRIEN
HARRY SMITH
US DEPARTMENT OF ENERGY (GRAND
JUNCTION)
FRANK ECKERSON
J ELLIS
US DEPARTMENT OF ENERGY (IDAHO
FALLS)
J P HAMRIC
J WHITSETT
US DEPARTMENT OF ENERGY (LAS
VEGAS)
-R D BETTERIDCE
J B COTTER
D DUNCAN
M E GATES
J R GlLPlN
K N JOY
M P KUNICH
H L MELANCON
R M NELSON JR
NEVADA TECHNICAL LIBRARY
R W NEWMAN
J ROBERTS
R W TAFT
T E WADE

US DEPARTMENT OF ENERGY (NEW

YORK)
CHARLES BAXTER

J 0 NEFF

us DEPARTMENT OFENERGY
(SAVANNAH RIVER)
LAWRENCE W FRY
T B HlNlMAN
US DEPARTMENT OF ENERGY-PUBLIC

READING/DOCUMENT ROOMS
ALBUQUERQUE OPERATIONS OFFICE
CHICAGO OPERATIONS OFFICE
DOE HEADQUARTERS
IDAHO OPERATIONS OFFICE
NEVADA OPERATIONS OFFICE
OAK RIDGE OPERATIONS OFFICE
RICHLAND OPERATIONS OFFICE
SAN FRANCISCO OPERATIONS OFFICE
SAVANNAH RIVER OPERATIONS
OFFICE
REGION IX OFFICE-SAN FRANCISCO
WASHINGTON DC

US DEPARTMENT OF ENERGY REGION IBOSTON

DUANE DAY
US DEPARTMENT OF ENERGY REGION
11-NEW YORK
LENORE L~DMAN
U S DEPARTMENT OF ENERGY REGION
Ill-PHILADELPHIA
MARIA MARKS

US DEPARTMENT OF ENERGY REGION

IV-ATLANTA
DAVID ALANIZ

US DEPARTMENT OF ENERGY REGION

V-CHICACO
PHILLIP T ZEN1
US DEPARTMENT OF ENERGY REGION
VI-DALLAS
WILLIAM NlKOLlS

US DEPARTMENT OF ENERGY REGION

VII-KANSAS CITY
D FONTANE
PATRICK HAND
U S DEPARTMENT OF ENERGY REGION
Vlll-LAKEWOOD
JLC GOSNEY
SIGRID HIGDON

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US DEPARTMENT OF ENERGY REGION

IX-SAN FRANCISCO
JAMES RUSSELL

US DEPARTMENT OF ENERGY REGION

X-SEATllE
LIBRARY
LEE JOHNSON
US DEPARTMENT OF ENERGY
(WASHINGTON DC)
W W BALLARD
EUGENE F BECKETT
C R COOLEY
J C DEMPSEY
JOHNM DEUTCH
WARREN EISTER
MARK W FREl
C H GEORGE
j L GILBERT
0 P GORMLEY
DONALD H GROELSEMA
S L HACK
C A HEATH
KEITH KLEIN
CYRUS KLINGSBERG
JIMLANDERS
ROGER LE GASSIE
J L LIVERMAN
E F MASTAL
BEN McCARTY
S MEYERS
W E MOTT
J F MULLANEY
CARL NEWTON
RAY NC
A G PETTIT
MURIEL SCARBOROUGH
J E SEYMOUR
OSCAR STRADINCER
RALPH STEIN
JIMTURl
D L VEITH
SUSAN WELLS
J B WORK
H H YOUNG

US M A
S GOLDBERG
A S GOLDIN
ANDREW J LETER
JAMES E MARTIN
PETER E McGRATH

D-7

US EPA (Continued)
JAMES NEIHEISEL
JOHNL RUSSELL
DSSMITH
W A WILLIAMS

USGS-BATON ROUGE
R L HOSMAN

USGS-DENVER
JOHND BREDEHOEFT
JEFFE CLEVELAND
WILLIAM W DUDLEY JR
JULES FRIEDMAN
L M GARD
ROBERT J HITE
D L HOOVER
JOHNC REED JR
G W SHURR
ROBERT I TILLING
USGS-HOUSTON
JERRY CARR
USGS-ITHACA
0 J COSNER
USGS-jACKSON
E H BOSWELL

USGS-LAKEWOOD
D O N R MABEY
WILLIAM S TWENHOFEL
RICHARD WADDELL
USGS-MENLO PARK
J D BYERLEE
GERRY CZAMANSKE
EVERETT JENNE
ARTHUR H LACHENBRUCH
JACOB RUBIN
USGS-RESTON
G D DEBUCHANANNE
ROBERT M HAMILTON
PETER R STEVENS
DAVID B STEWART
NEWELL J TRASK JR
WARREN W W O O D

U S NUCLEAR REGULATORY
COMMISSION
C BARTLEll
ORMEN E BASSEll
REGIS R BOYLE
ROBERT BUDNITZ
MICHAEL C CULLINGFORD
J J DAVIS
JAY B DURST
S FUCIGNA
E E HELD
H E LEFOURE
J MALAR0
MANAGER-WASTE ENVIRONMENTAL
STANDARDS PROGRAM
JOHN B MARTIN
7J NICKOLSON
EDWARD O'DONNELL
PROJECTOFFICER-SAFEGUARDS OF
HLW REPOSITORIES CONTRACTS
E RECNIER
GARY ROBBINS
D M ROHRER
SHELDON SCHWARTZ
S H SMILEY
U S NUCLEAR REGULATORY RESEARCH
CLYDE JUPITER
UTAH GEOLOGICALAND MINERAL
SURVEY
DONALD T MCMILLAN
UTAH STATE UNIVERSITY
JAY C ANDERSON
JACK T SPENCE
VANDERBILT UNIVERSITY
FRANK L PARKER
VAUGHN HANSEN ASSOCIATES
PAUL B BLACKER
VERMONT STATE GEOLOGJST
CHARLES A RATTE

VIRGINIA STATE GEOLOGIST

ROBERT C MlLlCl
WASHINGTON STATE GEOLOGIST
VAUGH E LIVINGSTON IR
WASTE ISOLATION PILOT PLANT
R K BROWN
WAYNE STATE UNIVERSITY
JAMES A WOODYARD
WESTINGHOUSE ELECTRIC
CORPORATION
P BRADBURY
A R HAKL
GEORGE P SABOL
WESTINGHOUSE HANFORD COMPANY
ALBERT G BLASEWITZ
WESTINGHOUSE WlPP PROJECT
C L HOHMANN
WEST VIRGINIA STATE GEOLOGIST
ROBERT B ERWIN
WISCONSIN GEOLOGICALAND
NATURAL HISTORY SURVEV
MEREDITH E OSTROM
WISCONSINSTATE ENERGY OFFICE
JOHNH THOMAN
WOODWARPCLYDE CONSULTANTS
HANS M EWOLDSEN
LIBRARY
WYOMING STATE GEOLOGIST
DANIEL N MILLER JR
VALE UNIVERSITY
ROBERT M CARRELS

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