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Transformation of halloysite and kaolinite into beidellite under hydrothermal condition

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Published/Copyright: May 6, 2017
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American Mineralogist
From the journal American Mineralogist Volume 102 Issue 5

Abstract

Understanding clay mineral transformation is of fundamental importance to unraveling geological and environmental processes and to better understanding the unique structure and property of phyllosilicates. To date, two pathways have been identified, i.e., the transformation among 2:1 type clay minerals (e.g., illitization of smectite) and from 2:1 type to 1:1 type (e.g., kaolinization of smectite). However, the transformation of 1:1 to 2:1 type is less commonly observed. In this study, hydrothermal experiments were conducted to investigate the possibility of the transformation of 1:1 type clay minerals (i.e., halloysite and kaolinite) into 2:1 ones (i.e., beidellite). The obtained products were characterized by XRD, TG, FTIR, 27Al and 29Si MAS NMR, and HRTEM. XRD patterns of the hydrothermal products display characteristic basal spacing of smectite group minerals at 1.2–1.3 nm with dramatic decrease/disappearance of the (001) reflection of halloysite and kaolinite. This is consistent with HRTEM observations, in which clay layers with a thickness of 1.2–1.4 nm are observed in all hydrothermal products and the Si/Al ratio determined by EDS analysis is close to that of beidellite. The basal spacing increases to ∼1.70 nm upon ethylene glycolation, displaying swelling ability of the resultant minerals. The consumption of surface OH in precursor minerals during the transformation leads to a dramatic decrease of mass loss of dehydroxylation and merging of the well resolved OH stretching vibrations in precursor minerals into one at ca. 3667 cm−1, which is indicative of beidellite. These results demonstrate that both halloysite and kaolinite can be converted to 2:1 beidellite under hydrothermal condition, and the transformation of halloysite is easier than that of kaolinite. Such transformation of 1:1 clay minerals to 2:1 ones could be a new pathway for the transformation of clay minerals in nature. Meanwhile, the substitution of Al3+ for Si4+ is found in all newly formed beidellite, suggesting the chemical composition of the newly formed Si-O tetrahedral sheet is different from the one inherited from the precursor clay minerals. This can well explain the formation of “polar layer” in mixed-layer phyllosilicates. These findings are of high importance for better understanding the transformation among clay minerals and unique structure of mixed-layer phyllosilicates.

Keywords: Clay transformation; hydrothermal condition; halloysite; kaolinite; beidellite

Acknowledgments

This is contribution No. IS-2358 from GIGCAS. This work was financially supported by National Natural Science Foundation of China (Grant Nos. 41530313, 41372048), CAS Key Research Program of Frontier Sciences (Grant No. QYZDJSSW-DQC023-1), and the CAS/SAFEA International Partnership Program for Creative Research Teams (Grant No. 20140491534).

References cited

Alexander, L.T., Faust, G.T., Hendricks, S.B., Insley, H., and Mcmurdie, H.F. (1943) Relationship of the clay minerals halloysite and endellite. American Mineralogist, 28, 1–18.Search in Google Scholar

Altaner, S.P., Weiss, C.A., and Kirkpatrick, R.J. (1988) Evidence from 29Si NMR for the structure of mixed-layer illite/smectite clay minerals. Nature, 331, 699–702.10.1038/331699a0Search in Google Scholar

Altschuler, Z.S., Dwornik, E.J., and Kramer, H. (1963) Transformation of montmorillonite to kaolinite during weathering. Science, 141, 148–152.10.1126/science.141.3576.148Search in Google Scholar

Amoruic, M., and Olives, J. (1998) Transformation mechanisms and interstratification in conversion of smectite to kaolinite: An HRTEM study. Clays and Clay Minerals, 46, 521–527.10.1346/CCMN.1998.0460505Search in Google Scholar

Aoudjit, H., Robert, M., Elsass, F., and Curmi, P. (1995) Detailed study of smectite genesis in granitic saprolites by analytical electron microscopy. Clay Minerals, 30, 135–148.10.1180/claymin.1995.030.2.05Search in Google Scholar

