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Do bentonites have contradictory characteristics? An attempt to answer unanswered questions

Published online by Cambridge University Press:  09 July 2018

G. E. Christidis
G. E. Christidis*
Affiliation:
Technical University of Crete, Department of Mineral Resources Engineering, 73100 Chania, Greece
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Abstract

The formation of bentonites via alteration of volcanic glassy rocks is associated with apparently contradictory mineralogical, geological and geochemical characteristics, which remain poorly understood. This contribution attempts to answer some of the questions based on the work carried out in our laboratory over the past 15 y. The first question concerns the formation of opal-CT-free bentonites from acidic precursors. It is suggested that the formation of opal-CT-free bentonites is closely related to the mechanism of eruption and emplacement of parent volcanic rocks if the temperature of the parent glass after emplacement is high and/or the establishment of hydraulic gradients coupled with high permeability after deposition of volcanic glass (i.e. diagenetic alteration) if the temperature of the parent glass is low. The second question pertains to the behaviour of Fe during bentonite formation. Based on mineralogical and geological characteristics of different bentonite deposits, it is suggested that Fe is present mainly as Fe2+ and hence may be mobilized during alteration. Oxidation of Fe may take place when bentonites are exposed to more oxidizing conditions close to the surface. Assignment of Fe as Fe2+ increases the layer charge of smectites and decreases significantly the range of layer charge. Thus the smectites may have considerably different properties when formed compared with their counterparts on the surface. The third question considers the possible influence of parent-rock chemistry on the crystal chemistry of smectites. It is proposed that the parent rock may affect the chemistry of the neoformed smectites to some degree; therefore the smectite chemistry may provide indications about the geochemical affinities of the parent rock.

Keywords

bentonitesmectitevolcanic glass alterationtemperature gradientFe oxidation stateparent-glass chemistry
Type
Research Article
Information
Clay Minerals , Volume 43 , Issue 4 , December 2008 , pp. 515 - 529
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2008

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References

Aagaard, P. & Helgeson, H.C. (1982) Activity/composition relations among silicates and aqueous solutions; II, Chemical and thermodynamic consequences of ideal mixing of atoms on homological sites in montmorillonites, illites, and mixed-layer clays. Clays and Clay Minerals, 31, 207–217.CrossRefGoogle Scholar
Berger, G., Shott, J. & Loubet, M. (1987) Fundamental processes controlling the first stage of alteration of basaltic glass by seawater: an experimental study between 200°C and 320°C. Earth and Planetary Science Letters, 84, 431–445.CrossRefGoogle Scholar
Berger, G., Claparols, C., Guy, C. & Daux, V. (1994) Dissolution rate of a basalt glass in silica-rich solutions: implications for long-term alteration. Geochimica et Cosmochimica Ada, 58, 4875–4886.Google Scholar
Berry, R.W. (1999) Eocene and Oligocene Otay-Type Waxy Bentonites of San Diego County and Baja California: Chemistry, mineralogy, petrology and plate tectonic implications. Clays and Clay Minerals, 47, 70–83.CrossRefGoogle Scholar
