Hostname: page-component-76fb5796d-2lccl Total loading time: 0 Render date: 2024-04-27T23:21:59.633Z Has data issue: false hasContentIssue false

An Experimentally Derived Kinetic Model for Smectite-to-Illite Conversion and Its Use as a Geothermometer

Published online by Cambridge University Press:  28 February 2024

Wuu-Liang Huang
Affiliation:
Exxon Production Research Company, P.O. Box 2189, Houston, Texas 77252-2189
John M. Longo
Affiliation:
Exxon Production Research Company, P.O. Box 2189, Houston, Texas 77252-2189
David R. Pevear
Affiliation:
Exxon Production Research Company, P.O. Box 2189, Houston, Texas 77252-2189

Abstract

The smectite-to-illite conversion during shale diagenesis has recently been used to constrain the estimate of a basin's thermal history. We have systematically investigated the kinetics for the conversion of a Na-saturated montmorillonite (SWy-1) to a mixed-layer smectite/illite as a function of KCl concentration (from 0.1 to 3 moles/liter) over a temperature range of 250° to 325°C at 500 bars in cold-seal pressure vessels using gold capsules. The results show that the conversion rate can be described by a simple empirical rate equation

-dS/dt = A · exp(-Ea/RT) · [K+] · S2

where S = fraction of smectite layers in the I/S, t = time in seconds, A = frequency factor = 8.08 × 10-4 sec-1, exp = exponential function, Ea = activation Energy = 28 kcal/mole, R = gas constant, 1.987 cal/deg-mole, T = temperature (degree Kelvin), [K+] = K+ concentration in molarity (M) in the fluid.

The results also show that Ca2+ in solutions barely affects the illitization rate, whereas Mg2+ significantly retards the rate. The retardation, however, is not as severe as previously reported. Na+ ion can significantly retard the rate only if the concentration is high.

We found that by assuming a range 0.0026-0.0052 moles/liter (100-200 ppm) of K+, concentrations similar to the value typically reported in oil field brines, the present kinetic model can reasonably predict the extent of the smectite-to-illite conversion for a number of basins from various depths and age. This narrow range of potassium concentrations, therefore, is used to model the smectite-to-illite conversion in shale when the actual chemical information of pore fluid is not available.

The kinetic equation has been tested using field data from a large variety of geologic settings worldwide (i.e., the Gulf of Mexico, Vienna Basin, Salton Trough Geothermal Area, East Taiwan Basin, Huasna Basin, etc). The results show that the equation reasonably predicts the extent of the reaction within our knowledge of the variables involved, such as burial history, thermal gradients, and potassium concentration.

