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On the Problems of Total Specific Surface Area and Cation Exchange Capacity Measurements in Organic-Rich Sedimentary Rocks

Published online by Cambridge University Press:  01 January 2024

Arkadiusz Derkowski  and
Thomas F. Bristow
Arkadiusz Derkowski*
Affiliation:
Institute of Geological Sciences, Polish Academy of Sciences, INGPAN, Senacka 1, PL-31002, Krakow, Poland
Thomas F. Bristow
Affiliation:
NASA Ames Research Center, Moffett Field, CA 94035, USA
*
*E-mail address of corresponding author: [email protected]
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Abstract

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The increasing exploration and exploitation of hydrocarbon resources hosted by oil and gas shales demands the correct measurement of certain properties of sedimentary rocks rich in organic matter (OM). Two essential properties of OM-rich shales, the total specific surface area (TSSA) and cation exchange capacity (CEC), are primarily controlled by the rock’s clay mineral content (i.e. the type and quantity). This paper presents the limitations of two commonly used methods of measuring bulk-rock TSSA and CEC, ethylene glycol monoethyl ether (EGME) retention and visible light spectrometry of Co(III)-hexamine, in OM-rich rocks. The limitations were investigated using a suite of OM-rich shales and mudstones that vary in origin, age, clay mineral content, and thermal maturity.

Ethylene glycol monoethyl ether reacted strongly with and was retained by natural OM, producing excess TSSA if calculated using commonly applied adsorption coefficients. Although the intensity of the reaction seems to depend on thermal maturity, OM in all the samples analyzed reacted with EGME to an extent that made TSSA values unreliable; therefore, EGME is not recommended for TSSA measurements on samples containing >3% OM.

Some evidence indicated that drying at ⩾200°C may influence bulk-rock CEC values by altering OM in early mature rocks. In light of this evidence, drying at 110°C is recommended as a more suitable pretreatment for CEC measurements in OM-rich shales. When using visible light spectrometry for CEC determination, leachable sample components contributed to the absorbance of the measured wavelength (470 nm), decreasing the calculated bulk rock CEC value. A test of sample-derived excess absorbance with zero-absorbance solutions (i.e. NaCl) and the introduction of corrections to the CEC calculation are recommended.

Keywords

BitumenCECEGMEKerogenOrganic MatterShaleSpecific Surface Area
Type
Article
Information
Clays and Clay Minerals , Volume 60 , Issue 4 , August 2012 , pp. 348 - 362
Copyright
Copyright © Clay Minerals Society 2012