Best, M.G. (1982) Igneous and Metamorphic Petrology. Freeman, New York, 630 pp.Google Scholar
Caballero, E., Reyes, E., Huertas, F., Linares, J. & Pozzuoli, A. (1991) Early stage smectites from pyroclastic rocks of Almeria, Spain. Chemical Geology, 89, 353–358.Google Scholar
Caballero, E., Jimenez de Cisneros, C., Huertas, F.J., Huertas, F., Pozzuoli, A. & Linares, J. (2005) Bentonites from Cabo de Gata, Almeria, Spain: a mineralogieal and geochemical overview. Clay Minerals, 40, 463–480.Google Scholar
Calarge, L., Lanson, B., Meunier, A. & Formoso, M.L. (2003) The smectitic minerals in a bentonite deposit from Melo (Uruguay). Clay Minerals, 38, 25–34.CrossRefGoogle Scholar
Calarge, L., Meunier, A., Lanson, B. & Formoso, M.L. (2006) Chemical signature of two Permian volcanic ash deposits within a bentonite bed from Melo, Uruguay. Anais da Academia Brasileira de Ciencias, 78, 525–541.Google Scholar
Cas, R.A.F. & Wright, J.V. (1988) Volcanic Successions Modern and Ancient. Unwin Hyman, London, 93–128.Google Scholar
Christidis, G.E. (1998) Comparative study of the mobility of major and trace elements during alteration of an andesite and a rhyolite to bentonite, in the islands of Milos and Kimolos, Aegean Greece. Clays and Clay Minerals, 46, 379–399.CrossRefGoogle Scholar
Christidis, G.E. (2001) Formation and growth of smectites in bentonites: a case study from Kimolos Island, Aegean, Greece. Clays and Clay Minerals, 49, 204–215.Google Scholar
Christidis, G.E. (2006) Genesis and compositional heterogeneity of smectites. Part III: Alteration of basic pyroclastic rocks — a case study from the Troodos Ophiolite Complex, Cyprus. American Mineralogist, 91, 685–701.Google Scholar
Christidis, G. & Dunham, A.C. (1993) Compositional variations in smectites. Part I. Alteration of intermediate rocks. A case study from Milos Island, Greece. Clay Minerals, 28, 255–273.Google Scholar
Christidis, G. & Dunham, A.C. (1997) Compositional variations in smectites. Part II. Alteration of acidic precursors. A case study from Milos Island, Greece. Clay Minerals, 32, 253–270.CrossRefGoogle Scholar
Christidis, G.E. & Scott, P.W. (1997) The origin and control of colour of white bentonites from the Aegean islands of Milos and Kimolos, Greece. Mineralium Deposita, 32, 271–279.Google Scholar
Christidis, G., Scott, P.W. & Marcopoulos Th. (1995) Origin of the bentonite deposits of Eastern Milos, Aegean, Greece: geological, mineralogieal and geochemical evidence. Clays and Clay Minerals, 43, 63–77.Google Scholar
Christidis, G.E., Marcopoulos, Th. & Foscolos, A. (1999) Origin, physical and chemical properties of a bentonite deposit of Chios Island, eastern Aegean, Greece. Proceedings of the 11th International Clay Conference, Ottawa, Canada, 75-82.Google Scholar
Christidis, G.E., Blum, A.E. & Eberl, D.D. (2006) Influence of layer charge and charge distribution of smectites on the flow behaviour and swelling of bentonites. Applied Clay Science, 34, 125–138.Google Scholar
Çiçel, B., Komadel, P., Bednarikova, E. & Madejová, J. (1992) Mineralogieal composition and distribution of Si, Al, Fe, Mg and Ca in the fine fractions of some Czech and Slovak bentonites. Geologica Carpathica-Series Clays, 1, 3–7.Google Scholar
Cravero, F., Keith, K.S., Murray, H.H. & Toth, T. (2000) A white bentonite from San Juan Province, Argentina — geology and potential industrial applications. Applied Clay Science, 16, 31–43.Google Scholar
