Carbon dioxide in clastic rocks and silicate hydrolysis

Ian Hutcheon
Department of Geology and Geophysics, University of Calgary, Calgary, Alberta T2N 1N4, Canada
Hugh Abercrombie
Institute of Sedimentary and Petroleum Geology, 3303 33rd Street, N.W., Calgary, Alberta T2L 2A7, Canada

ABSTRACT
The amount of carbon dioxide in clastic rocks in sedimentary
basins increases with depth. Organic matter, dissolved organic spe-
cies, and dissolution of carbonate minerals have been suggested as >>
o
sources of CQ 2 , which increases in abundance with depth and c
a)
temperature. Isotopic compositions of aqueous H C O J , gaseous CO2,
CT
and calcite from conventional hydrocarbon wells and steam-assisted Q>
recovery of heavy oil suggest that calcite, or other carbonate minerals,
are the source of C 0 2 , particularly at higher temperatures. Detailed
examination of the stability of diagenetic minerals such as kaolinite,
smectite, and analcime, among others, relative to the coexisting wa-
ters, indicates that silicate hydrolysis is the driving force for dissolu- • 1 • 1— * 1 1 r— . T ( ,

tion of carbonate minerals and the ultimate source of abundant CO2 in 60 -

A A
clastic rocks in diagenetic environments at temperatures over approx- 80 - â A
imately 100 °C. o A
A *
A
o 100 A
A ^
0 1 • • *
INTRODUCTION D 120 - • V A •
-»-»
The CO2 content of natural gases increases with depth and tempera- cfl W
aï 140 AA
ture in sedimentary basins (Franks and Forester, 1984; Lundegard and a. s
Land, 1986; Smith and Ehrenberg, 1989). Arnorsson et al. (1983) showed A S 13
C Wilcox Calcite
that the partial pressure of C 0 2 (PCO2) increases with temperature in
1 160 -

• 8 13
C Frio Calcite
-

t- A .
geothermal wells in basalts in Iceland. The source of C 0 2 is thought either 180 -

A
to be organic matter (Carothers and Kharaka, 1980; Kharaka et al., 1986;
Surdam et al., 1989; Franks and Forester, 1984) or mineral reactions (Zen, -12 -10 -8 -6 -4 -2 0 2 4
1959; Muffler and White, 1969; Hutcheon et al, 1980; McDowell and 13
Paces, 1985). In sedimentary rocks there are many sources of, and sinks
8 C Calcite
for, H + , including carboxylic acids, dissolved carbonate, carbonate miner- Figure 1. Carbon isotopic composition of calcite predicted from iso-
als, and silicate hydrolysis. All have different abilities to buffer pH, which topic composition of C 0 2 in formation waters from Frio and Wilcox vs.
is related to the amount of C 0 2 in formation fluids at greater burial depths temperature, calculated from data of Lundegard et al. (1984). For com-
parison, histograms show measured isotopic compositions of calcite
by calcite stability. It is often assumed that increase of PCO2 cause from Frio and Wilcox.
dissolution of carbonate, and, in the absence of some other control of pH,
this is correct. However, if pH is buffered, the addition of C 0 2 will cause
precipitation of carbonate. Kharaka et al. (1986), Surdam et al. (1989),
and Means and Hubbard (1987) have considered organic acids to be the Gulf Coast. In Figure 1, the isotopic composition and temperature (their
most effective pH buffer in sediment pore fluids. Lundegard and Land Fig. 2) are used to calculate the isotopic composition of calcite in equilib-
(1989) have simulated the effect of acetate and P c o 2 on carbonate-mineral rium with dissolved C 0 2 . Histograms of calcite isotopic compositions
solubility and have concluded that, for most conditions in sedimentary (their Fig. 3) show some overlap of measured and predicted isotopic
basins, increases in pco2 will cause calcite dissolution. None of these compositions of calcite.