Type
Research Article
Copyright
Copyright © 1993, The Clay Minerals Society

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Altaner, S. P., 1986 Comparison of rates of smectite unitization with rates of K-feldspar dissolution Clays & Clay Minerals 34 608611 10.1346/CCMN.1986.0340517.CrossRefGoogle Scholar
Altaner, S. P., 1989 Calculation of K diffusional rates in bentonite beds Geochim. Cosmochim. Acta 53 923931 10.1016/0016-7037(89)90037-9.CrossRefGoogle Scholar
Aronson, J. L. and Hower, J., 1976 Mechanism of burial metamorphism of argillaceous sediment: 2. Radiogenic argon evidence Geol. Soc. Amer. Bull. 87 738744 10.1130/0016-7606(1976)87<738:MOBMOA>2.0.CO;2.2.0.CO;2>CrossRefGoogle Scholar
Bethke, C. M. and Altaner, S. P., 1986 Layer-by-layer mechanism of smectite illitization and application to new rate law Clays & Clay Minerals 34 146154 10.1346/CCMN.1986.0340205.CrossRefGoogle Scholar
Bethke, C. M., Vergo, N. and Altaner, S. P., 1986 Pathways of smectite illitization Clays & Clay Minerals 34 125135 10.1346/CCMN.1986.0340203.CrossRefGoogle Scholar
Bodner, D. P. and Sharp, J. M. Jr., 1988 Temperature variations in south Texas subsurface Amer. Assoc. Petrol. Geologist Bull. 82 2132.Google Scholar
Boles, J. R. and Franks, S. G., 1979 Clay diagenesis in Wilcox Sandstones of Southwest Texas: Implications of Smectite Diagenesis on Sandstone Cementation J. Sed. Petrol. 49 5570.Google Scholar
Broecker, W. S. and Oversby, V. M., 1971 Chemical Equilibrium in the Earth New York McGraw-Hill Book Company.Google Scholar
Bruce, C. H., 1984 Smectite dehydration—Its relation to structural development and hydrocarbon accumulation in Northern Gulf of Mexico Basin Amer. Assoc. Petrol. Geologists Bull. 68 673683.Google Scholar
Carothers, W. W. and Kharaka, Y. K., 1978 Aliphatic acid anions in oilfield waters—Implications for origin of natural gas Am. Assoc. Petroleum Geologists Bull. 62 24412453.Google Scholar
Dorsey, R. J., Buchovecky, E. J. and Lundberg, N., 1988 Clay mineralogy and Pliocene-Pleistocene mudstone, eastern Taiwan: Combined effects of burial diagenesis and provenance unroofing Geology 16 944947 10.1130/0091-7613(1988)016<0944:CMOPPM>2.3.CO;2.2.3.CO;2>CrossRefGoogle Scholar
Eberl, D. D., 1977 The hydrothermal transformation of sodium and potassium smectite into mixed-layer clay Clays & Clay Minerals 25 215227 10.1346/CCMN.1977.0250308.CrossRefGoogle Scholar
Eberl, D. D., 1978 The reaction of montmorillonite to mixed-layer clay: The effect of interlayer alkali and alkaline earth cations Geochim. Cosmochim. Acta 42 17 10.1016/0016-7037(78)90210-7.CrossRefGoogle Scholar
Eberl, D. D. and Hower, J., 1976 Kinetics of illite formation Geol. Soc. Amer. Bull. 87 13261330 10.1130/0016-7606(1976)87<1326:KOIF>2.0.CO;2.2.0.CO;2>CrossRefGoogle Scholar
Eberl, D. D., Srodon, J., Kralik, M., Yaylor, B. E. and Peterman, Z. E., 1990 Ostwald ripening of clays and metamorphic minerals Science 248 474477 10.1126/science.248.4954.474.CrossRefGoogle Scholar
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 Data, and mathematical model results Amer. Assoc. Petrol. Geologists Bull. 75 436462.Google Scholar
Eslinger, E. V. and Pevear, D. R., 1988 Clay Minerals for Petroleum Geologists and Engineers 10.2110/scn.88.22.CrossRefGoogle Scholar
Garrels, R. M., 1984 Montmorillonite/illite stability diagrams Clays & Clay Minerals 3 161166 10.1346/CCMN.1984.0320301.CrossRefGoogle Scholar
Giiven, N. and Huang, W. L., 1991 Effect of octahedral Mg2+ and Fe3+ substitutions on hydrothermal illitization reactions Clays & Clay Minerals 39 387399 10.1346/CCMN.1991.0390408.CrossRefGoogle Scholar