Crovisier, J.L., Thomassin, J.H., Juteau, T., Eberhart, J.P., Touray, J.C. & Baillif, P. (1983) Experimental seawater—basaltic glass interaction at 50°C: study of early developed phases by electron microscopy and X-ray photoelectron spectrometry. Geochimica et Cosmochimica Ada, 47, 377–387.CrossRefGoogle Scholar
Crovisier, J.L., Honnorez, J. & Eberhart, J.P. (1987) Dissolution of basaltic glass in seawater: mechanism and rate. Geochimica et Cosmochimica Ada, 51, 2977–2990.Google Scholar
Daux, V., Guy, C., Advocat, T., Crovisier J-L. & Stille, P. (1997) Kinetic aspects of basaltic glass dissolution at 90°C: role of aqueous silicon and aluminium. Chemical Geology, 142, 109–126.Google Scholar
Ddani, M., Meunier, A., Zahraoui, M., Beaufort, D., El Wartiti, M., Fontaine, D., Boukili, B. & El Mahi, B. (2005) Clay mineralogy and chemical composition of bentonites from the Gourougou volcanic massif (northeast Morocco). Clays and Clay Minerals, 53, 250–267.Google Scholar
Drits, V.A. & Manceau, A. (2000) A model for the mechanism of Fe2+ to Fe2+ reduction in dioctahedral smectites. Clays and Clay Minerals, 48, 185–195.Google Scholar
Eberl, D.D., Środoń, J. & Northrop, R. (1986) Potassium fixation in smectite by wetting and drying. Pp. 296–326 in. Geochemical Processes at Mineral Surfaces (Davis, J.A. & Hayes, K.F., editors). ACS Symposium Series 323, American Chemical Society, Washington, D.C. Google Scholar
Elzea, J. & Murray, H.H. (1990) Variation in the mineralogical, chemical and physical properties of the Crétacéous Clay Spur bentonite in Wyoming and Montana. Applied Clay Science, 5, 229–248.Google Scholar
Elzea, J. & Murray, H.H. (1994) Clays: Bentonite. Pp. 233–246 in: Industrial Minerals & Rocks: 6 th edition (Carr, D.D., editor). Society of Mining Engineers, Littleton, Colorado, USA.Google Scholar
Fiore, S., Huertas, F.J., Tazaki, K., Huertas, F. & Linares, J. (1999) A low-temperature experimental alteration of a rhyolitic obsidian. European Journal of Mineralogy, 11, 455–469.Google Scholar
Fiore, S., Huertas, F.J., Huertas, F. & Linares, J. (2001) Smectite formation in rhyolitic obsidian as inferred by microscopic (SEM-TEM-AEM) investigation. Clay Minerals, 36, 489–500.Google Scholar
Fisher, R.V. & Schmincke, H.U. (1984) Pyroclastic Rocks. Springer Verlag, Berlin, 472 pp.CrossRefGoogle Scholar
Forster, G. & Smith, L. (1990) Fluid flow in tectonic regimes. Pp. 1–47 in: Short course on fluids in tectonically active regimes of the continental crust (Nesbitt, B.E., editor). Mineralogical Association of Canada, Ontario, Canada.Google Scholar
Foster, M.D. (1953) Geochemical studies of clay minerals: II relation between ion substitution and swelling in montmorillonites. American Mineralogist, 38, 994–1006.Google Scholar
Garrels, R.M. & Christ, C.L. (1965) Solutions, Minerals, and Equilibria. Harper, London. 450 pp.Google Scholar
Gislason, S.R. & Eugster, H.P. (1987) Meteoric water-basalt interactions. I: A laboratory study. Geochimica et Cosmochimica Acta, 51, 2827–2840.Google Scholar
Goodman, P.H., Nadeau, P.H. & Chadwick, J. (1988) Evidence for the multiphase nature of bentonites from Mössbauer and EPR spectroscopy. Clay Minerals, 23, 147–159.CrossRefGoogle Scholar
Grim, R.E. & Güven, N. (1978) Bentonites. Geology, Mineralogy, Properties and Uses. Elsevier, Amsterdam, pp. 143–155.Google Scholar
Güven, N. (1988) Smectite. Pp. 497–559 in: Hydrous Phyllosilicates (Bailey, S.W., editor). Reviews in Mineralogy, 19, Mineralogical Society of America, Washington, D.C.CrossRefGoogle Scholar
