Clays and Clay Minerals, Vol.47, No. 3, 286-296, 1999.

THE KINETICS OF THE S M E C T I T E TO ILLITE T R A N S F O R M A T I O N IN

CRETACEOUS BENTONITES, CERRO NEGRO, NEW MEXICO

W. CRAWFORD ELLIOTT, 1 ANDREA M . EDENFIELD, 1 J. MARION WAMPLER, 2 GERALD MATISOFF, 3 AND

PHILIP E. LONG 4
Department of Geology, Georgia State Univerity, Atlanta, Georgia 30303, USA
2 School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia 30332, USA
3 Department of Geological Sciences, Case Western Reserve University, Cleveland, Ohio 44106, USA
4 Pacific Northwest National Laboratory, MS K6-91, RO. Box 999, Richland, Washington 99352, USA

A b s t r a c t - - T h e thermal effects, as well as the survivability and origins of microorganisms in Cretaceous

rocks, are evaluated from the timing and extent of the smectite to illite transformation in Cretaceous
bentonites collected from cores outside the thermal aureole of the Pliocene Cerro Negro volcanic neck.
Overall, randomly ordered mixed-layered illite-smectite (I-S) is the predominant clay mineral in these
bentonites, and the K-Ar ages of I-S range from 36 to 48 Ma (21 analyses, two additional analyses were
outside this range). Increased temperature from burial is thought to be the primary factor forming I-S in
these bentonites. Kinetic model calculations of the smectite to illite transformation are also consistent
with I-S formed by burial without any appreciable thermal effects due to the emplacement of Cerro
Negro. In a core angled toward Cerro Negro, the percentages of illite layers in I-S from the bentonite
closest to Cerro Negro are slightly higher (32-37%) than in most other bentonites in this study. The K-
Ar ages of the closest I-S are slightly younger as a group (38-43 Ma; Average 41 Ma; N = 4) than
those of I-S further from Cerro Negro in the same core (41-48 Ma; Average = 44 Ma; N 6). A small
amount of illite in this I-S may have formed by heat from the emplacement of Cerro Negro, but most
illite formed from burial. Vitrinite reflectance, however, appears to record the effects of heating from
Cerro Negro better than 1-S. Tentatively, the temperature of this heat pulse, based on vitrinite data alone,
ranged from 100 to 125~ and this is most evident in the CNAR core. The upper temperature, 125~
approximates the sterilization temperatures for most microorganisms, and these temperatures probably
reduced a significant portion of the microbial population. Thermophiles may have survived the increased
temperatures from the combined effects of burial and the intrusion of Cerro Negro.
Key Words--Bentonite, Cerro Negro, Cretaceous, Illite, I-S, K-Ar, Kinetics, Microorganisms, New Mex-
ico, Smectite.

INTRODUCTION c o n v e n t i o n a l K - A r ages o f I-S are i n t e r p r e t e d as m e a n ,

Studies c o m b i n i n g m i n e r a l o g i c a n d c h r o n o l o g i c
data a n d m a t h e m a t i c a l m o d e l s were successful in in-
c r e a s i n g the u n d e r s t a n d i n g o f the f o r m a t i o n o f diage-
netic illite-smectite (I-S) in argillaceous rocks. T h e s e
results w e r e also useful in s t u d y i n g the t h e r m a l his-
tories o f s e d i m e n t a r y b a s i n s (e.g., H o f f m a n a n d H o w -
er, 1979; Pollastro, 1993; H u a n g et al., 1993; A l t a n e r
a n d Y l a g a n , 1997). T h e s t a c k i n g order o f I-S was u s e d
to c o n s t r a i n t h e m a x i m u m t e m p e r a t u r e o f burial,
w h e r e a s the a g e o f I-S signified the t i m e o f m a x i m u m
t e m p e r a t u r e due to b u r i a l (e.g., H o f f m a n a n d Hower,
1979; Elliott et al., 1991; Pollastro, 1993). T h e t i m i n g
of b a s i n - w i d e fluid m i g r a t i o n s a n d p e t r o l e u m g e n e r a -
tion a n d m i g r a t i o n was i n f e r r e d f r o m the K - A r ages
of I-S a n d d i a g e n e t i c illite (e.g., L e e et al., 1989;
B a r n e s e t al., 1992). T h e m e c h a n i s m ( s ) b y w h i c h
s m e c t i t e t r a n s f o r m s to I-S r e m a i n s a n o p e n q u e s t i o n
a n d this m e c h a n i s m m a y v a r y in d i f f e r e n t types o f
argillaceous r o c k s ( B o l e s a n d Franks, 1979; B e t h k e
and Altaner, 1986; E b e r l et al., 1990; A l t a n e r a n d Yla-
gan, 1997).
U n d e r burial d i a g e n e t i c t e m p e r a t u r e s < 1 5 0 ~ I-S
retains r a d i o g e n i c a l l y p r o d u c e d A r (i.e., *4~ and
or t i m e - i n t e g r a t e d , ages o f illitization ( A r o n s o n a n d
Hower, 1976). T h e d u r a t i o n o f the t r a n s f o r m a t i o n was
e s t i m a t e d i n several studies t h r o u g h m a t h e m a t i c a l
m o d e l s e m p l o y i n g A r r h e n i u s rate law e x p r e s s i o n s de-
s c r i b i n g the k i n e t i c s of this t r a n s f o r m a t i o n (Pytte a n d
R e y n o l d s , 1989; Elliott e t al., 1991; Velde a n d Vas-
seur, 1992; Elliott a n d M a t i s o f f , 1996). T h e ability to
derive b o t h t i m e a n d t e m p e r a t u r e o f m a x i m u m h e a t i n g
m a k e s d i a g e n e t i c I-S a useful m i n e r a l for b u r i a l a n d
b a s i n h i s t o r y r e c o n s t r u c t i o n s . O f note, D o n g et at.
(1995) f o u n d that the 4~ total gas age o f a dia-
genetic illite was c o n c o r d a n t w i t h the c o n v e n t i o n a l K-
A r age m e a s u r e d for that s a m e illite, s h o w i n g the po-
tential o f A r - A r m e t h o d s to p r o v i d e precise ages o f I-
S. T h e a p p l i c a t i o n o f the 4~ s t e p - h e a t i n g tech-
n i q u e to I-S h a s also the p o t e n t i a l to p r o v i d e a c c u r a t e
ages o f b o t h detrital a n d d i a g e n e t i c e n d - m e m b e r s o f
b i n a r y m i x t u r e s o f m u s c o v i t e a n d d i a g e n e t i c I-S. T h i s
t e c h n i q u e c a n p o t e n t i a l l y lead to i m p r o v e d age deter-
m i n a t i o n s o f d i a g e n e t i c illite in shales ( O n s t o t t et al.,
1997).
T h i s s t u d y is part o f a t h o r o u g h e v a l u a t i o n o f the
t h e r m a l h i s t o r y a n d t h e g e o m i c r o b i o l o g y of t h e C r e -
t a c e o u s r o c k s i n t r u d e d b y C e r r o N e g r o 3.39 M a . A n