Horton, R. B., Johns, W. D. and Kurzweil, H., 1985 Illite diagenesis in the Vienna Basin, Austria TMPM Tschermaks Min. Petr. Mitt. 34 239260 10.1007/BF01082964.CrossRefGoogle Scholar
Hower, J., Eslinger, E. V., Hower, M. E. and Perry, E. A., 1976 Mechanism of burial metamorphism of argillaceous sediments: 1. Mineralogical and chemical evidence Geol. Soc. Amer. Bull. 87 725737 10.1130/0016-7606(1976)87<725:MOBMOA>2.0.CO;2.2.0.CO;2>CrossRefGoogle Scholar
Howard, J. J. and Roy, D. M., 1985 Development of layer charge and kinetics of experimental smectite alteration Clays & Clay Minerals 33 8188 10.1346/CCMN.1985.0330201.CrossRefGoogle Scholar
Huang, W. L. and Otten, G. A., 1987 Smectite illitization: effect of smectite composition Program and Abstracts, 24th Annual Meeting, The Clay Minerals Society, Socorro, New Mexico 75.Google Scholar
Huang, W. L., 1989 Control on ordering of mixed-layer smectite/illite: An experimental study Program and Abstracts, 26th Annual Meeting, The Clay Minerals Society, Sacramento, California 94.Google Scholar
Huang, W. L., 1990 Experimental illitization of smectite and recrystallization of illite Programme and Abstracts, Research Conference on Phyllosilicates as Indicators of Very Low Grade Metamorphism and Diagenesis 10.Google Scholar
Huang, W. L., 1992 Illitic clay formation during experimental diagenesis of arkoses Origin, Diagenesis, and Petrophysics of Clay Minerals in Sandstones 47 4963 10.2110/pec.92.47.0049.CrossRefGoogle Scholar
Inoue, A. and Utada, M., 1978 Further Investigations of a conversion series of diochahedral mica/smectites in the Shinzan hydrothermal alteration area, northeast Japan Clays & Clay Minerals 31 400412.Google Scholar
Inoue, A., Kohyama, N., Kitagawa, R. and Watanabe, T., 1987 Chemical and morphological evidence for the conversion of smectite to illite Clays & Clay Minerals 35 111120 10.1346/CCMN.1987.0350203.CrossRefGoogle Scholar
Issler, D. R., Beaumont, C., Naeser, N. D. and McCulloh, T. H., 1989 Finite element model of the subsidence and thermal evolution of extensional basins: Application to the Labrador Continental Margin Thermal History of Sedimentary Basins New York Springer-Verlag 239267 10.1007/978-1-4612-3492-0_14.CrossRefGoogle Scholar
Jennings, S. and Thompson, G. R., 1986 Diagenesis of Plio-Pleistocene sediments of the Colorado River Delta, Southern California J. Sed. Petrol. 56 8998.Google Scholar
Johns, W. D. and Hoefs, J., 1985 Maturation of organic matter in Neogene sediments from the Aderklaa oilfield, Vienna Basin, Austria TMPM Tschemaks Min. Petr. Mitt. 34 143158 10.1007/BF01081558.CrossRefGoogle Scholar
Kablanow II, R. I. and Surdam, R. C., 1984 Diagenesis and hydrocarbon generation in the Monterey Formation, Huasna Basin, California SEPM Guidebook 2 5368.Google Scholar
Kacandes, G. H., Barnes, H. L. and Kump, L. R., 1991 The smectite to illite reaction: fluid & solids evolution under flow-through conditions Program and Abstracts, 28th Annual Meeting, The Clay Minerals Society, Houston, Texas 95.Google Scholar
Kharaka, Y. K., Mariner, R. H., Naeser, N. D. and McCulloh, T. H., 1989 Chemical geothermometers and their application to formation waters from sedimentary basins Thermal History of Sedimentary Basins New York Springer-Verlag 99117 10.1007/978-1-4612-3492-0_6.CrossRefGoogle Scholar
Ladwein, H. W., 1988 Organic geochemistry of Vienna Basin: Model for hydrocarbon generation in overthrust belts Am. Assoc. Petrol. Geologist Bull. 72 586599.Google Scholar
Lasaga, A. C., 1981 Rate laws of chemical reactions Kinetics of Geochemical Processes: Review of Mineralogy 8 168.Google Scholar