Hay, R.L. (1977) Geology of zeolites in sedimentary rocks. Pp. 53–64 in: Mineralogy and Geology of Natural Zeolites (Mumpton, F.A., editor), Reviews in Mineralogy, 4, Mineralogical Society of America. Washington, D.C. Google Scholar
Hay, R.L. & Sheppard, R.A. (2001) Occurrence of zeolites in sedimentary rocks: an overview. Pp. 217–232 in: Natural Zeolites: Properties, Applications and Uses (Bish, D.L. & Ming, D.W., editors). Reviews in Mineralogy and Geochemistry, 45, Mineralogical Society of America and the Geochemical Society, Washington, D.C. Google Scholar
Hein, J.R. & Scholl, D.W. (1978) Diagenesis and distribution of late Cenozoic volcanic sediments in the southern Bering Sea. Bulletin of the Geological Society of America, 89, 197–210.Google Scholar
Huff, W.D. (1983) Correlation of Middle Ordovician K-bentonites based on chemical fingerprinting. Journal of Geology, 91, 657–669.Google Scholar
Huff, W.D. & Kolata, D.R. (1989) Correlation of K-bentonite beds by chemical fingerprinting using multivariate statistics. Pp. 567–577 in: Quantitative Dynamic Stratigraphy (Cross, T.A., editor). Prentice Hall, New Jersey, USA.Google Scholar
Huff, W.D., Anderson, T.B., Rundle, C.C. & Odin, G.S. (1991) Chemostratigraphy, K-Ar ages and illitization of Silurian KO-bentonites from the Central Belt of the Southern Uplands-Down-Longford terrane, British Isles. Journal of Geological Society of London, 148, 861–868.Google Scholar
Huff, W.D., Merriman, R.J., Morgan, D.J. & Roberts, B. (1993) Distribution and tectonic setting of Ordovician K-bentonites in the United Kingdom. Geological Magazine, 130, 93–100.Google Scholar
Huff, W.D., Bergström, S.M., Kolata, D.R. & Sun, H. (1997) The Lower Silurian Osmundsberg K-bentonite. Part II: mineralogy, geochemistry, chemostratigraphy and tectonomagmatic significance. Geological Magazine, 135, 15–26.Google Scholar
Kawano, M., Tomita, K. & Kamino, Y. (1993) Formation of clay minerals during low temperature experimental alteration of obsidian. Clays and Clay Minerals, 41,431-441.CrossRefGoogle Scholar
Knechtel, M.M. & Patterson, S.H. (1962) Bentonite deposits of the Northern Black Hills District, Wyoming, Montana and South Dakota. Bulletin 1082-M, US Geological Survey, 893-1030.Google Scholar
Kokidis, N. (2006) Study of the Influence of Parent Rock Chemistry on the Chemical Composition of Smectites present in Bentonites. Unpublished Diploma Thesis. Technical University of Crete, Greece, 114 pp.Google Scholar
Kolata, D.R., Huff, W.D. & Bergstrom, S.M. (1996) Ordovician K-bentonites of eastern North America. Geological Society of America Special Paper, 313, 84 pp.Google Scholar
Komadel, P. (2003) Chemically modified smectites. Clay Minerals, 38, 127–138.Google Scholar
Komadel, P., Lear, P.R. & Stucki, J.W. (1990) Reduction and reoxidation of nontronite: extent of reduction and reaction rates. Clays and Clay Minerals, 38, 203–208.Google Scholar
Komadel, P., Anastacio, A.S., Andrejkovičova, S. & Stucki, J.W. (2008) Iron phases identified in bentonite from the Lieskovee deposit (Slovakia) by variable-temperature Mossbauer spectroscopy. Clay Minerals, 43, 107–115.Google Scholar
Kostka, J.E., Stucki, J.W., Nealson, K.H. & Wu, J. (1996) Reduction of structural Fe(III) in smectite, by a pure culture of the Fe-reducing bacterium Shewanella putrefaciens I strain MR-1. Clays and Clay Minerals, 44, 522–529.Google Scholar
Laird, D. A. (2006) Influence of layer charge on swelling of smectites. Applied Clay Science, 34, 74–87.Google Scholar