authors considered silicate hydrolysis as a buffer of pH. The Venture field in Cretaceous sandstones, offshore the east coast of
In this paper we examine the isotopic composition of carbon-bearing Canada, contains C 0 2 that we (Hutcheon and Abercrombie, 1989) inter-
species in formation fluids, carbonate minerals, and fluids produced during preted to originate from a reaction between kaolinite and carbonates to
thermal recovery of heavy oil. The relations between mineral reactions, produce chlorite and C 0 2 :
fluid chemistry, and the dissolution of carbonate minerals and production
of C 0 2 during diagenesis are examined. Finally, we consider the ability of 5FeC0 3 + S i 0 2 + Al 2 Si 2 0 5 (0H) 4 + 2 H 2 0 ;
carboxylic acids, dissolved carbonate, carbonate minerals, and silicate hy- Fe5Al2SÌ3O10(OH)8 + 5CO 2 . (1)
drolysis to buffer pH.
Hutcheon et al. (1980) showed how such reactions may intersect the C 0 2
I S O T O P I C DATA AND MINERAL REACTIONS miscibility surface in aqueous solutions and produce a C0 2 -rich vapor.
Lundegard et al. (1984) showed isotopic data for aqueous C 0 2 and Over temperatures that range from 80 to 180 °C, during steam-
carbonate minerals from the Frio and Wilcox Formations of the Texas assisted recovery of heavy oil, the large volumes of produced C 0 2 are in

GEOLOGY, v. 18, p. 541-544, June 1990 541

isotopie equilibrium with the reservoir calcite (Hutcheon et al., 1990).
Reaction 1 uses molecular species to calculate the intersection of clay-
carbonate reactions with the solubility surface of CO2 in an aqueous
solution. In an aqueous solution, ionic species such as HCO3 and H 4 SiO^
are present and mineral species are not pure. Hutcheon (1990) has used
mineral compositions to estimate the position of reaction 1. For CO2 to be
present in the gas over an aqueous phase, the solubility of CO2 must be
exceeded. If calcite dissolves in a solution saturated with CO2, the equilib-
rium can be written as
C a C 0 3 + 2H + ^ Ca 2 + + H 2 0 + C 0 2 , (2)
emphasizing the control of ah* on P c o v
Compositions of Produced Waters
To relate water compositions to silicate-mineral reactions, salinity,
and the generation of CO2, we use data from a steam-enhanced-recovery
pilot project at Tucker Lake (Hutcheon et al., 1989a, 1989b) in Alberta's
Cold Lake heavy-oil deposits. During steam-enhanced recovery, tempera-
tures reach 300 °C, but more commonly are between 100 and 200 °C.
After injection and a soaking stage, heated oil and water are recovered
from the injection well. The formation and the associated fluid cool con-
tinuously, and, because steam is fresh water, salinity increases as higher
proportions of more saline formation water return to the well. These pilot
projects are laboratories for some diagenetic processes: salinity and
temperature change through time, the process takes place over periods of
years, and the rocks and fluids are relatively easily sampled. Mineral
reactions occur in these lithoclastic sandstones during this process (Sedi-
mentology Research Group, 1981; Hutcheon et al., 1989a; Abercrombie,
1989), and evidence suggests that these mineral reactions produce CO2
(Abercrombie and Hutcheon, 1986; Gunter and Bird, 1988; Hutcheon et
al., 1990). By comparing analyses of produced water and mineral data
50 100 150
Temperature (°C)
Figure 2. Stability of kaolinite, smectite (paragonite activity, 0.2), and
analcime at 40 bar as function of temperature vs. a N a ,/a H + ratio. Sym-
bols denote a N a . / a H . ratios measured from waters produced from
steam-assisted-recovery pilot projects. Compositions of waters from
lithoclastic reservoirs (squares) follow smectite-analcime boundary;
waters from quartz-rich reservoirs (diamonds) follow kaolinite-smectite
boundary. Dashed line represents smectite-albite equilibrium. Because
total a N a , is controlled by mass flow, control of pH by silicate hydrolysis
reactions is inferred.