Copyright 9 1999, The Clay Minerals Society 286

Vol. 47, No. 3, 1999 Kinetics of the smectite transformation in Cretaceous bentonites
Figure 1. Geologic cross section of Cerro Negro showing Cretaceous Dakota Group and Mancos Shale, Cerro Negro, and
the locations of three wells (modified after Frederickson et al., 1997). The main vent of Cerro Negro is out of the plane of
cross section by 25.
original goal was to constrain the maximum temper-
atures caused by heat from Cerro Negro by studying
the timing and extent of the smectite to illite transfor-
mation. Such maximum temperature could be related
to the origins and survivability of microorganisms de-
scribed by Frederickson et al. (1997) and Krumholz et
al. (1997) in these Cretaceous rocks. Where the tem-
peratures derived from the emplacement of Cerro Ne-
gro were sufficiently high to have sterilized these
rocks (-->125~ then microorganisms found in adja-
cent strata must post-date the intrusion and must have
been transported into these rocks by groundwater flow.
Alternatively, if the rocks sampled never reached suf-
ficiently high temperatures to kill microorganisms,
then the in situ microorganisms may be endemic to
these strata.
GEOLOGIC SETTINGAND METHODS
Three wells (CNV, CNVR, and CNAR) were drilled
through Cretaceous rocks belonging to the Dakota
Group and Mancos Shale in proximity to Cerro Negro
(Figure 1). Two of these wells reached the Jurassic
Morrison Formation. The depositional ages of the Cre-
taceous strata studied herein span from 88 to 93 Ma.
The details regarding the drilling and collection of
cores were described by RE. Long and J.K. Frederick-
son (unpubl. data, 1995) and Frederickson et al.
(1997). The 4~ Ar plateau age of Cerro Negro is
3.39 + 0.02 Ma; the evolution and chronology of the
volcanic necks in the Rio Puerco Valley were sum-
marized by Hallett (1994) and Hallett et al. (1997).
Thin basaltic dikes transect the C N A R core in the low-
287
er Dakota Group and Morrison Formation (Figure 1).
The thicknesses of these dikes range from 0.2 to 1 m.
Abundant bentonites are found in the shale members
of the Dakota Group and in the Mancos Shale at Cerro
Negro and throughout the Western Interior Basin
(McGookey, 1972).
Burial curves for Cretaceous formations at Cerro
Negro were constructed by using "Subside! A Basin
Analysis Program" (Wilkerson and Hsui, 1989). This
program is a backstripping method that includes de-
compaction and sediment removal corrections (see
Sclater and Christie, 1980, for equations and deriva-
tions). The stratigraphic sequence (thickness data) for
the Cerro Negro region was used to derive these burial
curves (Baars et al., 1988). The thickness of Tertiary
sediments that may have overlain Cerro Negro is un-
certain, therefore a burial curve was constructed with-
out significant unconformities that best fit the time-
temperature history of these rocks in proximity to Cer-
ro Negro. The uplift and erosion history are less well
constrained than burial and are based primarily on re-
gional tectonic events, the level of erosion at present,
and the level of erosion at the time of emplacement
of Cerro Negro. The burial curves for the Oak Canyon
Shale Member of the Dakota Group and the Mancos
Shale at Cerro Negro are shown in Figure 2. These
burial curves were used to derive Lopatin time-tem-
perature index (TTI) values (Waples, 1980). Calculat-
ed vitrinite values and maximum temperatures were
estimated from the TTI using the nomographs for Easy
%Ro of Sweeney and Burnham (1990). In terms of the
estimation of Ro from TTI, the Easy %Ro method is
288
,35, ,8~ .... 7,5, , ,5,5 ,, ,5,5 ....
0.5
~ 0.75
1.25
1.75
,95 85
,
75
,
65
,
55
Time
Figure 2. Burial curves for Mancos Shale and Oak Canyon
Member sediments at Cerro Negro. The upper curve de-
scribes the burial of the Mancos Shale and the lower curve
describes the burial of the Oak Canyon Member. Cretaceous
rocks were buried progressively deeper during the late Cre-
taceous Period and into the early Tertiary Period as a result
of the Laramide Orogeny. Uplift to present depths began
slowly at 55 Ma and increased markedly at 15 Ma. Cerro
Negro later intruded these strata 3.4 Ma ago (Hallett et al.,
1997).
similar to the Lopatin method; the Easy %Ro method,
however, considers the rates of beating by different
geologic processes (e.g., hydrothermal heating, basinal
burial).
Twenty to thirty grams of each bentonite sample
were soaked overnight in deionized water and then
treated at 50~ to remove carbonate, organic carbon,
and iron oxides following the methods of Jackson
(1979). These treatments leave I-S Na-saturated but do
not have adverse effects on the K - A r systernatics of I-
S (e.g., Elliott and Aronson, 1987; Lee et al., 1989),
Sand and silt (>20 txm), coarse clay (2-20 p~m), and
clay ( < 2 I~m) size fractions were obtained by timed
settling and centrifugation. Submicron fractions were
obtained by centrifugation. The clay minerals were
identified using a Philips Model 12045 X-ray Diffrac-
tometer equipped with the MDI Databox. Air-dried,
glycol-solvated, and heated (550~ oriented clay min-
eral separates were analyzed on glass slides from 2 to
32 ~ at 1 ~ with C u K a X-radiation with a
graphite monochromator. The stacking order of illite
layers in I-S was determined by the procedures of
Hower (1981). The 002(10 A)/003(17 A) mixed-layer
peak was used to quantify the percentage of illite lay-
ers in I-S (Reynolds and Hower, 1970). To relate the
measured positions of this peak to percentages of illite
layers in I-S, a "best fit" curve was constructed
through points plotted from the percentage of illite lay-
ers versus the 002(10 ,~)/003(17 ,~) peak position data
listed in Table 7.3 of Moore and Reynolds (1989). Un-
certainties were also estimated from this "best fit"
curve by noting the distances between the "best fit"
curve and the points used to construct it (Moore and
Reynolds, 1989). The uncertainties range from < 5 %
illite layers for I-S with <20% illite layers to +5 %
Elliott et al. Clays and Clay Minerals
.~ .... 3,5 .... 2,5 .... 1,5 .... 5 -o
illite layers for I-S with > 2 0 % illite layers. The clay
mineralogy, stacking order of I-S, percentages of illite
layers in I-S, and bentonite depths measured from the
0,5 tops of cores are presented in Table 1.
0.75
Powdered samples of I-S for Ar isotopic analyses
and K analyses were weighed on a Sartorius micro-
balance. The sample sizes for these analyses ranged
.25 from 50 to 130 mg for Ar isotopic analyses and 9 to
13 mg for K. Potassium was determined by atomic
absorption spectrophotometry. I-S samples were dis-
,
45
.
35
.
25
. .
15 5
1.75 solved in a 10:1 HF:HC104 mixture and then heated
(Ma) to dryness. The resultant perchlorate salts of major el-
ements were diluted with a mixture of nitric acid (0.25
M), LiC1 (0.025 M), and CsC1 (0.0025 M). The ab-
sorption by K was measured from this diluted solution
and the concentration of K was determined by com-
paring the measured absorption to a calibration curve
developed from a series of reference solutions having
known K concentrations. The mean of four analyses
of the diluted solution was used to calculate the K
content reported for each sample.
For the Ar isotopic analyses, each I-S sample was
fused in a resistance heater after introduction of a
known amount of 3SAr into the extraction line. Two
U-tube traps, each featuring an inner finger containing
liquid O2 within an outer U-tube surrounded by liquid
N2, w e r e used sequentially to remove water and CO2
before the extracted gases reacted with heated Ti.
These traps were effective in removing water and CO2
and retained only a negligible amount of Ar. The
weight after vacuum drying was used for subsequent
age calculations. The LP-6 Biotite interlaboratory ref-
erence sample was analyzed twice for its radiogenic
Ar content (i.e., *4~ The amounts of *4~ mea-
sured from LP-6 were 19.14 and 19.28 nmol g 1, and
these values were very close to the accepted value of
19.30 nmol g-~ (Odin, 1982). Further details regarding
the K and Ar analyses are in Edenfield (1998).
Three mathematical models were used to simulate
the smectite to illite transformation in the Mancos
Shale and the Oak Canyon Member (i.e., Pytte, 1982;
Velde and Vasseur, 1992; Huang et al., 1993). Each
model features a different expression to describe the
kinetics of the transformation. The burial curves (Fig-
ure 2) and a pore water K concentration of 200 ppm
were used in all three models (Altaner, 1985); the ad-
ditional parameters as well as the applications of these
models to diverse geologic settings were described by
Elliott and Matisoff (1996). Two types of simulations
were employed for each of the three models. The first
employed a constant geothermal gradient of either
25~ km -1 or 35~ km 1 The second employed a con-
stant geothermal gradient from the date of deposition
to 4 Ma (approximately the time of intrusion of Cerro
Negro) followed by a higher geothermal gradient
(75~ km i or 105~ km -1) for the last 4 Ma to pre-
sent. This latter scenario describes hypothetical and
Vol. 47, No. 3, 1999 Kinetics of the smectite transformation in Cretaceous bentonites 289

Table 1. Clay mineralogy and percentage of illite layers in I-S.