Lear, P.R. & Stucki, J.W. (1985) The role of structural hydrogen in the reduction and reoxidation of iron in nontronite. Clays and Clay Minerals, 33, 539–545.CrossRefGoogle Scholar
Lear, P.R. & Stucki, J.W. (1989) Effects of iron oxidation state on the specific surface area of nontronite. Clays and Clay Minerals, 37, 547–552.Google Scholar
Maccioni, L., Marchi, M., Padalino, G. Palomba, M. & Sistu, G. (1995) Bentonite occurences in Tertiary volcanic rocks of Central Sardinia, Italy. Exploration and Mining Geology, 4, 73–79.Google Scholar
Maes, A. & Cremers, A. (1977) Charge density effects in ion exchange. Part 1. Heterovalent exchange equilibria. Faraday Transactions of the Royal Chemical Society, 73, 1807–1814.Google Scholar
Manceau, A., Drits, V.A., Lanson, B., Chateigner, G., Wu, J., Huo, D., Gates, W.P. & Stucki, J.W. (2000) Oxidation—reduction mechanisms of iron in dioctahedral smectites. I. Structural chemistry of oxidized reference nontronites. American Mineralogist, 85, 133–152.Google Scholar
Merriman, R.J. & Roberts, B. (1990) Metabentonites in the Moffat Shale Group, Southern Uplands of Scotland: Geochemical evidence of ensialic marginal basin volcanism. Geological Magazine, 127, 259–271.Google Scholar
Morgan, D.J., Highley, D.E. & Bland, D.J. (1979) A montmorillonite, kaolinite association in the Lower Crétacéous of South-East England. Pp. 301–310 in: International Clay Conference 1978 (Mortland, M.M. & Farmer, V.C., editors). Elsevier, Amsterdam.Google Scholar
Mottl, M.J. & Seyfried, W.E. (1980) Sub-seafloor hydrothermal systems: rock- vs. seawater-dominated. Earth and Planetary Science Letters, 66, 137–150.Google Scholar
Murad, E., Cashion, J.D. & Brown, L.J. (1990) Magnetic ordering in Garfield nontronite under applied magnetic fields. Clay Minerals, 25, 261–269.Google Scholar
Norton, D.L. (1984) Theory of hydrothermal systems. Annual Reviews in Earth and Planetary Science, 12, 155–177.CrossRefGoogle Scholar
Pauling, L. (1960) The Nature of the Chemical Bond. Cornell University Press, Ithaca, New York.Google Scholar
Pearce, J.A., Harris, N.B.W. & Tindle, A.G. (1984) Trace element discrimination diagrams for the tectonic discrimination of granitic rocks. Journal of Petrology, 25, 956–983.CrossRefGoogle Scholar
Pellenard, P., Deconinck, J.F., Huff, W.D., Thierry, J., Marchand, D., Fortwengler, D. & Trouiller, A. (2003) Characterization and correlation of Upper Jurassic (Oxfordian) bentonite deposits in the Paris Basin and the Subalpine Basin, France. Sedimentology, 50, 1035–1060.Google Scholar
Petit, J.C., Delia Mea, G., Dran, J.C., Magonthier, M.C., Mando, P.A. & Paccagnella, A. (1990) Hydrated-layer formation during dissolution of complex silicate glasses and minerals. Geochimica et Cosmochimica Ada, 54, 1941–1955.Google Scholar
Rozenson, I. & Heller-Kallai, L. (1978) Reduction and oxidation of Fe3+ in dioctahedral smectites. III. Oxidation of octahedral iron in montmorillonite. Clays and Clay Minerals, 26, 88–92.Google Scholar
Schultz, L.G. (1969) Lithium and potassium adsorption, dehydroxylation temperature and structural water content of aluminous smectites. Clays and Clay Minerals, 17, 115–149.Google Scholar
Senkayi, A.L., Dixon, J.B., Hossner, L.R., Abder-Ruhman, M. & Fanning, D.S. (1984) Mineralogy and genetic relationships of tonstein, bentonite and lignite strata in the Eocene Yegua Formation of east-central Texas. Clays and Clay Minerals, 32, 259–271.Google Scholar