542
from the field, some insights about how mineral reactions produce C 0 2 ,
and about diagenetic processes in general, can be obtained.
Hutcheon (1981) outlined the mechanism by which silicate-
hydrolysis reactions during diagenesis might mediate activity ratios of
aqueous species, such as K + and Na + , to H + . Figure 2, after Hutcheon et al.
(1989a), shows the stability of kaolinite, chalcedony, smectite, and anal-
cime, minerals observed to be present during steam injection (Sedimentol-
ogy Research Group, 1981), in terms of temperature and N a + / H + activity
(a) ratio (a Na ./aH*)- The dashed line is the smectite-albite reaction and
cannot be distinguished from the smectite-analcime reaction. Analcime is
observed to form during steam injection and therefore was used, but fluid
compositions also may represent dissolution of albite and precipitation of
smectite. The mineral phase boundaries were calculated from thermody-
namic parameters of Helgeson et al. (1978) by using EQCALC (Flowers,
1986). Calculated phase boundaries between kaolinite, Na-smectite (par-
agonite activity in smectite is 0.2), pyrophyllite, and analcime are
an
univariant lines that are functions of d temperature (pressure =
4 MPa). N a + / H + activity ratios, calculated from produced-fluid composi-
tions, tend to follow phase boundaries between kaolinite-smectite or
smectite-analcime. The reactions generally are of the type
Na + + silicate ^ Na-silicate + H 4 (3)
and Figure 2 demonstrates that the stability of two minerals such as
kaolinite and smectite at equilibrium is a function of temperature and
a N a ,/a H ». In 20 days, or less, the fluids achieved metastable equilibrium
with minerals observed to form during steam injection, suggesting strongly
that reactions among the minerals are mediating of the fluid. The
concentration of Na increases from 500 to 5000 mg/1, as temperature
decreases with production time. Flow of saline fluid, not mineral reactions,
controls the Na concentration of the waters (—103 mg/1). Mineral reac-
tions could be controlling the pH to maintain a N a ,/a H + ratios that follow
phase boundaries between minerals. Hutcheon et al. (1989a) reported
similar behavior for K- and Mg-bearing minerals such as illite, chlorite,
and K-feldspar. In general, diagenetic mineral reactions tend to favor the
mineral with the higher metal-ion concentration as temperature increases.
In other words, with increasing burial or temperature, progressive in-
log ( a C a J / ( a HH++ /)
Figure 3. Two reactions, CaC0 3 + 2H+ « Ca 2+ + C 0 2 + H 2 0 and kaolin-
ite + Ca 2+ Ca-smectite + 2H+, are shown as functions of temperature
and a Ca 2»/(a H ,) 2 ratio. Water compositions from pilot projects for
steam-assisted recovery are in apparent equilibrium with dissolution of
calcite. Circles denote fluid composition.
GEOLOGY, June 1990
creases in the amounts of diagenetic metal-bearing aluminosilicates are
expected (e.g., illite forming from kaolinite).
The progress of diagenesis to form minerals such as illite, chlorite, and
K-feldspar should correspond to rising ah», and increasing dissolution of
calcite should occur. The dissolution rate of calcite in a C02-saturated
fluid will be faster than silicate reaction rates. Thus, the a C a 2 + /(a H t ) 2 ratio
of produced fluids will be controlled by reaction 2, rather than by a silicate
reaction. Figure 3 shows the a Ca2 V(«H>) 2 ratio vs. temperature at constant
pressure for reaction 2 and a reaction between Ca-smectite and kaolinite.
Reaction 2, which is metastable with respect to kaolinite-smectite, includes
the activity of CO2. The fluid compositions (circles) are in equilibrium
with calcite dissolution, confirming the more rapid reaction rate. As sil-
icate reactions progress to produce less aluminous minerals during dia-
genesis, the H + generated should be continuously consumed by carbonate
to produce CO2.
