Skip to main content
SpringerLink
Log in

Hydrothermal Stability of Layered Silicates in Neutral and Acidic Media: Effect on Engineered-Barrier Safety

  • Published:
Clays and Clay Minerals

Abstract

Many environmental applications in the inorganic remediation field are based on the swelling and ion-exchange capacities of smectites, even though these can be affected by hydrothermal treatment in water and acidic media. Here a systematic study of the properties of layered silicates that could affect their hydrothermal stability at different pH is described: type of layers, octahedral occupancy, layer charge, and origin of the layer charge. The silicates studied were selected on the basis of their different characteristics associated with these properties. Kanemite (1:0 phyllosilicate), kaolinite (1:1 phyllosilicate), and pyrophyllite and talc (2:1 phyllosilicates with no-layer charge) were examined in order to determine the effect of layer structure, whereas the hydrothermal reactivity of silicates with different layer charge was analyzed by comparing the talc-hectorite-Laponite1 and talc-saponite-trioctahedral vermiculite series. Samples were treated hydrothermally at 300ºC for 48 h in pure water and in a 0.01 M HNO3 solution and the final products were analyzed by X-ray diffraction, scanning electronic microscopy, and solid-state nuclear magnetic resonance spectroscopy. All layered silicates, except for kanemite, were found to remain intact after hydrothermal treatment in water and acidic media, with only minimal short-range structural changes observed. The extent of the structural changes depended on the octahedral sheet occupancy (greater extent) and the number of isomorphic substitutions (lesser extent), both of which weaken the structure.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Adams, J.M. (1987) Synthetic organic chemistry using pillared, cation-exchanged and acid treated montmorillonite catalysts — A review. Applied Clay Science, 2, 309–342.

    Article  Google Scholar 

  • Alba, M.D. and Chain, P. (2007) Persistence of lutetium disilicate. Applied Geochemistry, 22, 192–201.

    Article  Google Scholar 

  • Alba, M.D., Becerro, A.I., Castro, M.A., and Perdigon, A.C. (2001a) Hydrothermal reactivity of Lu-saturated smectites: Part I. A long-range order study. American Mineralogist, 86, 115–123.

    Article  Google Scholar 

  • Alba, M.D., Becerro, A.I., Castro, M.A., and Perdigon, A.C. (2001b) Hydrothermal reactivity of Lu-saturated smectites: Part II. A short-range order study. American Mineralogist, 86, 124–131.

    Article  Google Scholar 

  • Alba, M.D., Becerro, A.I., Castro, M.A., Perdigon, A.C., and Trillo, J.M. (2003) Inherent acidity of aqua metal ions in solids: assay in layered aluminosilicates. Journal of Physical Chemistry B, 107, 3996–4001.

    Article  Google Scholar 

  • Alba, M.D., Chain, P., and Pavón, E. (2006) Synthesis and characterization of gallium containing kanemite. Microporous and Mesoporous Materials, 94, 66–73.

    Article  Google Scholar 

  • Allen, C.C. and Wood, M.I. (1988) Bentonite in nuclear waste disposal: A review of research in support of the basalt waste isolation project. Applied Clay Science, 3, 11–30.

    Article  Google Scholar 

  • Ames, L.L., Sand, L.B., and Goldich, S.S. (1958) A contribution on the Hector, California bentonite deposit. Economic Geology, 53, 22–37.

    Article  Google Scholar 

  • Bauer, A., Scha¨fer, T., Dohrmann, R., Hoffmann, H., and Kim, J.I. (2001) Smectite stability in acid salt solutions and the fate of Eu, Th, and U in solution. Clay Minerals, 36, 93–103.

    Article  Google Scholar 

  • Bentabol, M., Cruz, M.D.R., Huerta, F.J., and Linares, J. (2003) Hydrothermal transformation of kaolinite at 200 and 300 degrees C. Clay Minerals, 38, 161–172.

    Article  Google Scholar 

  • Bergaya, F., Theng, B.K.G., and Lagaly, G. (editors) (2006) Handbook of Clay Science. Developments in Clay Science, 1. Elsevier, New York.

    Google Scholar 

  • Blasco, T., Corma, A., Navarro, M.T., and Pariente, J.P. (1995) Synthesis, characterization, and catalytic activity of Ti-MCM-41 structures. Journal of Catalysis, 156, 5–74.