Bates, T.F., Hildebrand, F.A., and Swineford, A. (1950) Morphology and structure of endellite and halloysite. American Mineralogist, 35, 463–484.Search in Google Scholar

Bauer, A., Velde, B., and Berger, G. (1998) Kaolinite transformation in high molar KOH solutions. Applied Geochemistry, 13, 619–629.10.1016/S0883-2927(97)00094-2Search in Google Scholar

Bentabol, M., Ruiz Cruz, M.D., Huertas, F.J., and Linares, J. (2003a) Hydrothermal transformation of kaolinite to illite at 200 and 300 °C. Clay Minerals, 38, 161–172.10.1180/0009855033820086Search in Google Scholar

Bentabol, M., Ruiz Cruz, M.D., Huertas, F.J., and Linares, J. (2003b) Characterization of the expandable clays formed from kaolinite at 200 °C. Clay Minerals, 38, 445–458.10.1180/0009855033840108Search in Google Scholar

Bentabol, M., Ruiz Cruz, M.D., Huertas, F.J., and Linares, J. (2006) Chemical and structural variability of illitic phases formed from kaolinite in hydrothermal conditions. Applied Clay Science, 32, 111–124.10.1016/j.clay.2005.12.003Search in Google Scholar

Bergaya, F., Theng, B.K.G., and Lagaly, G. (2006) Clays in industry. In F. Bergaya, B.K.G. Theng and G. Lagaly, Eds., Handbook of Clay Science, p. 499–622. Elsevier, Kidlington, Oxford.10.1016/S1572-4352(05)01015-9Search in Google Scholar

Breen, C., Madejová, J., and Komadel, P. (1995) Correlation of catalytic activity with infra-red, 29Si MAS NMR and acidity data for HCl-treated fine fractions of montmorillonites. Applied Clay Science, 10, 219–230.10.1016/0169-1317(95)00024-XSearch in Google Scholar

Brindley, G.W., and Sempels, R.E. (1977) Preparation and properties of some hydroxy-aluminium beidellite. Clay Minerals, 12, 229–237.10.1180/claymin.1977.012.3.05Search in Google Scholar

Chermak, J.A., and Rimstidt, J.D. (1990) The hydrothermal transformation rate of kaolinite to muscovite/illite. Geochimica et Cosmochimica Acta, 54, 2979–2990.10.1016/0016-7037(90)90115-2Search in Google Scholar

Christidis, G., and Dunham, A.C. (1993) Compositional variation in smectites: Part I. Alteration of intermediate volcanic rocks. Acase study from Milos Island, Greece. Clay Minerals, 28, 255–273.10.1180/claymin.1993.028.2.07Search in Google Scholar

Cuadros, J., and Altaner, S.P. (1998) Characterization of mixed-layer illite-smectite from bentonites using microscopic, chemical, and X-ray methods: Constraints on the smectite-to-illite transformation mechanism. American Mineralogist, 83, 762–774.10.2138/am-1998-7-808Search in Google Scholar

Cuadros, J., and Linares, J. (1995) Some evidence supporting the existence of polar layers in mixed-layer illite/smectite. Clays and Clay Minerals, 43, 467–473.10.1346/CCMN.1995.0430410Search in Google Scholar

Dudek, T., Cuadros, J., and Fiore, S. (2006) Interstratified kaolinite-smectite: Nature of the layers and mechanism of smectite kaolinization. American Mineralogist, 91, 159–170.10.2138/am.2006.1897Search in Google Scholar

Dunoyer de Segonzac, G. (1970) The transformation of clay minerals during diagenesis and low-grade metamorphism: A review. Sedimentology, 15, 281–346.10.1111/j.1365-3091.1970.tb02190.xSearch in Google Scholar

Dutta, P.K., and Suttner, L.J. (1986) Alluvial sandstone composition and paleoclimate, II. Authigenic mineralogy. Journal of Sedimentary Research, 56, 346–358.Search in Google Scholar