References

Asadu, C.L.A. Diels, J. and Vanlauwe, B., 1997 A comparison of the contributions of clay, silt, and organic matter to the effective CEC of soils of Subsaharan Africa Soil Science 162 785–794.CrossRefGoogle Scholar
Ashida, R. Painter, P. and Larsen, J.W., 2005 Kerogen chemistry 4. Thermal decarboxylation of kerogens. Energy & Fuels 19 1954–1961.CrossRefGoogle Scholar
Bardon, C. Bieber, M.T. Cuiec, L. Jacquin, C. Courbot, A. Deneuville, G. Simon, J.M. Voirin, J.M. Espy, M. Nectoux, A. and Pellerin, A., 1993 Recommandations pour la détermination experérimentale de la capacité d’échange de cations des milieux argileux Revue de l’Institut Francais du Pétrole 38 621–626.Google Scholar
Bergmann, J. Friedel, P. and Kleeberg, R., 1998 BGMN a new fundamental parameter-based Rietveld program for laboratory X-ray sources, its use in quantitative analysis and structure investigations Commission of Powder Diffraction, International Union of Crystallography, CPD Newsletter 20 5–8.Google Scholar
Blum, A.E. and Eberl, D.D., 2004 Measurement of clay surface areas by polyvinylpyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance Clays and Clay Minerals 52 589–602.CrossRefGoogle Scholar
Bristow, T.F. Kennedy, M.J. Derkowski, A. Droser, M. Jiang, G. and Creaser, R.A., 2009 Mineralogical constraints on the paleoenvironments of the Ediacaran Doushantuo Formation Proceedings of the National Academy of Sciences of the USA 106 13190–13195.CrossRefGoogle ScholarPubMed
Bristow, T.F. Bonifacie, M. Derkowski, A. Eiler, J.M. and Grotzinger, J.P., 2011 A hydrothermal origin for isotopically anomalous cap dolostone cements from South China Nature 747 68–72.CrossRefGoogle Scholar
Chapman, H.D., 1965 Cation-exchange capacity Methods of Soil Analysis — Chemical and Microbiological Properties 9 891–901.Google Scholar
Chiou, C.T. and Rutheford, D.W., 1997 Effects of exchanged cation and layer charge on the sorption of water and EGME vapors on montmorillonite clays Clays and Clay Minerals 45 867–880.CrossRefGoogle Scholar
Chiou, C.T. Kile, D.E. and Malcolm, R.L., 1988 Sorption of vapors of some organic liquids on soil humic acid and its relation to partitioning of organic compounds in soil organic matter Environmental Science & Technology 22 298–303.CrossRefGoogle ScholarPubMed
Chiou, C.T. Lee, J.F. and Boyd, S.A., 1990 The surface area of soil organic matter Environmental Science & Technology 24 1164–1166.CrossRefGoogle Scholar
Chiou, C.T. Rutherford, D.W. and Manes, M., 1993 Sorption of N2 and EGME vapors on some soils, clays, and mineral oxides and determination of sample surface areas by use of sorption data Environmental Science & Technology 27 1587–1594.CrossRefGoogle Scholar
Cihacek, L.J. and Bremner, J.M., 1979 Simplified ethylene glycol monoethyl ether procedure for assessment of soil surface area Soil Science Society of America Journal 43 821–822.CrossRefGoogle Scholar
Compton, J.S., 1991 Origin and diagenesis of clay minerals in the Monterey formation, Santa Maria basin area, California Clays and Clay Minerals 39 449–466.CrossRefGoogle Scholar
Cornelissen, G. Gustafsson, Bucheli, T.D. Jonker, M.T.O. Koelmans, A.A. and Van Noort, P.C.M., 2005 Extensive sorption of organic compounds to black carbon, coal, and kerogen in sediments and soils: mechanisms and consequences for distribution, bioaccumulation, and biodegradation Environmental Science & Technology 39 6881–6895.CrossRefGoogle ScholarPubMed
Czímerová, A. Bujdák, J. and Dohrmann, R., 2006 Traditional and novel methods for estimating the layer charge of smectites Applied Clay Science 34 2–13.CrossRefGoogle Scholar
De Jonge, H. and Mittelmeijer-Hazeleger, M.C., 1996 Adsorption of CO2 and N2 on soil organic matter: nature of porosity, surface area, and diffusion mechanisms Environmental Science & Technology 30 408–413.CrossRefGoogle Scholar
Derkowski, A. Franus, W. Waniak-Nowicka, H. and Czámerová, A., 2007 Textural properties vs CEC and EGME retention of Na-X zeolite prepared from fly ash at room temperature. International Journal of Mineral Processing 82 57–68.Google Scholar