Seyfried, W.E. Jr. & Mottl, M.J. (1982) Hydrothermal alteration of basalt by seawater under seawater-dominated conditions. Geochimica et Cosmochimica Ada, 46, 985–1002.Google Scholar
Shiraki, R. & Iiyama, J.T. (1990) Na-K ion exchange reaction between rhyolitic glass and (Na,K)Cl aqueous solutions under hydrothermal conditions. Geochimica et Cosmochimica Ada, 54, 2923–2931.Google Scholar
Shiraki, R., Sakai, H., Endoh, M. & Kishima, N. (1987) Experimental studies on rhyolite— and andesite—sea-water interactions at 300°C and 1000 bars. Geochemical Journal, 21, 139–148.Google Scholar
Sparks, R.S.J., Sigurdsson, H. & Carey, S.N. (1978) Theoretical modeling of the generation, movement and emplacement of pyroclastic flows by column collapse. Journal of Geophysical Research, 83, 1727–1739.Google Scholar
Stucki, J.W. (2006) Properties and behaviour of iron in clay minerals. Pp. 423–475 in: Handbook of Clay Science (Bergaya, F., Theng, B.K.G. & Lagaly, G., editors). Elsevier, Amsterdam.Google Scholar
Stucki, J.W. & Roth, C.B. (1977) Oxidation-reduction mechanism for structural iron in nontronite. Soil Science Society of America Journal, 41, 808–814.Google Scholar
Stucki, J.W., Komadel, P. & Wilkinson, H.T. (1987) Microbial reduction of structural iron(III) in smectites. Soil Science Society of America Journal, 51, 1663–1665.CrossRefGoogle Scholar
Stucki, J.W., Lee, K., Zhang, L. & Larson, R.A. (2002) Effects of iron oxidation states on the surface and structural properties of smectites. Pure and Applied Chemistry, 74, 2145–2158.Google Scholar
Taylor, K.G. & Curtis, C.D. (1995) Stability and facies association of early diagenetic mineral assemblages: an example from a Jurassic ironstone-mudstone succession, U.K. Journal of Sedimentary Research, 65, 358–368.Google Scholar
Weaver, C.E. (1989) Clays, Muds, and Shales. Developments in Sedimentology, 44, Elsevier, Amsterdam.Google Scholar
Weaver, C.E. & Pollard, L.D. (1973) The Chemistry of Clay Minerals. Elsevier, Amsterdam, pp. 55–77.Google Scholar
White, A.F. (1983) Surface chemistry and dissolution kinetics of glassy rocks at 25°C. Geochimica et Cosmochimica Ada, 47, 805–815.Google Scholar
White, A.F. & Claesen, H.C. (1980) Kinetic model for the short-term dissolution of a rhyolitic glass. Chemical Geology, 28, 91–109.CrossRefGoogle Scholar
Williams, F.J., Elsley, B.C. & Weintritt, D.J. (1953) The variations of Wyoming bentonite beds as a function of the overburden. Clays and Clay Minerals, 2, 141–151.Google Scholar
Winchester, J. A. & Floyd, P.A. (1977) Geochemical discrimination of different magma series and their differentiation products using immobile elements. Chemical Geology, 20, 235–243.Google Scholar
Wray, D.S. (1999) Identification and long-range correlation of bentonites in Turonian—Coniacian (Upper Crétacéous) chalks of northwest Europe. Geological Magazine, 136, 361–371.Google Scholar
Yanagisawa, N., Fujimoto, K., Nakashima, S., Kurata, Y. & Sanada, N. (1997) Micro FT-IR study of the hydration-layer during dissolution of silica glass. Geochimica et Cosmochimica Acta, 61, 1165–1170.Google Scholar
Yildiz, A. & Kugcu, M. (2007) Mineralogy, chemistry and physical properties of bentonites from Ba§6ren, Kiitahya, W. Anatolia, Turkey. Clay Minerals, 42, 399–414.Google Scholar
Zielinski, R.A. (1982) The mobility of uranium and other elements during alteration of rhyolite ash to montmorillonite: a case study in the Troublesome Formation, Colorado, USA. Chemical Geology, 35, 185–204.Google Scholar