    Article  Google Scholar 

  • Breen, C. (1988) The acidity of trivalent cation-exchanged montmorillonite. II. Desorption of mono- and di-substituted pyridines. Clay Minerals, 23, 323–328.

    Article  Google Scholar 

  • Breen, C. (1991a) Thermogravimetric study of the desorption of cyclohexylamine and pyridine from an acid treated Wyoming bentonite. Clay Minerals, 26, 473–486.

    Article  Google Scholar 

  • Breen, C. (1991b) Thermogravimetric and infrared study of the desorption of butylamine, cyclohexylamine and pyridine from Ni- and Co-exchanged montmorillonite. Clay Minerals, 26, 487–496.

    Article  Google Scholar 

  • Breen, C., Deane, A.T., and Flynn, J.J. (1987) The acidity of trivalent cation-exchanged montmorillonite. Temperature-programmed desorption and infrared studies of pyridine and n-butylamine. Clay Minerals, 22, 169–178.

    Article  Google Scholar 

  • Cetisli, H. and Gedikbey, T. (1990) Dissolution kinetics of sepiolite from Eskisehir (Turkey) in hydrochloric and nitric acids. Clay Minerals, 25, 207–215.

    Article  Google Scholar 

  • Cicel, B. and Novak, I. (1977) Dissolution of smectites in HCI: I. Half-time of dissolution as a measure of reaction rate. Proceedings of the 7th Conference on Clay Mineralogy and Petrology, Karlovy Vary, Czech Republic, pp. 163–171.

    Google Scholar 

  • Cicel, B., Novak, I., and Pivovarnícˇek, F. (1965) Dissolution of montmorillonites in HCI and its possible application in the study of their activation. Silikcity, 9, 130–139.

    Google Scholar 

  • Corma, A., Mifsud, A., and Sanz E. (1987) Influence of the chemical composition and textural characteristic of paly-gorskite on the acid leaching of octahedral cations. Clay Minerals, 22, 225–232.

    Article  Google Scholar 

  • Corma, A., Mifsud, A., and Sanz, E. (1990) Kinetics of the acid leaching of palygorskite: Influence of the octahedral sheet composition. Clay Minerals, 25, 197–205.

    Article  Google Scholar 

  • Cuadros, J. (2008) Clays as sealing material in nuclear waste repositories. Geology Today, 24, 90–103.

    Article  Google Scholar 

  • Engelhardt, G. and Michel, D. (editors) (1987) High-resolution Solid-State NMR of Silicates and Zeolites. John Wiley & Sons, New York.

    Google Scholar 

  • Fahn, R. (1973) Influence of the structure and morphology of bleaching earths on their bleaching action on oils and fats. Fette, Seifen, Anstrichmit. 75, 77–82.

    Article  Google Scholar 

  • Fahn, R. and Fenderl, K. (1983) Reaction products of organic dye molecules with acid treated montmorillonite. Clay Minerals, 18, 447–458.

    Article  Google Scholar 

  • García, M., Gancedo, J.I., Marco, J.F., Franco, M.J., Mendioroz, S., and Pajares J.A. (1989) Mössbauer study of iron removal in a montmorillonite. Hyperfine Interactions, 46, 629–634.

    Article  Google Scholar 

  • Glasser, F.P. (2001) Mineralogical aspects of cement in radioactive waste disposal. Mineralogical Magazine, 65, 621–633.

    Article  Google Scholar 

  • Gregor, M. and Cicel, B. (1969) Bleaching earth. Pp. 218–254 in: Bentonite and its Application. Publishing House SAS, Bratislava, Czech Republic.

    Google Scholar 

  • Grim, R.E. (1968) Clay Mineralogy, 2nd edition. McGraw Hill, New York.

    Google Scholar 

  • Grim, R.E. and Gu¨ven, N. (1978) Bentonites — Geology, Mineralogy, Properties and Uses. Developments in Sedimentology, 24. Elsevier, New York.

    Google Scholar 

  • Gu¨ler, C. and Sarier, N. (1990) Kinetics of the thermal dehydration of acid-activated montmorillonite by the rising temperature technique. Thermochimica Acta, 159, 29–33.

    Article  Google Scholar 

  • Jennings, S. and Thompson, G.R. (1986) Diagenesis of Plio-Pleistocene sediments of the Colorado River Delta, southern California. Journal of Sedimentary Petrology, 56, 89–98.