Measured Size
depth ~ fraction Clay 1 in I-S
Well, formation (m) (Ixm) mineralogy (%)

CNAR, Mancos Sh. 95.79-95.97 <2 I-S (random), kaolinite <2

CNAR Whitewater Arroyo Sh. 307.70 307.77 <2 kaolinite, I-S (random) 45 -+ 5
CNAR Whitewater Arroyo Sh. 307.70-307.77 <0.25 I-S (random), kaolinite 32 _+ 5
CNAR Whitewater Arroyo Sh. 313.32-313.35 <2 I-S (random), kaolinite 19 + 5
CNAR Whitewater Arroyo Sh. 313.32-313.35 1-2 I-S (random), kaolinite 20 + 5
CNAR Whitewater Arroyo Sh. 313.32 313.35 <0.25 I-S (random), kaolinite 10 -+ <5
CNAR Oak Canyon Member 407.16-407.31 <2 I-S (random), kaolinite 4 _+ <5
CNAR Oak Canyon Member 420.73-420.90 <2 I-S (random), kaolinite 33 _+ 5
CNAR Oak Canyon Member 420.73-420.90 <0.25 I-S (random), kaolinite 26 _+ 5
CNAR, Oak Canyon Member 441.31-441.34 <2 I-S (random), kaolinite 37 _+ 5
CNAR, Oak Canyon Member 441.31-441.34 <0.25 I-S (random), kaol (tr.) 32 + 5
CNV, Whitewater Arroyo Sh. 142.3-143.6 <2 I-S (random), kaolinite 14 _+ <5
CNV, Whitewater Arroyo Sh. 148.4 150.0 <2 kaolinite, I-S (random) 13 -+ <5
CNV, Oak Canyon Member 202.2 <2 I-S (random), kaolinite 30 _+ 5
CNV, Oak Canyon Member 202.2 <0.25 I-S (random), kaolinite 20 -+ 5
CNVR, Oak Canyon Member 202.75-203.25 <2 I-S (random), kaolinite 23 +- 5
CNVR, Oak Canyon Member 202.75-203.25 1-2 I-S (random), kaolinite 26 +- 5
CNVR, Oak Canyon Member 202.75-203.25 <0.25 I-S (random), kaolinite 26 _+ 5
CNVR, Oak Canyon Member 226.30-226.32 <2 I-S (random), kaolinite 35 -+ 5
CNVR, Oak Canyon Member 226.30-226.32 1-2 I-S (random), kaolinite 45 _+ 5
CNVR, Oak Canyon Member 226.30-226.32 <0.25 I-S (random) 20 + 5
CNVR, Oak Canyon Member 226.50-226.52 <2 I-S (random) 6 _+ <5
CNVR, Oak Canyon Member 226.52-226.56 <2 I-S (random) 8 -+ <5
CNVR, Oak Canyon Member 226.65-226.68 <2 I-S (random) 8 _+ <5
CNVR, Oak Canyon Member 226.72-226.76 <2 I-S (random) 13 + <5
CNVR, Oak Canyon Member 226.80-226.82 <2 I-S (random) 18 _+ <5
CNVR, Oak Canyon Member 226.82-226.84 <2 I-S (random), kaol (tr.) 18 + <5
CNVR, Oak Canyon Member 227.38-227.40 <2 I-S (random), kaolinite 7 -+ <5

For CNAR, depths are those measured from top of core.

m a x i m u m heating d e r i v e d f r o m the e m p l a c e m e n t o f 30%, than in W h i t e w a t e r A r r o y o Shale (Table 1; Fig-

Cerro Negro.
Vitrinite reflectances ( V R o ) w e r e m e a s u r e d on ker-
o g e n p r e p a r e d b y standard techniques. K e r o g e n w a s
isolated b y sink-float at 1.8 g ml -t. In t h e s e cores, the
k e r o g e n type w a s vitrinite d e r i v e d f r o m " w o o d y "
plant precursors. T w e n t y reflectance points w e r e m e a -
sured on each s a m p l e using rotational polarization.
Partially o x i d i z e d organic matter, inertinite, and weath-
ered vitrinite w e r e not m e a s u r e d . Vitrinite reflectance
data w e r e m e a s u r e d b y C a r b o n C o n s u l t a n t s Interna-
tional, Murphysboro, Illinois u n d e r contract to Pacific
N o r t h w e s t National Laboratory.
RESULTS
Clay mineralogy
R a n d o m l y o r d e r e d I-S is the p r e d o m i n a n t clay m i n -
eral in t h e s e b e n t o n i t e s a l t h o u g h kaolinite is a m i n o r
p h a s e in m a n y o f the clay fractions (Table 1). T h e
p e r c e n t a g e o f illite layers in I-S ranges f r o m < 2 % (es-
sentially smectite) to 45%. In the C N V well, three b e n -
tonites w e r e collected, t w o f r o m the W h i t e w a t e r Ar-
royo Shale at 1 4 2 . 3 - 1 4 3 . 6 m and at 1 4 8 . 4 - 1 5 0 . 0 m, a
third f r o m the Oak C a n y o n M e m b e r at 202.2 m (Table
1; Figure 3a). T h e p e r c e n t a g e o f illite layers in I-S is
slightly h i g h e r in the d e e p e r O a k C a n y o n M e m b e r , to
ure 3a). I-S o f the < 0 . 2 5 ixm-fraction o f the d e e p e s t
b e n t o n i t e has a s m a l l e r p e r c e n t a g e o f illite layers
(20%) than the < 2 ixm-fraction (30%). A s s h o w n be-
low, the K - A r ages o f t h e s e t w o size fractions o f this
I-S are essentially equal.
In well C N V R , t w o b e n t o n i t e s w e r e collected f r o m
the O a k C a n y o n M e m b e r , at 2 0 2 . 7 5 - 2 0 3 . 2 5 m and at
2 2 6 . 3 0 - 2 2 6 . 8 4 m (basal c o n t a c t at 227.10 m), and a
shale was c o l l e c t e d at 2 2 7 . 3 8 - 2 2 7 . 4 0 m (Table 1; Fig-
ure 3a). The p e r c e n t a g e o f illite layers in I-S f r o m the
h i g h e s t b e n t o n i t e ( 2 0 2 . 7 5 - 2 0 3 . 2 5 m) in this core was
26%. S e v e n s u b s a m p l e s w e r e c o l l e c t e d f r o m the thick
b e n t o n i t e at 2 2 6 . 3 0 - 2 2 7 . 1 0 m, and the p e r c e n t a g e s o f
illite in I-S r a n g e f r o m a high o f 4 5 % in the u p p e r m o s t
b e n t o n i t e s u b s a m p l e ( 2 2 6 . 3 0 - 2 2 6 . 3 2 rn) to 6 - 8 % illite
in I-S in the three s u b s a m p l e s c o l l e c t e d f r o m the in-
t e n o r o f this thick b e n t o n i t e at 2 2 6 . 5 0 - 2 2 6 . 6 8 m. T h e
p e r c e n t a g e s o f illite layers in I-S i n c r e a s e again t o w a r d
the basal c o n t a c t o f this b e n t o n i t e to 18% at 2 2 6 . 8 2 -
226.84 m, still nearly 30 c m a b o v e the basal c o n t a c t
at 227.10 m. The d e e p e s t s a m p l e ( 2 2 7 . 3 8 - 2 2 7 . 4 0 m )
is a clayey-silty shale in w h i c h the p e r c e n t a g e o f illite
in I-S is 7%.
Six b e n t o n i t e s w e r e c o l l e c t e d f r o m the a n g l e d well,
C N A R (Figure 1; Table 1). T h e d e p t h s o f the b e n t o n -
290 Elliott et al. Clays and Clay Minerals

a b
De~h Vertical Component
Below
Surface (m) Lithology of Depth Below
Surface (m)
Lithology
Stratigraphy
%1 in I/S & (WAge)
<21.t 1-2~t <.25~t %1 in I/S & (WAge)
<2~t 1-2p~ <.251

50 m <2

3os Shale
n body)

