Jump to ContentJump to Main Navigation
Show Summary Details
More options …

American Mineralogist

Journal of Earth and Planetary Materials

Ed. by Baker, Don / Xu, Hongwu / Swainson, Ian


IMPACT FACTOR 2017: 2.645

CiteScore 2018: 2.55

SCImago Journal Rank (SJR) 2018: 1.355
Source Normalized Impact per Paper (SNIP) 2018: 1.103

Online
ISSN
1945-3027
See all formats and pricing
More options …
Volume 102, Issue 5

Issues

Transformation of halloysite and kaolinite into beidellite under hydrothermal condition

Hongping He
  • Corresponding author
  • Key Laboratory of Mineralogy and Metallogeny, Chinese Academy of Sciences and Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou Institute of Geochemistry, Guangzhou 510640, China
  • University of Chinese Academy of Sciences, Beijing 100049, China
  • Email
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Shichao Ji
  • Key Laboratory of Mineralogy and Metallogeny, Chinese Academy of Sciences and Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou Institute of Geochemistry, Guangzhou 510640, China
  • University of Chinese Academy of Sciences, Beijing 100049, China
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Qi Tao
  • Key Laboratory of Mineralogy and Metallogeny, Chinese Academy of Sciences and Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou Institute of Geochemistry, Guangzhou 510640, China
  • University of Chinese Academy of Sciences, Beijing 100049, China
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Jianxi Zhu
  • Key Laboratory of Mineralogy and Metallogeny, Chinese Academy of Sciences and Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou Institute of Geochemistry, Guangzhou 510640, China
  • University of Chinese Academy of Sciences, Beijing 100049, China
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Tianhu Chen
  • School of Resources and Environmental Engineering, Hefei University of Technology, Hefei 230009, China
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Xiaoliang Liang
  • Key Laboratory of Mineralogy and Metallogeny, Chinese Academy of Sciences and Guangdong Provincial Key Laboratory of Mineral Physics and Materials, Guangzhou Institute of Geochemistry, Guangzhou 510640, China
  • University of Chinese Academy of Sciences, Beijing 100049, China
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Zhaohui Li / Hailiang Dong
Published Online: 2017-05-06 | DOI: https://doi.org/10.2138/am-2017-5935

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

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.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.Google Scholar

  • Altschuler, Z.S., Dwornik, E.J., and Kramer, H. (1963) Transformation of montmorillonite to kaolinite during weathering. Science, 141, 148–152.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.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.Google Scholar

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

  • Bauer, A., Velde, B., and Berger, G. (1998) Kaolinite transformation in high molar KOH solutions. Applied Geochemistry, 13, 619–629.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.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.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.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.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.Google Scholar

  • Brindley, G.W., and Sempels, R.E. (1977) Preparation and properties of some hydroxy-aluminium beidellite. Clay Minerals, 12, 229–237.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.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.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.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.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.Google Scholar

  • Dunoyer de Segonzac, G. (1970) The transformation of clay minerals during diagenesis and low-grade metamorphism: A review. Sedimentology, 15, 281–346.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.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.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.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.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.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.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.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.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.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.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.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.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.Google Scholar

  • Mantovani, M., Escudero, A., and Becerro, A.I. (2010) Effect of pressure on kaolinite illitization. Applied Clay Science, 50, 342–347.Google Scholar

  • McAtee, J.L. (1958) Heterogeneity in montmorillonite. Clays and Clay Minerals, 5, 279–288.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.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.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.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.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.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.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.Google Scholar

  • Singer, A. (1980) The paleoclimatic interpretation of clay minerals in soils and weathering profiles. Earth-Science Reviews, 15, 303–326.Google Scholar

  • Sommer, F. (1978) Diagenesis of Jurassic sandstones in the Viking Graben. Journal of the Geological Society, 135, 63–67.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.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.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.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.Google Scholar

  • 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.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.Google Scholar

  • Sudo, T., Hayashi, H., and Shimoda, S. (1962) Mineralogical problems of intermediate clay minerals. Clays and Clay Minerals, 9, 378–392.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.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.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.Google Scholar

About the article

Received: 2016-08-18

Accepted: 2016-12-23

Published Online: 2017-05-06

Published in Print: 2017-05-24


Citation Information: American Mineralogist, Volume 102, Issue 5, Pages 997–1005, ISSN (Online) 1945-3027, ISSN (Print) 0003-004X, DOI: https://doi.org/10.2138/am-2017-5935.

Export Citation

© 2017 by Walter de Gruyter Berlin/Boston.

Comments (0)

Please log in or register to comment.
Log in