Ferrage, E., Lanson, B., Sakharov, B.A., Geoffroy, N. Jacquot, E., and Drits, V.A. (2007) Investigation of dioctahedral smectitie hydration properties by modeling of X-ray diffracion profiles: Influence of layer charge and charge location. American Mineralogist, 92, 1731–1743.10.2138/am.2007.2273Search in Google Scholar

Galán, E., and Ferrell, R.E. (2013) Genesis of clay minerals. In F. Bergaya and G. Lagaly, Eds., Handbook of Clay Science, p. 83–126. Elsevier, Oxford.10.1016/B978-0-08-098258-8.00003-1Search in Google Scholar

He, H.P., Guo, J.G., Zhu, J.X., and Hu, C. (2003) 29Si and 27Al MAS NMR study of the thermal transformations of kaolinite from North China. Clay Minerals, 38, 551–559.10.1180/0009855033840114Search in Google Scholar

He, H.P., Tao, Q., Zhu, J.X., Yuan, P., Shen, W., and Yang, S.Q. (2013) Silylation of clay mineral surfaces. Applied Clay Science, 71, 15–20.10.1016/j.clay.2012.09.028Search in Google Scholar

He, H.P., Li, T., Tao, Q., Chen, T.H., Zhang, D., Zhu, J.X., Yuan, P., and Zhu, R.L. (2014) Aluminum ion occupancy in the structure of synthetic saponites: Effect on crystallinity. American Mineralogist, 99, 109–116.10.2138/am.2014.4543Search in Google Scholar

Huang, W.L. (1993) The formation of illitic clays from kaolinite in KOH solution from 225 °C to 350 °C. Clays and Clay Minerals, 41, 645–654.10.1346/CCMN.1993.0410602Search in Google Scholar

Kloprogge, J.T., and Frost, R.L. (2000) The effect of synthesis temperature on the FT-Raman and FT-IR spectra of saponites. Vibrational Spectroscopy, 23, 119–127.10.1016/S0924-2031(00)00056-4Search in Google Scholar

Lanson, B., Beaufort, D., Berger, G., Baradat, J., and Lacharpagen, J.C. (1996) Illitization of diagenetic kaolinite-to-dickite conversion series: Late-stage diagenesis of the Lower Permian Potliegend sandstone reservoir, offshore of the Netherlands. Journal of Sedimentary Researh, 66, 501–518.Search in Google Scholar

Lanson, B., Beaufort, D., Berger, G., Bauer, A., Cassagnabère, A., and Meunier, A. (2002) Authigenic kaolin and illitic minerals during burial diagenesis of sandstones: A review. Clay Minerals, 37, 1–22.10.1180/0009855023710014Search in Google Scholar

Madejová, J., and Komadel, P. (2001) Baseline studies of the clay minerals society source clays: infrared methods. Clays and Clay Minerals, 49, 410–432.10.1346/CCMN.2001.0490508Search in Google Scholar

Malek, Z., Balek, V., Garfinke-Shweky, D., and Yariv, S. (1997) The study of the dehydration and dehydroxylation of smectites by emanation thermal analysis. Journal of Thermal Analysis, 48, 83–92.10.1007/BF01978968Search in Google Scholar

Mantovani, M., and Becerro, A.I. (2010) Illitization of kaolinite: The effect of pressure on the reaction rate. Clays and Clay Minerals, 58, 766–771.10.1346/CCMN.2010.0580604Search in Google Scholar

Mantovani, M., Escudero, A., and Becerro, A.I. (2010) Effect of pressure on kaolinite illitization. Applied Clay Science, 50, 342–347.10.1016/j.clay.2010.08.024Search in Google Scholar

McAtee, J.L. (1958) Heterogeneity in montmorillonite. Clays and Clay Minerals, 5, 279–288.10.1346/CCMN.1956.0050123Search in Google Scholar

Odin, G.S. (1988) Glaucony from the Gulf of Guinea. In G.S. Odin, Ed., Green Marine Clays: Oolitic Ironstone Facies, Verdine Facies, Glaucony Facies and Celadonite-bearing Facies—A Comparative Study, p. 225–248. Elsevier, Amsterdam.10.1016/S0070-4571(08)70066-9Search in Google Scholar