100--

14 (36, 36) Is
13 150-- ne

45 (100) 32 (77)
19 20(43) 10(4t) rArroyo

mdstone
200-~"
a Shale

;andstone
30 (44,43) 20 (43) 4
23 26 (41) 26 (41)
33 (44, 45) 26 (45,48) LkCanyon
~mber
250-- 37 (41, 41) 32 (39,43)

18 (40) 45 (47) 20 (40]

T.D.
2323 son Fm.
[]Claystone [ ] Siltstone D Sandstone
xxxxxxxxxxx Bentonite layer (stratigmphic marker bed)
3OO

~Claystone IS~Siltstone Sandstone

xxxxxxxx Bentonite layer
I~ Basalt Dike

Figure 3. Stratigraphic descriptions of wells CNV, CNVR (Figure 3a), and CNAR (Figure 3b) showing the Mancos Shale,
Dakota Group, the percentage of illite layers in I-S and the K-Ar ages of I-S. Note, the K-Ar ages of I-S are in parentheses.
Sections drawn are from lithologic descriptions from RE. Long and J.K. Frederickson (unpubl. data, 1995). In Figure 3a, the
vertical depth is the same as the measured depths of bentonite samples. In Figure 3b, the depths of bentonites measured from
the top of the core are shown to the right of the stratigraphic column, and they differ from the vertical depth components on
the left edge. Arrowheads in Figure 3b denote the locations of basaltic dikes.

ites w e r e m e a s u r e d f r o m the top o f the well a n d r a n g e d in the b e n t o n i t e s f r o m C N A R ; m i n o r a m o u n t s o f ka-

f r o m 95.79 to 441.31 m. T h e m e a s u r e d d e p t h s f r o m
the t o p o f this a n g l e d well a n d the d e r i v e d vertical
c o m p o n e n t s o f these m e a s u r e d d e p t h s are b o t h s h o w n
in F i g u r e 3b. T h e b e n t o n i t e s c o l l e c t e d in b o t h o f the
vertical h o l e s (CNV, C N V R ) a n d the a n g l e d h o l e
( C N A R ) w e r e at similar vertical d e p t h s e n a b l i n g c o m -
p a r i s o n o f clay m i n e r a l data (e.g., p e r c e n t a g e o f illite
layers in I-S) a n d K - A r ages of I-S f r o m b e n t o n i t e s
c o l l e c t e d f r o m all three cores. A s in C N V a n d C N V R ,
r a n d o m l y o r d e r e d I-S is the p r e d o m i n a n t clay m i n e r a l
olinite w e r e f o u n d in m o s t clay fractions. T h e I-S
r a n g e f r o m n e a r l y p u r e s m e c t i t e at 4 0 7 . 1 6 - 4 0 7 . 3 1 m
to 4 5 % illite layers in I-S at 3 0 7 . 7 0 - 3 0 7 . 7 7 m (Table
1). E x c e p t for the k a o l i n i t e - r i c h b e n t o n i t e at 3 0 7 . 7 0 m
w h i c h a r g u a b l y c o n t a i n s detrital I-S as d i s c u s s e d be-
low, the 1-S f r o m the d e e p e s t b e n t o n i t e ( 4 4 1 . 3 1 -
4 4 1 . 3 4 m ) h a s the h i g h e s t p e r c e n t a g e o f illite layers
( 3 2 - 3 7 % ) . T h i s b e n t o n i t e is closest to C e r r o N e g r o
a n d a few m e t e r s f r o m b a s a l t dikes l o w e r in this core
(Figure 3b).
Vol. 47, No. 3, 1999 Kinetics of the smectite transformation in Cretaceous bentonites 291

Table 2. K-Ar age data of I-S.

Measured Size
depth I fraction I in I-S % K *~X~Ar *~Ar K - A t age
Well, formation (m) Qxm) (%) (wt. %) (%) (pmol g ~) (Ma)

CNAR Whitewater Arroyo Sh. 307.70-307.77 <2 45 1.95 68.5 348.1 100 + 2
CNAR Whitewater Arroyo Sh. 307.70-307.77 <0.25 32 2.52 69.5 343.4 77 -+ 1
CNAR Whitewater Arroyo Sh. 313.32-313.35 1 2 20 2.17 75.6 165.0 43 + 1
CNAR Whitewater Arroyo Sh. 313.32-313.35 <0.25 10 2.21 65.9 158.7 41 • 1
CNAR Oak Canyon Member 420.73-420.90 <2 33 2.62 67.8 221.9 44 -+ 1
CNAR Oak Canyon Member 420.73 420.90 <2 33 2.72 80.1 216.0 45 • 1
CNAR, Oak Canyon Member 420.73-420.90 <0.25 26 2.57 75.5 205.7 45 -+ 1
CNAR, Oak Canyon Member 420.73 420.90 <0.25 26 2.41 80.1 202.9 48 + 1
CNAR, Oak Canyon Member 441.31-441.34 <2 37 3.36 53.6 245.5 41 -+ 1
CNAR, Oak Canyon Member 441.31-441.34 <2 37 3.42 69.9 246.7 41 + 1
CNAR, Oak Canyon Member 441.31-441.34 <0.25 32 3.14 75.2 213.9 39 -+ 1
CNAR, Oak Canyon Member 441.31 441.34 <0.25 32 2.84 77.3 214.6 43 • 1
CNV, Whitewater Arroyo Sh. 142.3 143.6 <2 14 1.56 26.4 105.2 36 • 2
CNV, Whitewater Arroyo Sh. 142.3-143.6 <2 14 1.56 43.5 105.0 36 -+ 1
CNV, Oak Canyon Member 202.2 <2 30 2.69 43.9 208.4 44 + 1
CNV, Oak Canyon Member 202.2 <2 30 2.69 41.3 202.2 43 • 1
CNV, Oak Canyon Member 202.2 <0.25 20 2.50 67.4 188.6 43 • 1
CNVR Oak Canyon Member 202.75-203.25 1-2 26 2.83 72.4 204.1 41 + I
CNVR Oak Canyon Member 202.75 203.25 <0.25 26 2.39 56.5 169.7 41 +- l
CNVR Oak Canyon Member 226.30-226.32 1 2 45 3.60 78 297.9 41 -2-- 1
CNVR Oak Canyon Member 226.30 226.32 <0.25 20 3.02 74.4 213.9 40 • 1
CNVR Oak Canyon Member 226.82-226.84 <2 18 2.81 56.8 198.0 40 + 1
CNVR Oak Canyon Member 226.82 226.84 <2 18 2.81 66.7 195.8 40-+ 1

t For CNAR, depths are those measured from top of core.

K - A r ages c e n t a g e s o f illite are taken to r e p r e s e n t the p e r c e n t a g e s