    Google Scholar 

  • Johan, Z. and Maglione, G.F. (1972) Kanemite a new hydrated sodium silicate. Bulletin de la Societé Française Mineralogie et de Cristallographie, 95, 371–382

    Google Scholar 

  • Jovanovic, N. and Janackovic, J. (1991) Pore structure and adsorption properties of an acid activated bentonite. Applied Clay Science, 6, 59–68.

    Article  Google Scholar 

  • Jozefaciuk, G. and Bowanko, G. (2002) Effect of acid and alkali treatments on surface areas and adsorption energies of selected minerals. Clays and Clay Minerals, 50, 771–783.

    Article  Google Scholar 

  • Laporte Industries Ltd. (1990) Laponite Technological Bulletin, L104/90/A, 1.

    Google Scholar 

  • Levitz, P., Lecolier, E., Mourchid, A., Delville, A., and Lyonnard, S. (2000) Liquid-solid transition of laponite suspension at very low ionic strength: Long-range electrostatic stabilization of anisotropic colloids. Europhysics Letters, 49, 672–677.

    Article  Google Scholar 

  • Luce, R.W. and Parks, G.A. (1972) Dissolution kinetics of magnesium silicates. Geochimica et Cosmochimica Acta, 36, 35–50.

    Article  Google Scholar 

  • Mantovani, M., Escudero, A., Alba, M.D., and Becerro, A.I. (2009) Stability of phyllosilicates in Ca(OH)2 solution: Influence of layer nature, octahedral occupation, presence of tetrahedral Al and degree of crystallinity. Applied Geochemistry, 24, 1251–1260

    Article  Google Scholar 

  • Massiot, D., Fayon, F., Capron, M., King, I., Le Calvé, S., Alonso, B., Durand, J.O., Bujoli, B., Gan, Z., and Hoatson, G. (2002) Modelling one- and two-dimensional solid-state NMR spectra. Magnetic Resonance in Chemistry, 40, 70–76.

    Article  Google Scholar 

  • Mather, J.D., Chapman, N.A., Black, J.H., and Lintern, B.C. (1982) The geological disposal of high-level radioactive waste — a review of the Institute of Geological Sciences Research programme. Nuclear Energy, 21, 167–173.

    Google Scholar 

  • Morgan, D.A., Shaw, D.B., Sidebottom, M.J., Soon, T.C., and Taylor, R.S. (1985) The function of bleaching earths in the processing of palm, palm kernel and coconut oil. Journal of the American Oil Chemical Society, 62, 292–299.

    Article  Google Scholar 

  • Murray, H.H. (1991) Overview — Clay Mineral Applications. Applied Clay Science, 29, 379–395.

    Article  Google Scholar 

  • Murray, H.H. (1999) Applied clay mineralogy today and tomorrow. Clay Minerals, 34, 39–49.

    Article  Google Scholar 

  • Murray, H.H. (2000) Traditional and new applications for kaolin, smectite, and palygorskite: a general overview. Applied Clay Science., 17, 207–221.

    Article  Google Scholar 

  • Nagy, K.L. (1995) Dissolution and precipitation kinetics of sheet silicates. Pp. 173–225 in: Chemical Weathering Rates of Silicate Weathering (F.W. White and S.L. Brantley, editors). Reviews in Mineralogy, 31. Mineralogical Society of America, Washington, D.C.

    Chapter  Google Scholar 

  • Novak, I. and Cicel, B. (1978) Dissolution of smectites in HCl: II. Dissolution rate as a function of crystallochemical composition. Clays and Clay Minerals, 26, 341–344.

    Article  Google Scholar 

  • Petit, S., Martin, F., Wiewióra, A., De Parseval, P., and Decarreau, A. (2004) Crystal-chemistry of talc: A near infrared (NIR) spectroscopy study. American Mineralogist, 89, 319–326.

    Article  Google Scholar 

  • Prost, J.L. (1984) Saponite from near Ballarat, California. Clays and Clay Minerals, 32, 147–153.

    Article  Google Scholar 

  • Pusch, R. and Yong, R. (2003) Water saturation and retention of hydrophilic clay buffer-microstructural aspects. Applied Clay Science, 23, 61–68.

    Article  Google Scholar 

  • Pusch, R., Zwahr, H., Gerber, R., and Schomburg, J. (2003) Interaction of cement and smectite clay — theory and practice. Applied Clay Science, 23, 203–210

    Article  Google Scholar 

  • Pusch, R., Kasbohm, J., Pakovsky, J., and Cechova, Z. (2007) Are all smectite clays suitable as “buffers”. Physics and Chemistry of the Earth, 32, 116–122.