Ramos, M.E., Garcia-Palma, S., Rozalen, M., Johnston, C.T., and Huertas, F.J. (2014) Kinetics of montmorillonite dissolution: An experimental study of the effect of oxalate. Chemical Geology, 363, 283–292.10.1016/j.chemgeo.2013.11.014Search in Google Scholar

Rocha, J., and Klinowski, J. (1990) 29Si and 27Al magic-angle-spinning NMR studies of the thermal transformation of kaolinite. Physics and Chemistry of Minerals, 17, 179–186.10.1007/BF00199671Search in Google Scholar

Rozalén, M.L., Huertas, F.J., Brady, P.V., Cama, J., García-Palma, S., and Linares, J. (2008) Experimental study of the effect of pH on the kinetics of montmorillonite dissolution at 25 °C. Geochimica et Cosmochimica Acta, 72, 4224–4253.10.1016/j.gca.2008.05.065Search in Google Scholar

Russell, J.D. (1987) Infrared methods. In M.J. Wilson, Ed., A handbook of determinative methods in clay mineralogy, 133–173. Blackie, Glasgow and London.Search in Google Scholar

Ryan, P.C., and Huertas, F.J. (2009) The temporal evolution of pedogenic Fe-smectite to Fe-kaolin via interstratified kaolin-smectite in a moist tropical soil chronosequence. Geoderma, 151, 1–15.10.1016/j.geoderma.2009.03.010Search in Google Scholar

Schoonheydt, R.A., and Johnston, C.T. (2013) Surface and interface chemistry of clay minerals. In F. Bergaya and G. Lagaly, Eds., Handbook of Clay Science, 142–148. Elsevier, Kidlington, Oxford.10.1016/B978-0-08-098258-8.00005-5Search in Google Scholar

Singer, A. (1980) The paleoclimatic interpretation of clay minerals in soils and weathering profiles. Earth-Science Reviews, 15, 303–326.10.1016/0012-8252(80)90113-0Search in Google Scholar

Sommer, F. (1978) Diagenesis of Jurassic sandstones in the Viking Graben. Journal of the Geological Society, 135, 63–67.10.1144/gsjgs.135.1.0063Search in Google Scholar

Środoń, J. (1999) Nature of mixed-layer clays and mechanisms of their formation and alteration. Annual Review of Earth and Planetary Sciences, 27, 19–53.10.1146/annurev.earth.27.1.19Search in Google Scholar

Środoń, J., Eberl, D.D., and Drits, V.A. (2000) Evolution of fundamental-particle size during illitization of smectite and implications for reaction mechanism. Clays and Clay Minerals, 48, 446–458.10.1346/CCMN.2000.0480405Search in Google Scholar

Stern, L.A., Chamberlain, C.P., Reynolds, R.C., and Johnson, G.D. (1997) Oxygen isotope evidence of climate change from pedogenic clay minerals in the Himalayan molasse. Geochimica et Cosmochimica Acta, 61, 731–744.10.1016/S0016-7037(96)00367-5Search in Google Scholar

Stixrude, L., and Peacor, D.R. (2002) First-principles study of illite-smectite and implications for clay mineral systems. Nature, 420, 165–168.10.1038/nature01155Search in Google Scholar PubMed

Komadel, P., Madejová, J., Janek, M., Gates, W.P., Kirkpatrick, R.J., and Stucki, J.W. (1996) Dissolution of hectorite in inorganic acids. Clays and Clay Minerals, 44, 228–236.10.1346/CCMN.1996.0440208Search in Google Scholar

Šucha, V., Elsass, F., Eberl, D.D., Kuchta, L., Madejová, J., Gates, W.P., and Komadel, P. (1998) Hydrothermal synthesis of ammonium illite. American Mineralogist, 83, 58–67.10.2138/am-1998-1-206Search in Google Scholar

Sudo, T., Hayashi, H., and Shimoda, S. (1962) Mineralogical problems of intermediate clay minerals. Clays and Clay Minerals, 9, 378–392.10.1016/B978-1-4831-9842-2.50028-6Search in Google Scholar