T h e K - A r ages o f I-S range f r o m 36 to 48 M a ex-
c e p t for t w o a n o m a l o u s old ages (77 M a and 100 Ma)
for two size fractions o f the s a m e b e n t o n i t e at 3 0 7 . 7 0 -
307.77 m f r o m the C N A R core (Table 2). T h e a n o m -
alous K - A r ages and the high p e r c e n t a g e s o f illite
(32% and 4 5 % ) in I-S indicate that this b e n t o n i t e con-
tains a significant a m o u n t o f detrital I-S, i m p l y i n g a
s e c o n d a r y or r e w o r k e d b e n t o n i t e (e.g., Jeans et al.,
1982). For the b e n t o n i t e closest to the n e c k at 4 4 1 . 3 1 -
441.34 m, the K - A r ages range f r o m 39 to 43 M a
( M e a n = 41 Ma, N = 4). The K - A r ages o f the o t h e r
I-S s a m p l e s f r o m C N A R range f r o m 41 to 48 M a
( M e a n = 44 Ma, N = 6).
In the C N V R core, the ages o f I-S r a n g e f r o m 40
to 47 M a (Table 2; Figure 3a). T h e one age at 47 M a
appears a n o m a l o u s , and the s a m p l e also has a h i g h e r
p e r c e n t a g e o f illite layers (45%). A g e s o f all other I-
S r a n g e f r o m 40 to 41 Ma. The older age and the
h i g h e r p e r c e n t a g e o f illite layers in I-S indicate the
p r e s e n c e o f small a m o u n t s o f detrital illite in the
coarse fraction ( 1 - 2 ~ m ) w h i l e the age o f the finest
fraction ( < 0 . 2 5 ~ m ) is similar to the K - A r ages o f I-
S m e a s u r e d f r o m this thick bentonite. In the C N V
core, the K - A r ages o f I-S r a n g e f r o m 36 to 43 Ma.
Mathematical models
T h e ages and p e r c e n t a g e s o f illite calculated f r o m
the m a t h e m a t i c a l m o d e l s are s h o w n in Table 3. A s in
p r e v i o u s efforts u s i n g t h e s e m o d e l s , the calculated per-
o f illite layers in I-S (e.g., Altaner, 1985; Elliott and
Matisoff, 1996). T h e calculated p e r c e n t a g e s o f illite
layers in I-S for a g e o t h e r m a l g r a d i e n t o f 25~ k i n -
are 4 3 % ( M a n c o s Shale) and 54% (Oak C a n y o n M e m -
ber) by using the m o d e l o f Velde and V a s s e u r (1992),
25% ( M a n c o s Shale) and 4 9 % (Oak C a n y o n M e m b e r )
b y the m o d e l o f H u a n g et al. (1993) and f r o m 20%
( M a n c o s Shale) and 38% (Oak C a n y o n M e m b e r ) b y
the m o d e l o f Pytte (1982). O f the three m o d e l s used,
the results f r o m the m o d e l o f Pytte c o m p a r e m o s t fa-
v o r a b l y to the m e a s u r e d p e r c e n t a g e s o f illite layers in
I-S d e r i v e d f r o m X - r a y d i f f r a c t i o n data ( X R D ) (Table
1). P e r c e n t a g e s w e r e also calculated w i t h a h i g h e r g e o -
t h e r m a l g r a d i e n t (35~ k m ~) resulting in m u c h h i g h e r
p e r c e n t a g e s than those m e a s u r e d f r o m X R D . The cal-
culated ages w e r e older than the m e a s u r e d K - A r ages
r e g a r d l e s s o f the m o d e l used.
The e f f e c t o f heating b y the C e r r o N e g r o intrusion
w a s s i m u l a t e d b y i n c r e a s i n g the g e o t h e r m a l g r a d i e n t
b y 50~ k m -~ or 70~ krn 1 for the last 4 Ma. Two
sets o f simulations w e r e e m p l o y e d : o n e w i t h a geo-
t h e r m a l g r a d i e n t o f 25~ k m 1 i n c r e a s e d to 75~ krn-
for the last 4 M a , one using a g e o t h e r m a l g r a d i e n t o f
35~ k m i i n c r e a s e d to 105~ k m -1 for the last 4 Ma.
F r o m the burial curve, the m a x i m u m t e m p e r a t u r e s o f
the O a k C a n y o n M e m b e r at 4 M a are 72~ and 91~
u s i n g the h i g h g e o t h e r m a l gradients r e s p e c t i v e l y (75~
k m -1 or 105~ k m J) and a surface t e m p e r a t u r e o f
25~ (Figure 2). This duration (4 M a ) and e x t r e m e l y
292 Elliott et al. Clays and Clay Minerals

Table 3. Calculated ages of illite by three models.

0- Mancos Shale Bentonite
Calcu-
Calcu-
lated
~k "Y-"= 50.9 Ma
lated ages of 25-
Model Formation
GTG
(~ km ~)
illite2
(%)
illite
(Ma)
~. ~ , Oak Canyon Bentonite
,~,.~ ~ = 56.0 Ma
Velde and Mancos Sh. 25 43 53 a~ 50-
Vasseur 35 57 61
(1992) 25/75 t 43 53
35/105 z 57 61 75-
Oak Canyon 25 54 59
A
35 63 67 100 I I I I I
25/751 54 59 0 1 2 3 4 5
35/1051 63 67 K/Ar age contribution (Ma)
Pytte (1982) Mancos Sh. 25 20 51
35 47 58
25/751 20 51
35/1051 47 58 0- Mancos Shale Bentonite
Oak Canyon 25 38 56 T. = 58.4 Ma
35 66 66 25-
25/75 ~ 38 55
35/1051 67 65 5.2 M a
v
Huang et al. Mancos Sh. 25 25 49 I1)
50-
~r~
(1993) 35 63 56 <
25/75 ~ 25 49 75-
35/1051 63 56
Oak Canyon 25 49 53 B
35 87 65 100 I I I I I
25/751 50 52 1 2 3 4 5
35/105 ~ 88 65 K/Ar age contribution (Ma)
i Signifies increased geothermal gradient for the last 4 Ma. Figure 4. The contributions to the K-Ar age as a function
These models calculate the amount of illite from the loss of of geologic time by the model of Pytte. The calculated mean
smectite. ages of illitization (~) are those given for both the Mancos
2 The percent illite is taken to be equivalent to the percent Shale (dashed lines) and Oak Canyon Members (solid lines)
illite layers in I-S. using the model of Pytte (1982) in Table 3, Figure 4a shows
results using a 25~ km t geothermal gradient. Figure 4b
shows results using the highest geothermal gradient (35~
high geothermal gradients comprise a hypothetical km 1 increased to 105~ km -1 4 Ma ago) and using the model
maximum time and temperature history of increased of Pytte (1982). Time step is 1 Ma.
h e a t flow f r o m Cerro Negro. E v e n w i t h t h e s e h i g h e r
g e o t h e r m a l gradients o v e r the l o n g e s t p o s s i b l e t i m e o f
4 M a for a K pore fluid c o n c e n t r a t i o n o f 2 0 0 p p m , to the m e a s u r e d K - A r ages for I-S. T h e ages o f illite
t h e r e was virtually n o a d d i t i o n a l f o r m a t i o n o f illite c a l c u l a t e d b y t h e s e m o d e l s w i t h h i g h g e o t h e r m a l gra-
(Table 3). H i g h e r K p o r e w a t e r c o n c e n t r a t i o n s c o m - dients for the last 4 M a are not a p p r e c i a b l y y o u n g e r
b i n e d w i t h a h i g h g e o t h e r m a l g r a d i e n t w o u l d result in t h a n the ages c a l c u l a t e d w i t h a c o n s t a n t , lower, geo-
an i n c r e a s e in the a m o u n t o f illite layers f o r m e d in I- t h e r m a l g r a d i e n t (i.e., 25~ k m 1 or 35~ k n l - 1 ) , C o n -
S in a short p e r i o d of time. F o r e x a m p l e , at the S a l t o n sequently, t h e s e m o d e l s i m u l a t i o n s s h o w that an in-
Sea, Elliott a n d M a t i s o f f ( 1 9 9 6 ) d e m o n s t r a t e d that I-S crease i n g e o t h e r m a l g r a d i e n t d u r i n g the past 4 M a
w i t h as low as 2 0 % illite layers c a n b e t r a n s f o r m e d r e s u l t e d in little or n o a d d i t i o n a l f o r m a t i o n o f illite.
c o m p l e t e l y to illite u n d e r a h i g h g e o t h e r m a l g r a d i e n t The models, however, provided insight regarding
(75~ krn -1) in the p r e s e n c e o f h i g h K p o r e w a t e r con- the d u r a t i o n o f the t r a n s f o r m a t i o n a n d the t i m e at
c e n t r a t i o n s ( 3 2 0 0 p p m ) in - 2 0 , 0 0 0 years. w h i c h illite s h o u l d h a v e f o r m e d rapidly. T h e contri-
T h e ages o f illite c a l c u l a t e d b y these m o d e l s r a n g e b u t i o n to the c a l c u l a t e d m e a n age o f illitization at e a c h
f r o m 49 M a ( M a n c o s Shale) to 67 M a ( O a k C a n y o n t i m e step is s h o w n for the O a k C a n y o n a n d M a n c o s
M e m b e r ) , w h e r e a s the m e a s u r e d K - A r ages r a n g e S h a l e b e n t o n i t e s in F i g u r e 4 a a n d 4b. B y the m o d e l o f
f r o m 36 to 48 M a in Table 2 ( W h i t e w a t e r A r r o y o Pytte, for g e o t h e r m a l g r a d i e n t s o f e i t h e r 25 or 35~
M e m b e r a n d O a k C a n y o n M e m b e r ) e x c l u d i n g the t w o k m 1, illite f o r m a t i o n w o u l d h a v e p e a k e d at - 7 0 Ma.
a n o m a l o u s ages. A s a group, t h e c a l c u l a t e d ages are T h i s is w h e n these C r e t a c e o u s r o c k s first a p p r o a c h e d
< 5 to 15 M a older t h a n the oldest m e a s u r e d ages o f t h e i r m a x i m u m d e p t h a c c o r d i n g to the burial history.
I-S. T h e results for the O a k C a n y o n M e m b e r u s i n g the S i n c e the initial rates at 7 0 M a w o u l d b e g r e a t e r u n d e r
m o d e l s o f Pytte (56 M a ) a n d H u a n g et al. (53 M a ) the h i g h e r g e o t h e r m a l g r a d i e n t (35~ k i n - l ) , relatively
w i t h a g e o t h e r m a l g r a d i e n t o f 25~ k m -1 are closest m o r e illite w o u l d h a v e f o r m e d early to p r o d u c e the
Vol. 47, No. 3, 1999 Kinetics of the smectite transformation in Cretaceous bentonites 293