    Article  Google Scholar 

  • Ramírez, S., Cuevas, J., Vigil, R., and Leguey, S. (2002) Hydrothermal alteration of “La Serrata” bentonite (Almería, Spain) by alkaline solutions. Applied Clay Science, 21, 257–269.

    Article  Google Scholar 

  • Read, D., Glasser, F.P., Ayora, C., Guardiola, M.T., and Sneyers, A. (2001) Mineralogical and microstructural changes accompanying the interaction of boom clay with ordinary Portland cement. Advanced Cement Research, 13, 175–183.

    Article  Google Scholar 

  • Sánchez-Soto, P.J., Justo, A., and Pérez-Rodríguez, J.L. (1994) Grinding effect on kaolinite-pyrophyllite-illite natural mixtures and its influence on mullite formation. Journal of Materials Science, 29, 1276–1283.

    Article  Google Scholar 

  • Sanz, J. and Serratosa, J.M. (1984) Si-29 and Al-27 High-Resolution MAS-NMR spectra of phyllosilicates. Journal of the American Chemical Society, 106, 4790–4793.

    Article  Google Scholar 

  • Savage, D. and Chapman, N.A. (1982) Hydrothermal behaviour of simulated waste glass- and waste-rock interaction under repository conditions. Chemical Geology, 36, 59–86.

    Article  Google Scholar 

  • Savage, D., Noy, D., and Mihara, M. (2002) Modelling the interaction of bentonite with hyperalkaline fluids. Applied Geochemistry, 17, 207–223.

    Article  Google Scholar 

  • Siddiqui, M.K.H. (1968) Bleaching Earths. Pergamon Press, Oxford, UK, 86 pp.

    Book  Google Scholar 

  • Stein, D.J. and Spera, F.J. (1993) Experimental rheometry of melts and supercooled liquids in the system NaAlSiO4-SiO2-Implications for structure and dynamics. American Mineralogist, 78, 710–723.

    Google Scholar 

  • Weiss, C.A., Altaner, S.P., and Kirkpatrick, R.J. (1987) High-resolution Si NMR spectroscopy of 2:1 layer silicates: Correlations among chemical shift, structural distortions, and chemical variations. American Mineralogist, 72, 935–942.

    Google Scholar 

  • Wheeler, P.A., Wang, J., Baker, J., and Mathias, L.J. (2005) Synthesis and characterization of covalently functionalized Laponite clay. Chemistry and Materials, 17, 3012–3018.

    Article  Google Scholar 

  • White, G.N., Dixon, J.B., Weaver, R.M., and Kunkle, A.C. (1992) Sedimentary structure in gray kaolins of Georgia. Clays and Clay Minerals, 40, 555–560.

    Article  Google Scholar 

  • Williams-Daryn, S., Thomas, R.K., Castro, M.A., and Becerro, A. (2002) The structures of complexes of a vermiculite intercalated by cationic surfactants, a mixture of cationic surfactants, and a mixture of cationic and non-ionic surfactants. Journal of Colloid and Interface Science, 256, 314–324.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Departamento de Química Inorgánica, Instituto Ciencia de los Materiales de Sevilla, CSIC-Universidad de Sevilla, Avda. Américo Vespucio, 49, 41092, Sevilla, Spain

    María D. Alba, Miguel A. Castro, Pablo Chain, M. Mar Orta & Esperanza Pavón

  2. Laboratorio de Catálisis Heterogénea, Departamento de Química, Universidad Nacional de Colombia, A.A. 14490, Bogotá, D.C., Colombia

    M. Carolina Pazos

Authors
  1. María D. Alba
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Miguel A. Castro
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Pablo Chain
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. Mar Orta
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. M. Carolina Pazos
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Esperanza Pavón
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to María D. Alba.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Alba, M.D., Castro, M.A., Chain, P. et al. Hydrothermal Stability of Layered Silicates in Neutral and Acidic Media: Effect on Engineered-Barrier Safety. Clays Clay Miner. 58, 501–514 (2010). https://doi.org/10.1346/CCMN.2010.0580405

Download citation

  • Received:

  • Revised:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1346/CCMN.2010.0580405

Key Words

Search

Navigation