Suquet, H., de la Calle, C., and Pezerat, H. (1975) Swelling and structural organization of saponite. Clays and Clay Minerals, 23, 1–9.10.1346/CCMN.1975.0230101Search in Google Scholar

Tunney, J.J., and Detellier, C. (1996) Chemically modified kaolinite. Grafting of methoxy groups on the interlamellar aluminol surface of kaolinite. Journal of Materials Chemistry, 6, 1679–1685.10.1039/jm9960601679Search in Google Scholar

Wilson, M.J. (1999) The origin and formation of clay minerals in soils: Past, present and future perspectives. Clay Minerals, 34, 7–25.10.1180/000985599545957Search in Google Scholar

Received: 2016-8-18
Accepted: 2016-12-23
Published Online: 2017-5-6
Published in Print: 2017-5-24

© 2017 by Walter de Gruyter Berlin/Boston

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https://doi.org/10.2138/am-2017-5935
Keywords for this article
Clay transformation; hydrothermal condition; halloysite; kaolinite; beidellite

Articles in the same Issue

  1. Highlights and Breakthroughs
  2. Defining minerals in the age of humans
  3. Highlights and Breakthroughs
  4. Bottled samples of Earth’s lower mantle
  5. Highlights and Breakthroughs
  6. Two ways of looking at chemical bonding
  7. Highlights and Breakthroughs
  8. Diamonds from the lower mantle?
  9. Review
  10. A review and update of mantle thermobarometry for primitive arc magmas
  11. Special collection: New advances in subduction zone magma genesis
  12. Using mineral geochemistry to decipher slab, mantle, and crustal input in the generation of high-Mg andesites and basaltic andesites from the northern Cascade Arc
  13. Special collection: From magmas to ore deposits
  14. Sperrylite saturation in magmatic sulfide melts: Implications for formation of PGE-bearing arsenides and sulfarsenides
  15. Special collection: Water in nominally hydrous and anhydrous minerals
  16. Water transport by subduction: Clues from garnet of Erzgebirge UHP eclogite
  17. Special collection: Apatite: A common mineral, uncommonly versatile
  18. Single-track length measurements of step-etched fission tracks in Durango apatite: “Vorsprung durch Technik”
  20. Transformation of halloysite and kaolinite into beidellite under hydrothermal condition
  22. Controls on trace-element partitioning among co-crystallizing minerals: Evidence from the Panzhihua layered intrusion, SW China
  24. Using mineral equilibria to estimate H2O activities in peridotites from the Western Gneiss Region of Norway
  26. Rowleyite, [Na(NH4,K)9Cl4][ V25+,4+(P,As)O8]6⋅n[H2O,Na,NH4,K,Cl], a new mineral with a microporous framework structure
  28. Textures and high field strength elements in hydrothermal magnetite from a skarn system: Implications for coupled dissolution-reprecipitation reactions
  30. X-ray spectroscopy study of the chemical state of “invisible” Au in synthetic minerals in the Fe-As-S system
  32. Dry annealing of metamict zircon: A differential scanning calorimetry study
  34. Tightly bound water in smectites
  36. Mineralogical controls on antimony and arsenic mobility during tetrahedrite-tennantite weathering at historic mine sites Špania Dolina-Piesky and Ľubietová-Svätodušná, Slovakia
  38. Deep mantle origin and ultra-reducing conditions in podiform chromitite: Diamond, moissanite, and other unusual minerals in podiform chromitites from the Pozanti-Karsanti ophiolite, southern Turkey
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  46. Acceptance of the 2016 Roebling Medal of the Mineralogical Society of America
  48. Presentation of the Mineralogical Society of America Award for 2016 to Anat Shahar
  50. Acceptance of the Mineralogical Society of America Award for 2016
  52. Presentation of the Dana Medal of the Mineralogical Society of America for 2016 to Sumit Chakraborty
  54. Acceptance of the Dana Medal of the Mineralogical Society of America for 2016
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