Capacity to Buffer pH
Organic acids have been proposed as pH buffers that control the
dissolution of carbonate and contribute CO2 during diagenesis (Surdam et
al., 1984,1989; Kharaka et al., 1986; Surdam and Crossey, 1987; Means
and Hubbard, 1987). Abercrombie (1989) has considered the pH buffer-
ing capacity of silicates relative to carbonates. To these calculations we
have added the pH buffering capacity of acetate at 100 and 10000 mg/1,
the total range observed in most formation waters (Fig. 4). The buffering
capacity, or the ability of a reaction to control pH as H + is added to the
system, has been calculated at 100 °C by using methods outlined in
Stumm and Morgan (1981). Generally, silicate equilibria (albite-smectite
is shown) have higher pH buffering capacities than carbonates or organic
acids. The 10000 mg/1 curve for acetate is near the maximum, high
concentrations of 3500 mg/1 being more likely (Lundegard and Land,
1989) and corresponding to lower pH buffering capacity. If silicate reac-
tion rates are sufficiently fast, and the steam-flood data indicate they are,
equilibria among silicates should control carbonate stability.
Silicate Equilibria and P c o 2
Figure 2 shows that silicate reactions proceed toward the Na-bearing
side with increasing temperature, producing H + as diagenesis proceeds. If a
>
H Q
O)
z CM
Acetate(10_000jing/1)_
LLI
t-
cr
LLI
A c e t a t e ( 1 0 0 rng/l)
PH
Figure 4. Butter intensity, defined according to Stumm and Morgan
(1981), for calcite, dissolved carbonate (10"^ mol), two acetate con-
centrations (100 and 10000 mg/l), and hydrolysis reaction between
albite and smectite are shown as function of pH at 100 °C. Over normal
range of pH (neutral pH = 6.1 at 100 °C), silicates generally have higher
pH buffer intensity.
542 GEOLOGY, June 1990
more saline fluid moves into a rock containing less saline fluids, the sil-
icates will attempt to maintain constant a N a . / a H . and, since will
increase, H + will be generated as the silicates come to equilibrium. This
process could produce local dissolution of carbonates near salt domes or at
unconformities where fluid flow between units containing waters of very
different salinity might be possible, as in the Alberta basin (Hitchon et al.,
1971).
Figure 5 shows p c o 2 temperature data from the Gulf Coast
(Smith and Ehrenberg, 1989) and data from Iceland collected by Amors-
son et al. (1983), who suggest that the source of C 0 2 is calcite. Parallel
trends are evident but the data are not coincident, waters from sedimentary
basins giving higher pccn values at any temperature. Regardless of how
pH is controlled, P c o i w ' " correspond to the equilibrium solubility at a
given pressure, temperature, and fluid composition. The variables control-
ling calcite stability at any temperature and pressure are the fugacity of
CO2 and the ratio of ac a2 ./(flu*) 2 - The solubility of CO2 in water in-
creases with increasing pressure and decreases with increasing salinity and
temperature. The difference in P c o 2 at any temperature for sedimentary
waters and geothermal waters may reflect differences in salinity and pres-
sure at a particular temperature and/or control of a H . by different silicate
equilibria. Figure 2 (Hutcheon et al., 1989a) shows that waters in quartz-
rich reservoirs tend to be in equilibrium with kaolinite-smectite, whereas
waters from lithoclastic rocks tend to be in equilibrium with smectite-
analcime. At similar Na + concentrations, temperatures, and pressures, the
kaolinite-smectite equilibrium requires a higher (lower pH) than the
smectite-analcime equilibrium. If a H , increases at constant temperature
and aCil2+, then pco^ must increase to maintain equilibrium with calcite.