McBride, E. F., Land, L. S. and Mack, L. E., 1987 Diagenesis of eolian and fluvial feldspathic sandstones, Norphlet Formation (Upper Jurassic), Rankin County, Mississippi, and Mobile County, Alabama Amer. Assoc. Petrol. Geologist Bull. 71 10191034.Google Scholar
Muffler, L J P and Doe, B. R., 1968 Composition and mean age of detritus of the Colorado River delta in the Salton Trough, southeastern California J. Sed. Petrol. 38 384399.Google Scholar
Nadeau, P. H., Wilson, M. J., McHards, W. J. and Tait, J. M., 1984 Interparticle diffractions: A new concept for interstratified clays Clay Miner. 19 757769 10.1180/claymin.1984.019.5.06.CrossRefGoogle Scholar
Pevear, D. R. and Kharaka, Y., 1992 Illite age analysis, a new tool for basin thermal history analysis Proceeding 7th International Symposium on Water-Rock Interaction 12511254.Google Scholar
Pytte, A. M., Reynolds, R. C., Naeser, N. D. and McCulloh, T. H., 1989 The thermal transformation of smectite to illite Thermal History of Sedimentary Basins New York Springer-Verlag 133140 10.1007/978-1-4612-3492-0_8.CrossRefGoogle Scholar
Reesman, A. L., 1978 Extrapolation of aqueous dissolution data to determine comparative free energies of formation (C ΔGf°) and relative mineral stabilities Clays & Clay Minerals 26 217226 10.1346/CCMN.1978.0260305.CrossRefGoogle Scholar
Reynolds, R. C. Jr., 1981 Mixed-layered illite-smectite in a contact metamorphic environment Program and Abstracts, 28th Annual Meeting, The Clay Minerals Society, Urbana, Illinois 5.Google Scholar
Reynolds, R. C. Jr., Brindley, G. W. and Brown, G., 1980 Interstratified layer minerals Crystal Structures of Clay Minerals and their X-ray Identification 249303.CrossRefGoogle Scholar
Reynolds, R. C. Jr. and Hower, J., 1970 The nature of interlayering in mixed-layer illite-montmorillonites Clays & Clay Minerals 18 2526 10.1346/CCMN.1970.0180104.CrossRefGoogle Scholar
Roberson, H. E. and Lahann, R. W., 1981 Smectite to illite conversion rates: Effect of solution chemistry Clays & Clay Minerals 29 129135 10.1346/CCMN.1981.0290207.CrossRefGoogle Scholar
Robinson, P. T., Elders, W. A. and Muffler, L. P. J., 1976 Quaternary volcanism in the Salton Sea Geothermal Field, Imperial Valley, California Geol. Soc. Amer. Bull. 87 347360 10.1130/0016-7606(1976)87<347:QVITSS>2.0.CO;2.2.0.CO;2>CrossRefGoogle Scholar
Sass, B. M., Rosenberg, P. E. and Kittrick, J. A., 1987 The stability of illite/smectite during diagenesis: An experimental study Geochim. Cosmochim. Acta 51 21032115 10.1016/0016-7037(87)90259-6.CrossRefGoogle Scholar
Środoń, J. and Eberl, D. D., 1984 Illite Mica: Review of Mineralogy 13 495539 10.1515/9781501508820-016.Google Scholar
Truesdell, A. H., Thompson, J. M., Coplen, T. B., Nehring, N. L. and Janik, C. J., 1981 The origin of the Cerro Prieto Geothermal Brine Geothermics 10 225238 10.1016/0375-6505(81)90006-7.CrossRefGoogle Scholar
Van Olphen, H. and Fripiat, J. J., 1979 Data Handbook for Clay Materials and other Non-metallic Minerals New York Pergamon Press.Google Scholar
Velde, B. and Vasseur, G., 1992 Estimation of the dia-genetic smectite illite transformation in time-temperature space Amer. Mineral. 77 967976.Google Scholar
Whitney, G. and Northrop, H. R., 1988 Experimental investigation of the smectite to illite reaction: Dual reaction mechanisms and oxygen-isotope systematics Amer. Mineral. 73 7790.Google Scholar
Yau, Y., Peacor, D. R. and McDowell, S. D., 1987 Smectite to illite reactions in Salton Sea shales: A transmission and analytical electron microscopic study J. Sed. Petrol. 57 335342.Google Scholar