Table 4. Vitrinite reflectance values. solution-reprecipitation scheme or by Ostwald ripen-

Measured Vitrinite ing at m a x i m u m burial temperatures (e.g., Boles and
depth reflectance,
Well Formation (m) VRo (%) Franks, 1979; Eberl et al., 1990), then one m i g h t ex-
pect ages of illite to be closer to the time of uplift (15
CNAR Mancos Shale 92.9 1.141 Ma) p r o v i d e d the K - A t age o f I-S dates the incorpo-
Whitewater Arroyo Sh. 293.9 1.024
Oak Canyon Member 402.9 1.129 ration of K into the interlayer f o l l o w i n g c o m p l e t e dis-
Oak Canyon Member 424.6 1.054 solution o f K and r e m o v a l of A r f r o m all previously
Oak Canyon Member 441.7 1.166 f o r m e d illite. Since the measured K - A t ages of illite
CNV Whitewater Arroyo Sh. 151.2 0.825 in I-S are roughly in the mid-point of the period of
Oak Canyon Member 197.0 0.947 deep burial and the measured percentages of illite lay-
CNVR Oak Canyon Member 206.5 1.046 ers in I-S are not large, it is plausible to suggest in-
Oak Canyon Member 224.9 0.908 stead that the K - A r ages reflect a m e a n age o f illite
Oak Canyon Member 229.9 0.930 formation via transformation (e.g., A r o n s o n and H o w -
er, 1976).
The transformation was simulated best using the
sharper peaks seen in Figure 4b, and the m e a n ages m o d e l f r o m Pytte (1982) e m p l o y i n g the burial curves
are thus greater. Similarly, the m e a n ages for the Oak in Figure 2. The kinetic expression (Pytte, 1982; Pytte
C a n y o n M e m b e r are older because the initial rate of and Reynolds, 1989) also best simulated the smectite
illite formation would have been greater than in the to illite transformation in Cretaceous bentonites in the
M a n c o s Shale (Table 3). D e n v e r Basin (Elliott et al., 1991). As in the D e n v e r
Basin, the Cretaceous rocks at Cerro N e g r o w e r e bur-
DISCUSSION ied deeply for a prolonged duration. It is possible that
The c o m b i n e d clay mineral, K-Ar, and mathematical a high-order kinetic expression with K concentrations
m o d e l results present convincing e v i d e n c e that illite - 2 0 0 p p m in pore waters, typically used in conjunc-
f o r m e d primarily by increased temperature in response tion with the m o d e l of Pytte (1982), best describes the
to burial during the Cretaceous and early Tertiary pe- transformation(s) having a prolonged duration while
riods w h e n these rocks were most deeply buried (Fig- lower-order kinetic expressions using higher concen-
ure 2). The e m p l a c e m e n t of Cerro N e g r o was not the trations of K (--3200 ppm) better describe the trans-
m a j o r cause of illite formation in these Cretaceous formation in burial settings having a shorter duration,
bentonites. In angled core C N A R , the deepest benton- such as the Salton Sea or the G u l f Coast (Huang et
ite had slightly higher percentages of illite layers in I- aL, 1993; Elliott and Matisoff, 1996). If a higher order
S and the K - A r ages of I-S were slightly younger rel- kinetic expression (Pytte, 1982) is eventually found to
ative to the other I-S f r o m nearby bentonites in that simulate m o r e cases of prolonged burial such as Cerro
well. These differences are only slightly greater than N e g r o or D e n v e r Basin, then the m o d e l results should
the estimated ranges of analytical error. It is possible be generally useful to indicate the important parame-
that a small amount of younger illite was f o r m e d by ters forming illite in such settings. For now, the agree-
the flux of heat and fluids resulting f r o m the emplace- ment of the m o d e l results with the measured data can
m e n t of Cerro Negro. Such a radial flux of heat was be used to indicate that burial was sufficient to f o r m
not represented by the kinetic models. Alternatively, the bulk o f illite found in these bentonites.
this small amount of illite may have f o r m e d f r o m ad- Outside the thermal aureole, the migration of heat
ditional heat supplied by the nearby basaltic dikes generated f r o m the e m p l a c e m e n t of Cerro N e g r o was
(Figures 1 and 3b). Otherwise, burial explains suffi- recorded better by vitrinite reflectance (VRo) than by
ciently the formation and ages of illite in bentonites the ages and extent o f the smectite to illite transfor-
collected f r o m these cores, especially those further mation. V R o increases toward Cerro N e g r o f r o m
f r o m Cerro Negro. 0 . 8 2 5 - 1 . 1 6 6 % within the formations sampled f r o m
The Cretaceous Dakota Group rocks were buried to these cores (Table 4) to 2 - 2 . 5 % within the aureole
a m a x i m u m depth of 1.75 k m and heated to a maxi- itself (EE. L o n g and J.K. Frederickson, unpubl, data,
m u m burial temperature of 6 0 - 7 0 ~ assuming the geo- 1995). Outside the aureole, the lowest and the highest
thermal gradient was 25~ k m -1 and the ambient sur- m e a s u r e d V R o values correspond to T T I values of --6
face temperature was 2 0 - 2 5 ~ The presence o f ran- ( V R o = 0.8%) and 20 ( V R o = 1.1%) using a basinal
d o m l y ordered I-S is consistent with this burial and burial rate m o d e l and Easy % R o ( S w e e n e y and Burn-
heating (e.g., H o f f m a n and Hower, 1979). The K - A r ham, 1990). The T T I values derived f r o m the mea-
ages of I-S range from 36 to 48 M a (Table 2), and sured V R o are greater than TTI values calculated for
these m e a n ages of I-S correspond approximately to the base o f the M a n c o s Shale (TTI = 2.1) and for the
the mid-point ( - 4 5 Ma) of the period of deep burial base of the O a k C a n y o n M e m b e r (TTI = 3.9) using
extending f r o m the late Cretaceous Period (75 Ma) to the m e t h o d of Lopatin and the burial curves in Figure
- 1 5 M a (Figure 2). If illite in I-S f o r m e d via a dis- 2 (Waples, 1980). The m e a s u r e d V R o values ( 0 . 8 -
294 Elliott et al.
1.16%) are also greater than VRo (0.68% and 0.75%)
derived from the calculated TTI values (2.1 and 3.9)
using a basinal burial rate model and Easy %Ro
(Sweeney and Burnham, 1990). By application of the
Lopatin-type TTI analysis, burial alone could not have
produced the high measured VRo values (0.8-1.1%)
seen outside the aureole, particularly for C N A R whose
measured VRo increased toward Cerro Negro. The
VRo values measured from CNAR are likely due to
heat from burial and the emplacement of Cerro Negro.
For CNV and CNVR, however, the difference between
the calculated VRo and the measured VRo might re-
flect an increased regional thermal gradient caused by
increased volcanic activity associated with the Mount
Taylor flow, the Mesa Prieta and Mesa Chivato tra-
chyte flows, and the emplacement of volcanic necks
just prior to and younger than Cerro Negro (Hallett et
al., 1997).
The percentages of illite layers in I-S also do not
reflect the combined effects of heat from burial and
the emplacement of Cerro Negro. TTI values of --6
and 20, derived from the measured VRo of 0.8-1.1%,
also correspond to a range of illite layers in I-S from