Waters from quartz-rich sedimentary rocks are more likely to be in equi-
librium with kaolinite than analcime, requiring higher and higher
PCO2 ^ a n waters in contact with basalts. The waters in volcanic rocks are
more likely to be in equilibrium with smectite-analcime or smectite-albite,
requiring lower a H , and lower P c o Y To test this suggestion, carefully
collected rocks and waters should be examined in terms of the stability of
the authigenic minerals relative to calcite and the solubility of CO2.
;.
2 <DO
CO 1
a
o
0
O
o
CL -1
O)
o -2 o p C 0 2 Gulf Coast Sediments
-3 0 p C 0 2 Icelandic Volcanics
100 150 200 250 300
Temperature (°C)
Figure 5. There are consistently increasing, but different, values of Pco 2
with increasing temperature for sediments from the Gulf Coast (after
Smith and Ehrenberg, 1989) and waters from geothermal wells in basal-
tic volcanic rocKS in Iceland (after Arnorsson et al., 1983). Comparison
with Figure 2 suggests that lower pH set by quartz-rich sediments of
Gulf Coast, when compared to basaltic rocks from Iceland, has set
higher p C 0 2 for equilibrium with calcite.
CONCLUSIONS
H y d r o l y s i s of silicates c a n p r o d u c e C O j in d e e p l y b u r i e d , h i g h e r
t e m p e r a t u r e , clastic s e d i m e n t a r y r o c k s . A l u m i n o u s m i n e r a l s s u c h a s k a o l i -
n i t e r e a c t t o f o r m m e t a l - b e a r i n g a l u m i n o u s silicates i n c l u d i n g s m e c t i t e ,
illite, chlorite, a n d f e l d s p a r a n d a r e a s o u r c e of H + . S t e a m - i n j e c t i o n d a t a
suggest t h a t m e t a s t a b l e e q u i l i b r i u m is possible f o r silicates a t higher
temperatures in s h o r t t i m e s . R e a c t i n g silicates c a n b e in shales or
sandstones.
F l u i d s in s e d i m e n t a r y r o c k s a p p r o a c h m e t a s t a b l e e q u i l i b r i u m w i t h
silicates, b u t c a r b o n a t e s h a v e m o r e r a p i d r e a c t i o n rates. D i f f e r e n t a u t o -
g e n i c silicate r e a c t i o n s , t h e n a t u r e of w h i c h is d e t e r m i n e d b y t h e b u l k
c o m p o s i t i o n of t h e r o c k , set d i f f e r e n t a ^ , v a l u e s a t a g i v e n a N a . . F l u i d s in
l i t h o c l a s t i c o r v o l c a n i c r o c k s s h o u l d h a v e l o w e r a H . , set b y e q u i l i b r i u m
w i t h a n a l c i m e - s m e c t i t e o r smectite-albite, a n d t h u s l o w e r Pcor Fluids in
quartz-rich rocks should h a v e h i g h e r a H » , set b y e q u i l i b r i u m with
k a o l i n i t e - s m e c t i t e o r kaolinite-illite, a n d t h u s h i g h e r p QQ2.
T w o processes m a y o c c u r d u r i n g diagenesis t h a t c a n c a u s e d i s s o l u t i o n
of c a l c i t e b y e s t a b l i s h i n g e q u i l i b r i u m w i t h silicates. A s t e m p e r a t u r e i n -
creases, t h e silicates t e n d t o c o e x i s t w i t h f l u i d s t h a t r e q u i r e h i g h e r a H , a t a
g i v e n salinity, p o t e n t i a l l y resulting in calcite d i s s o l u t i o n . If salinities in-
c r e a s e (e.g., b o r d e r i n g salt d o m e s ) , t h e c o n t r o l o f a ^ . / a ^ , b y silicate
h y d r o l y s i s will increase a H . , l e a d i n g t o dissolution of calcite.
REFERENCES CITED
Abercrombie, H.J., 1989, Water-rock interaction during diagenesis and thermal
recovery, Cold Lake, Alberta [Ph.D. thesis]: Calgary, Alberta, University of
Calgary, 183 p.