Derkowski, A. Drits, V.A. and McCarty, D.K., 2012 Rehydration of dehydrated-dehydroxylated smectite in a low water vapor environment American Mineralogist 97 110–127.CrossRefGoogle Scholar
Dohrmann, R., 2006 Cation exchange capacity methodology II: A modified silver-thiourea method Applied Clay Science 3 38–46.CrossRefGoogle Scholar
Dohrmann, R. and Kaufhold, S., 2009 Three new, quick CEC methods for determining the amounts of exchangeable calcium cations in calcareous clays Clays and Clay Minerals 57 338–352.CrossRefGoogle Scholar
Dyal, R.S. and Hendricks, S.B., 1950 Total surface area of clays in polar liquids as a characteristic index Soil Science 69 421–432.CrossRefGoogle Scholar
Eltantawy, I.M. and Arnold, P.W., 1974 Ethylene glycol sorption by homoionic montmorillonites Journal of Soil Science 25 99–110.CrossRefGoogle Scholar
Ferrage, E. Lanson, B. Sakharov, B.A. Geoffroy, N. Jacquot, E. and Drits, V.A., 2007 Investigation of dioctahedral smectite hydration properties by modeling of X-ray diffraction profiles: Influence of layer charge and charge location American Mineralogist 92 1731–1743.CrossRefGoogle Scholar
Helling, C.S. Chesters, G. and Corey, R.B., 1964 Contribution of organic matter and clay to soil cationexchange capacity as affected by the pH of the saturating solution Soil Science Society of America Journal 28 517–520.CrossRefGoogle Scholar
Isaacs, C., 1984 Hemipelagic Deposits in a Miocene basin, California: Towards a model of Lithologic Variation and Sequence 15 481–496.Google Scholar
Jackson, M.L., 1969 Soil Chemical Analysis — Advanced Course 2 Wisconsin, USA University of Madison.Google Scholar
Jones, R.L. and Blatt, H., 1984 Mineral dispersal patterns in the Pierre Shale Journal of Sedimentary Research 54 17–28.Google Scholar
Kaufhold, S. Dohrmann, R. and Klinkenberg, M., 2010a Water-uptake capacity of bentonites Clays and Clay Minerals 58 37–43.CrossRefGoogle Scholar
Kaufhold, S. Dohrmann, R. Klinkenberg, M. Siegesmund, S. and Ufer, K., 2010b N2-BET specific surface area of bentonites Journal of Colloid and Interface Science 349 275–282.CrossRefGoogle Scholar
Kennedy, M.J. and Wagner, T., 2011 A clay mineral continental amplifier for marine carbon sequestration in a greenhouse ocean Proceedings of the National Academy of Sciences of the USA 108 9776–9781.CrossRefGoogle Scholar
Kennedy, M.J. Pevear, D.R. and Hill, R.J., 2002 Mineral surface control of organic carbon in black shale Science 295 657–660.CrossRefGoogle ScholarPubMed
Laird, D.A., 1999 Layer charge influences on the hydration of expandable 2:1 phyllosilicates Clays and Clay Minerals 47 630–636.CrossRefGoogle Scholar
Larsen, J.W. and Li, S., 1997 Changes in the macromolecular structure of a type I kerogen during maturation Energy & Fuels 11 897–901.CrossRefGoogle Scholar
Larsen, J.W. Parikh, H. and Michels, R., 2002 Changes in the cross-link density of Paris Basin Toarcian kerogen during maturation Organic Geochemistry 33 1143–1152.CrossRefGoogle Scholar
Larsen, J.W. Islas-Flores, C. Aida, M.T. Opaprakasit, P. and Painter, P., 2005 Kerogen chemistry 2. Low-temperature anhydride formation in kerogens. Energy & Fuels 19 145–151.Google Scholar
Lewan, M.D., 1983 Effects of thermal maturation on stable organic carbon isotopes as determined by hydrous pyrolysis of Woodford Shale Geochimica et Cosmochimica Acta 47 1471–1479.CrossRefGoogle Scholar
Lewan, M.D., 1986 Stable carbon isotopes of amorphous kerogens from Phanerozoic sedimentary rocks Geochimica et Cosmochimica Acta 50 1583–1591.CrossRefGoogle Scholar
LeBoeuf, E.J. Weber, W.J. Jr, 2000 Macromolecular characteristics of natural organic matter 1. Insights from glass transition and enthalpic relaxation behavior. Environmental Science & Technology 34 3623–3631.Google Scholar
Mikutta, R. Kleber, M. Kaiser, K. and Jahn, R., 2005 Review: organic matter removal from soils using hydrogen peroxide, sodium hypochlorite, and disodium peroxodisulfate Soil Science Society of America Journal 69 120–135.CrossRefGoogle Scholar