20 to 60% (Waples, 1980). These estimated percent-
ages are higher than the range of measured percent-
ages of illite layers (10-45%) in I-S in this study. Ad-
ditionally, the measured percentage of illite layers did
not increase significantly toward Cerro Negro with the
exception of the bentonite closest to Cerro Negro (Ta-
ble 1). Consequently, the overall thermal-maturity lev-
el reflected by the clay mineralogy of the bentonites
is less than the thermal maturity reflected by vitrinite.
The differences in temperature indicated by vitrinite
reflectance versus the measured percentages of illite in
I-S is enigmatic though not unique (e.g., Velde and
Lanson, 1993). At Cerro Negro, this phenomenon may
be attributed to the retardation of the progressive for-
mation of I-S by one or some combination of the fol-
lowing: the presence of K-poor pore fluids, a high sil-
ica content derived from the adjacent sandstones and
shales (Abercrombie et al., 1994), limited availability
of K + by diffusion into thick bentonites (Altaner et al.,
1984; Altaner, 1989), and heating in the absence of
fluids. The effects of diffusion of K + is observed best
in the thick bentonite, in core CNVR at 226.3-227.1
m, where the percentage of illite layers ranges from
6-8% in the interior to 45% at the contacts with the
adjacent shale. Diffusion of K + from the upper and
lower contacts apparently limited the progressive for-
mation of I-S.
In C N A R , the flow of heat from Cerro Negro is also
reflected better by VRo than by the formation of I-S,
and this flow is certainly capable of sterilizing rocks
within the metamorphic aureole as suggested by the
high VRo of 2-2.5% indicative of T ~ x > 125~ Out-
side the aureole, the heat from burial over 60 Ma is
believed to have produced VRo between 0.68-0.75%,
Clays and Clay Minerals
and heat from the emplacement of Cerro Negro and
other nearby volcanic activity is proposed to have in-
creased VRo to 0.8-1.1% in a time period of < 3 Ma.
Using the nomograph of Sweeney and B u m h a m
(1990, their Figure 5) and measured VRo's, these
rocks are tentatively projected as heated between 100-
125~ significantly reducing microbial populations.
Thermophiles, however, may have survived these tem-
peratures,
Lastly, although significant amounts of illite were
not formed outside the metamorphic aureole because
of the emplacement of Cerro Negro, the formation of
illite in shales in proximity to intrusions is documented
elsewhere in the Western Interior Basin (e.g., Nadeau
and Reynolds, 1981; Pytte, 1982; Pytte and Reynolds,
1989). For example, diagenetic illite was formed in
shales and bentonites more than 1 km away from the
Cerrillos Intrusion (Nadeau and Reynolds, 1981).
Pytte (1982), however, noted a local and sharp de-
crease in percentage of illite layers in I-S from nearly
pure illite within late Cretaceous Pierre Shales adja-
cent to the Walsenburg Dike to I-S with only 20% illite
layers a few meters from the dike. The gradient in
percent illite in I-S versus distance from an intrusion
is clearly related to the size and geometry of the in-
trusion as expected from standard thermal models
(e.g., Carslaw and Jager, 1986). The Cerrillos Intrusion
is - 1 km in radius whereas the Walsenburg dike is
8.5 m in width (Nadeau and Reynolds, 1981; Pytte,
1982). Cerro Negro is --50 m in diameter at the sur-
face, and the thermal aureole is not clearly delineated
but likely extends - 1 0 0 - 1 5 0 m (PE. Long and J.K.
Frederickson, unpubl, data, 1995). In addition, it is
possible that Cerro Negro is smaller in diameter at
depth (Figure 1). Given these considerations and by
comparison to the Cerrillos Intrusion and the Walsen-
burg Dike, it is unlikely that significant amounts of
illite in I-S would form in the bentonites at distances
>100 m from Cerro Negro.
CONCLUSIONS
K-Ar ages, clay mineral data, and mathematical
model simulations indicate that the emplacement of
Cerro Negro did not cause appreciable amounts of new
illite to be formed in the Cretaceous bentonites outside
the aureole. Using the models of Waples (1980) and
Sweeney and Burnham (1990), the VRo values of
0.825-1.166% indicate that the bentonites were ex-
posed to higher temperatures than indicated by percent
illite in I-S, and these VRo values are higher than VRo
values expected from burial alone. Thus, in this case,
the timing and extent of the smectite to illite transfor-
mation at Cerro Negro reflects prolonged effects of
burial, whereas VRo values record the combined heat
effects from burial and from emplacement of Cerro
Negro. Tentatively, heat from Cerro Negro probably
led to significant reduction in microbial populations
Vol. 47, No. 3, 1999 Kinetics of the smectite transformation in Cretaceous bentonites
for s o m e d i s t a n c e outside the m e t a m o r p h i c aureole
p r e s u m a b l y to the d e e p e s t d e p t h s o f C N A R w h e r e a s
t h e r m o p h i l e s m a y h a v e s u r v i v e d the c o m b i n e d heat
d e r i v e d f r o m b o t h burial and the e m p l a c e m e n t o f Cer-
ro Negro.
ACKNOWLEDGMENTS
This study was supported by subcontract 300614-A-F8
from the Subsurface Science Program (E Wobber, Program
Manager) of the Department of Energy through Pacific North-
west National Laboratory (PNNL) to Case Western Reserve
University (G. Matisoff) and to Georgia State University
(W.C. Elliott). PNNL is operated by Battelle Memorial Insti-
tute for the U.S. Department of Energy. The Chancellor's Ini-
tiative Fund at Georgia State University contributed salary
support for Edenfield. The authors thank T.C. Onstott, S.R
Altaner, W.H. Hudnall, and S. Guggenheim for their com-
ments.
REFERENCES
Abercrombie, H.J., Hutcheon, I.E., Bloch, J.D., and deCaritat,
P. (1993) Silica activity and the smectite to illite reaction.
Geology, 22, 539-542.
Altaner, S.R (1985) Potassium metasomatism and diffusion in
Cretaceous K-bentonite from the disturbed belt, northwest-
ern Montana and in the Middle Devonian Tioga K-benton-
ite, eastern United States, Ph.D. dissertation, University of
Illinois, Urbana, Illinois, 193 pp.
Altaner, S.P (1989) Calculation of K diffusional rates in ben-
tonite beds. Geochimica et Cosmochimica Acta, 53, 923-
931.
Altaner, S.R, Hower, J., Whitney, G., and Aronson, J.L.
(1984) Model for K-bentonite formation: Evidence from
zoned K-bentonites in the Disturbed Belt, Montana. Geol-
ogy, 12, 412-415.
Altaner, S.P, and Ylagan, R.E (1997) Comparison of struc-
tural models of mixed-layer illite-smectite and reaction
mechanisms of smectite illitization. Clays and Clay Min-
eral.s', 45, 517-534.
Aronson, J. L., and Hower, J. (1976) The mechanisms of buri-
al metamorphism of argillaceous sediments: 2. Radiogenic
argon evidence. Geological Society o f America Bulletin, 87,
738-744.
Baars, D.L., Bartleson, B.L., Chaping, C.E., Curtis, B.E, De
Voto, R.H., Everett, J.R., Johnson, R.C., Molenaar, C.M.,
Peterson, E, Schenk, C.J., Love, J.D., Merin, I.S., Rose,
PR., Ryder, R.T., Waechter, N.B., and Woodward, L.A.