Abercrombie, H., and Hutcheon, I., 1986, Remote monitoring of water-rock-
bitumen interactions during steam-assisted heavy oil recovery, in Fifth Interna-
tional Symposium on Water-Rock Interaction: Reykjavik, Orkustofnum,
p. 1-4.
Arnorsson, S., Gunnlaugsson, E., and Svavarsson, H., 1983, The chemistry of
geothermal waters in Iceland: III. Chemical geothermometry in geothermal
investigation: Geochimica et Cosmochimica Acta, v. 47, p. 567-577.
Carothers, W.W., and Kharaka, Y.K., 1980, Stable carbon isotopes of HCO~ in oil
field waters—Implications for the origin of C 0 2 : Geochimica et Cosmochim-
ica Acta, v. 44, p. 323-332.
Flowers, G.C., 1986, Computation of thermodynamic properties of reactions in-
volving minerals and aqueous solutions with the aid of a personal computer:
Computers & Geosciences, v. 12, p. 361-380.
Franks, S.G., and Forester, R.W., 1984, Relationships among secondary porosity,
pore-fluid chemistry and carbon dioxide, Texas Gulf Coast, in MacDonald,
D.A., and Surdam, R.C., eds., Clastic diagenesis: American Association of
Petroleum Geologists Memoir 37, p. 6 3 - 7 9 .
Gunter, W.G., and Bird, G.W., 1988, C 0 2 production in tar sand reservoirs under
in-situ steam temperatures: Reactive calcite dissolution: Chemical Geology,
v. 70, p. 301-311.
Helgeson, H.C., Delany, J.M., Nesbitt, H.W., and Bird, D.K., 1978, Summary and
critique of the thermodynamic properties of rock-forming minerals: American
Journal of Science, v. 278A, 229 p.
Hitchon, B., Billings, G.K., and Klovan, J.E., 1971, Geochemistry and origin of
formation waters in the western Canada sedimentary basis: III. Factors con-
trolling chemical composition: Geochimica et Cosmochimica Acta, v. 35,
p. 567-598.
Hutcheon, I., 1981, Applications of thermodynamics to clay-mineral and
authigenic-mineral assemblages, in Longstaffe, F.J., ed., Clays and the resource
geologist: Mineralogical Association of Canada Short Course Notes, v. 7,
p. 169-193,
1990, Clay-carbonate reactions in the Venture area, Scotian Shelf, Nova
Scotia, Canada, in Fluid-mineral interactions: A tribute to H. P. Eugster: Geo-
chemical Society Special Publication 2 (in press).
Hutcheon, I., and Abercrombie, H.J., 1989, The role of silicate hydrolysis in the
origin of C 0 2 in sedimentary basins, in Proceedings of the Sixth International
Symposium on Water-Rock Interaction: Rotterdam, Balkema, p. 321-324.
544 Printed in U.S.A.
Hutcheon, I., Oldershaw, A., and Ghent, E., 1980, Diagenesis of sandstones of the
Kootenay Formation at Elk Valley (southeastern British Columbia) and
Mount Allan (southwestern Alberta): Geochimica et Cosmochimica Acta,
v. 44, p. 1425-1435.
Hutcheon, I., Abercrombie, H., Shevalier, M., and Nahnybida, C., 1989a, A com-
parison of formation reactivity in quartz-rich and quartz-poor reservoirs during
steam assisted recovery, in Meyer, R.F., and Wiggins, E.J., eds., Fourth Inter-
national U N I T A R / U N D P Conference on Heavy Crude and Tar Sands: Ed-
monton, Alberta Oil Sands Technology and Research Authority, v. 2,
p. 747-759.
Hutcheon, I., Abercrombie, H., Putnam, P., Krouse, H.R., and Gardner, R., 1989b,
The sedimentology and diagenesis of heavy oil bearing sands in the Tucker
Lake area: Bulletin of Canadian Petroleum Geology, v. 37, p. 83-97.