Moore, D.M. and Reynolds, R.C., 1997 X-Ray Diffraction and the Identification and Analysis of Clay Minerals 2 New York Oxford University Press.Google Scholar
Morton, J.P., 1985 Rb-Sr dating of diagenesis and source age of clays in Upper Devonian black shales of Texas Geological Society of America Bulletin 96 1043–1049.2.0.CO;2>CrossRefGoogle Scholar
Okiongbo, K.S. Aplin, A.C. and Larter, S.R., 2005 Changes in type II kerogen density as a function of maturity: evidence from the Kimmeridge Clay Formation Energy & Fuels 19 2495–2499.CrossRefGoogle Scholar
Orsini, L. and Remy, J.C., 1976 Utilisation du chlorure de cobaltihexammine pour la dé ermination simultanée de la capacité d’échange et des bases échangeables des sols Science du Sol 4 269–275.Google Scholar
Peters, K.E. Cunningham, A.E. Walters, C.C. Jigang, J. and Zhaoan, F., 1996 Petroleum systems in the Jiangling-Dangyang area, Jianghan Basin, China Organic Geochemistry 24 1035–1060.CrossRefGoogle Scholar
Quirk, J.P. and Murray, R.S., 1999 Appraisal of the ethylene glycol monoethyl ether method for measuring hydratable surface area of clays and soils Soil Science Society of America Journal 63 839–849.CrossRefGoogle Scholar
Rashid, M.A., 1969 Contribution of humic substances to the cation exchange capacity of different marine sediments Maritime Sediments 5 44–50.Google Scholar
Rengasamy, P. Churchman, G.J., Peverill, K.I. Sparrow, L.A. and Reuter, D.J., 1999 Cation exchange capacity, exchange cations and sodicity Soil Analysis, an Interpretation Manual Australia CSIRO Publishing 147–157.Google Scholar
Reynolds, R.C. Jr, 1989 Principles and techniques of quantitative analysis of clay minerals by X-ray powder diffraction Quantitative Mineral Analysis of Clays 1 4–36.Google Scholar
Schultz, L.G., 1978 Mixed-layer Clay in the Pierre Shale and Equivalent Rocks, Northern Great Plains Region.CrossRefGoogle Scholar
Szczerba, M.S. Środoń, J. Skiba, M. and Derkowski, A., 2010 One-dimensional structure of exfoliated polymerlayered silicate nanocomposites: A polyvinylpyrrolidone (PVP) case study Applied Clay Science 47 235–241.CrossRefGoogle Scholar
Środoń, J., 2009 Quantification of illite and smectite and their layer charges in sandstones and shales from shallow burial depth Clay Minerals 44 421–434.CrossRefGoogle Scholar
Środoń, J. and Eberl, D.D., 1984 Illite Micas 13 495–544.CrossRefGoogle Scholar
Środoń, J. and McCarty, D.K., 2008 Surface area and layer charge of smectite from CEC and EGME/H2O-retention measurements Clays and Clay Minerals 56 155–174.CrossRefGoogle Scholar
Środoń, J. Elsass, F. McHardy, W.J. and Morgan, D.J., 1992 Chemistry of illite-smectite inferred from TEM measurements of fundamental particles Clay Minerals 27 137–158.CrossRefGoogle Scholar
Środoń, J. Drits, V.A. McCarty, D.K. Hsieh, J.C.C. and Eberl, D.D., 2001 Quantitative XRD analysis of clay-rich rocks from random preparations Clays and Clay Minerals 49 514–528.CrossRefGoogle Scholar
Środoń, J. Zeelmaekers, E. and Derkowski, A., 2009 The charge of component layers of illite-smectite in bentonites and the nature of end-member illite Clays and Clay Minerals 57 650–672.CrossRefGoogle Scholar
Tiller, K.G. and Smith, L.H., 1990 Limitations of EGME retention to estimate the surface area of soils Australian Journal of Soil Research 28 1–26.CrossRefGoogle Scholar
Tissot, B.P. and Welte, D.H., 1984 Petroleum Formation and Occurrence Berlin Springer-Verlag 160–169.CrossRefGoogle Scholar
Vandenbroucke, M. and Largeau, C., 2007 Kerogen origin, evolution and structure Organic Geochemistry 38 719–833.CrossRefGoogle Scholar
Wagner, T. and Pletsch, T., 1999 Tectono-sedimentary controls on Cretaceous black shale deposition along the opening of the Equatorial Atlantic Gateway (ODP 159) The Oil and Gas Habitats of the South Atlantic 153 241–265.Google Scholar
Woodruff, W.F. and Revil, A., 2011 CEC-normalized claywater sorption isotherm Water Resources Research 47 1–15.CrossRefGoogle Scholar