(1988) Basins of the Rocky Mountain region. In Sedimen-
tary Cover--North American Craton, US. The Geology o f
North America D-2, L.L. Sloss ed., Geological Society of
America. Boulder, Colorado, 109-220.
Barnes, D.A., Girard, J.-P., and Aronson, J.L. (1992) K-Ar
dating of illite diagenesis in middle Ordovician St. Peter
Sandstone, Michigan Basin, U.S.A. Implications for ther-
mal history. In Origin, Diagenesis, and Petrophysics o f
Clay Minerals in Sandstones, D. Houseknecht and E.D.
Pittman, eds., Special Publication of the Society Economic
Paleontologists and Mineralogists, 47, 35-48.
Bethke, C.M., and Altaner, S.P (1986) Layer-by-layer mech-
anism of smectite illitization and application to a new rate
law. Clays and Clay Minerals, 34, 136-145.
Boles, J.R., and Franks, S.G. (1979) Clay diagenesis in Wil-
cox sandstones of southwestern Texas: Implications of
smectite diagenesis on sandstone cementation. Journal o f
Sedimentary Petrology, 49, 55-70.
295
Carslaw, H.S., and Jaeger, J.C. 1986. Conduction o f Heat in
Solids, 2nd edition. Oxford University Press, New York,
520 pp.
Dong, H., Hall, C.M., Peacor, D.R., and Halliday, A.N.
(1995) Mechanisms of argon retention in clays revealed by
laser 4~ dating. Science, 267, 355-359.
Eberl, D.D., Srodofi, J., Kralik, M., Taylor, B.E., and Peter-
man, Z.E. 1990. Ostwald ripening of clays and metamor-
phic minerals. Science, 248, 474-477.
Edenfield, A.M. (1998) Kinetics of the Smectite to Illite
Transformation at Cerro Negro, New Mexico. M.S. thesis,
Georgia State University, Atlanta, Georgia 77 pp.
Elliott, W.C., and Aronson, J.L. (1987) Alleghanian episode
of K-bentonite illitization in the Southern Appalachian Ba-
sin. Geology, 15, 735-739.
Elliott, W.C., Aronson, J. L., Matisoff, G., and Gautier, D. L.
(1991) Kinetics of the smectite to illite transformation in
the Denver Basin: Clay mineral, K-Ar and mathematical
model results. American Association o f Petroleum Geolo-
gists Bulletin, 75, 436-462.
Elliott, W.C. and Matisoff, G. (1996) Evaluation of kinetic
models for the smectite to illite transformation. Clays and
Clay Minerals, 44, 77-87.
Frederickson, J.K., McKinley, J.P., Bjornstad, B.N., Long,
RE., Ringelberg, D.B., White, D.C., Krumholz, L.R., Sul-
fita, J.M., Colwell, ES., Lehman, R.M., and Phelps, T.J.
(1997) Pore-size constraints on the activity and survival of
subsurface bacteria in a late Cretaceous shale-sandstone se-
quence, northwestern New Mexico. Geomicrobiology Jour-
nal, 14, 183-202.
Hallett, R.B. (1994) Volcanic geology, paleomagnetism, geo-
chronology, and geochemistry of the Rio Puerco necks,
West-central New Mexico. Ph.D. dissertation, New Mexico
Institute of Mining and Technology, Sorocco, New Mexico,
340 pp.
Hallett, R.B., Kyle, ER., and McIntosh, W.C. (1997) Paleo-
magnetic and 4~ age constraints on the chronologic
evolution of Rio Puerco volcanic necks and Mesa Prieta,
west-central New Mexico: Implications for transition zone
magmatism. Geological Society o f America Bulletin, 109,
95-106.
Hoffman, J. and Hower, J. (1979) Clay mineral assemblages
as low-grade metamorphic geothermometers, application to
the thrust faulted Disturbed Belt of Montana, U.S.A. In
Aspects ofDiagenesis, P.A. Scholle and ER. Schluger, eds.,
Society of Economic Paleontologists and Mineralogists
Special Publication 26, 55-79.
Hower, J. (1981) X-ray diffraction of mixed layer clay min-
erals. In Clays and the Resource Geologist, EJ. Longstaffe,
ed, Mineralogical Society of Canada Short Course Hand-
book 7, 39-59.
Huang, W-L., Longo, J.M., and Pevear, D.R (1993) An ex-
perimentally derived kinetic model for smectite-to-illite
conversion and its use as a geothermometer. Clays and
Clay Minerals, 41, 162-177.
Jackson, M.L. (1979) Soil Chemical Analysis--Advanced
Course. M.L. Jackson, Madison, Wisconsin, 895 pp.
Jeans, C.V., Merriman, R.J., Mitchell, J.G., and Bland, D.J.
(1982) Volcanic clays in the Cretaceous of southern Eng-
land and northern Ireland. Clay Minerals, 17, 105-156.
Krumholz, L.R., McKinley, J.R, Ulrich, G.A., and Suflita,
J.M. (1997) Confined subsurface microbial communities in
Cretaceous rocks. Nature, 386, 64-66.
Lee, M., Aronson, J.L., and Savin, S.M. (1989) Timing and
conditions of Permian Rotliegendes Sandstone diagenesis,
southern North Sea: K-Ar and oxygen isotope data. Amer-
ican Association Petroleum Geologists Bulletin, 73, 195-
213.
296 Elliott et al.
McGookey, D.P. (1972) Cretaceous system. In Geologic Atlas
of the Rocky Mountain Region, Rocky Mountain Associa-
tion of Geologists, 190-228.
Moore, D.M. and Reynolds, R.C., Jr. (1989) X-ray Diffraction
and Identification and Analysis o f Clay Minerals. Oxford
University Press, New York, 331 pp.
Nadeau, P.H. and Reynolds, R.C., Jr. (1981) Burial and con-
tact metamorphism in the Mancos Shale. Clays and Clay
Minerals, 29, 249-259.
Odin, G.S. (1982) Numerical Dating in Stratigraphy. John
Wiley & Sons, New York, 1040 pp.
Onstott, T.C., Mueller, C., Vrolijk, PJ., and Pevear, D.P
(1997) Laser 4~ microprobe analyses of fine-grained
illite. Geochimica et Cosmochimica Acta, 61, 3851 3862.
Pollastro, R.M. (1993) Considerations and applications on the
illite-smectite goethermometer in hydrocarbon bearing
rocks from Miocene to Mississippian age. Clays and Clay
Minerals, 41, 119-133.
Pytte, A. (1982) The kinetics of the smectite to illite reaction
in contact metamorphic shales. M.A. thesis, Dartmouth
College, Hanover, New Hampshire, 78 pp.
Pytte, A. and Reynolds, R.C., Jr. (1989) The kinetics of the
smectite to illite reaction in contact metamorphic shales. In
The Thermal History o f Sedimentary Basins: Methods and
Case Histories, N.D. Naeser and T.H. McCulloch, eds,
Springer-Verlag, New York, 133-140.
Clays and Clay Minerals"
Reynolds, R.C., Jr. and Hower, J. (1970) The nature of inter-
layering in mixed layer illite-montmorillonite. Clays and
Clay Minerals, 18, 25-36.
Sclater, J.G. and Christie, RA.E (1980) Continental stretching
and explanation of the post mid-Cretaceous subsidence of
the central North Sea Basin. Journal o f Geophysical Re-
search, 85, 3711-3739.
Sweeney, A.K. and Burnham, J.J. (1990) Evaluation of a sim-
ple model of a vitrinite reflectance based on chemical ki-
netics. American Association o f Petroleum Geologists Bul-
letin, 74, 1559 1570.
Velde, B. and Lanson, B. (1993) A comparison of I-S trans-
formation and maturity of organic matter at elevated tem-
peratures. Clays and Clay Minerals, 41, 178-183.
Velde, B. and Vasseur, G. (1992) Estimation of the diagenetic
smectite to illite transformation in time-temperature space.
American Mineralogist, 77, 967-976.
Waples, D.W. (1980) Time and temperature in petroleum for-
mation: Application of Lopatin's method to petroleum ex-
ploration. American Association o f Petroleum Geologists
Bulletin, 64, 916-926.
Wilkerson, M. and Husi, A.T. (1989) Subside! A Basin Anal-
ysis Program, 1st edition. Available from Rockware, Inc.,
221 East St., Golden, Colorado 80401. URL:
www.Rockware.com.
(Received 2 March 1998; accepted 30 September," Ms. 98-
030)