Hutcheon, I., Abercrombie, H., and Krouse, H.R., 1990, Inorganic origin of carbon
dioxide during low temperature thermal recovery of bitumen: Chemical and
isotopic evidence: Geochimica et Cosmochimica Acta, v. 54 (in press).
Kharaka, Y.K., Law, L.M., Carothers, W.W., and Goerlitz, D.F., 1986, Role of
organic species dissolved in formation waters from sedimentary basins in
mineral diagenesis, in Gautier, D.L., ed., Roles of organic matter in sediment
diagenesis: Society of Economic Paleontologists and Mineralogists Special
Publication 38, p. 111-122.
Lundegard, P.D., and Land, L.S., 1986, Carbon dioxide and organic acids: Their
role in porosity enhancement and diagenesis, Paleogene of the Texas Gulf
Coast, in Gautier, D.L., ed., Roles of organic matter in sediment diagenesis:
Society of Economic Paleontologists and Mineralogists Special Publication 38,
p. 129-146.
1989, Carbonate equilibria and pH buffering by organic acids—Response to
changes in Pc02- Chemical Geology, v. 74, p. 277-287.
Lundegard, P.D., Land, L.S., and Galloway, W.E., 1984, Problem of secondary
porosity: Frio Formation (Oligocene), Texas Gulf Coast: Geology, v. 12,
p. 399-402.
McDowell, S.D., and Paces, J.B., 1985, Carbonate alteration minerals in the Salton
Sea geothermal system, California, USA: Mineralogical Magazine, v. 49,
p. 469-479.
Means, J.L., and Hubbard, N., 1987, Short-chain aliphatic acid anions in deep
subsurface brines: A review of their origin, occurrence, properties, and impor-
tance and new data on their distribution and geochemical implications in the
Palo Duro basin, Texas: Organic Geochemistry, v. 11, p. 177-191.
Muffler, L.P.J., and White, D.E., 1969, Active metamorphism of upper Cenozoic
sediments in the Salton Sea geothermal field and the Salton Trough, southeast-
ern California: Geological Society of America Bulletin, v. 80, p. 157-182.
Sedimentology Research Group, 1981, The effects of in situ steam injection on Cold
Lake oil sands: Bulletin of Canadian Petroleum Geology, v. 29, p. 447-478.
Smith, J.T., and Ehrenberg, S.N., 1989, Correlation of carbon dioxide abundance
with temperature in clastic hydrocarbon reservoirs: Relationship to inorganic
chemical equilibrium: Marine and Petroleum Geology, v. 6, p. 129-135.
Stumm, W., and Morgan, J.J., 1981, Aquatic chemistry: New York, Wiley Inter-
science, 780 p.
Surdam, R.C., and Crossey, L.J., 1987, Integrated diagenetic modeling: A process-
oriented approach for clastic systems: Annual Review of Earth and Planetary
Sciences, v. 15, p. 141-170.
Surdam, R.C., Boese, S.W., and Crossey, L.J., 1984, The chemistry of secondary
porosity, in MacDonald, D.A., and Surdam, R.C., eds., Clastic diagenesis:
American Association of Petroleum Geologists Memoir 37, p. 127-149.
Surdam, R.C., Crossey, L.J., Hagen, E.S., and Heasler, H.P., 1989, Organic-
inorganic interactions and sandstone diagenesis: American Association of
Petroleum Geologists Bulletin, v. 73, p. 1-23.
Zen, E-An, 1959, Clay mineral-carbonate relations in sedimentary rocks: American
Journal of Science, v. 257, p. 2 9 - 4 3 .
ACKNOWLEDGMENTS
Supported financially by NSERC and AOSTRA. We thank J. R. Boles, P. R.
Lundegard, R. C. Surdam, and R. K. Suchecki for critical comments. Geological
Survey of Canada Contribution No. 28989.
Manuscript received June 12, 1989
Revised manuscript received December 20, 1989
Manuscript accepted January 12, 1990
GEOLOGY, June 1990