Abstract
Smectites are considered to be an important component in backfill barriers due to their marked swelling and high cation exchange capacity. Both properties are affected considerably when these clays transform under natural conditions. However, we have recently described a chemical interaction between high-activity radionuclide simulators and smectites which could prove to be effective at immobilizing radionuclides definitively. Investigating the efficiency of this mechanism, independent of bentonite ageing, is a challenge. For this purpose, the reactivity shown by a non-expandable layered aluminosilicate, muscovite, has been compared to that shown by an expandable one, beidellite. Both samples were treated hydrothermally with a solution of lutetium nitrate, and the transformations were studied by X-ray diffraction, nuclear magnetic resonance and scanning electron microscopy/energy dispersive X-ray analysis. Lutetium cations react with the silicon framework of both 2:1 layered aluminosilicates under hydrothermal conditions, and new phases, lutetium disilicate, kaolinite, boehmite and natrosilite are generated. The results demonstrate that the efficiency of the chemical mechanism is not determined by the swelling and the cation exchange capacity of 2:1 layered aluminosilicates. Thus, the rare earth disilicate formation might account for the success of the clay barrier, once bentonite has lost its swelling and cation exchange capacity.
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Alba, M.D., Becerro, A.I., Castro, M.A. and Perdigön, A.C. (2001) Hydrothermal reactivity of Lu-saturated smectites: Part I. A long-range order study. American Mineralogist, 86, 115–123
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
Ames, L.L., McGarrah, J.E., Walker, B.A. and Salter, P.F. (1982) Sorption of uranium and cesium by Hanford basalts and associated secondary smectite. Chemical Geology, 35, 205–225.
Ames, L.L., McGarrah, J.E. and Walker, B.A. (1983) Sorption of trace constituents from aqueous-solutions onto secondary minerals. 1. Uranium. Clays and Clay Minerals, 31, 321–324.
Bailey, S.W. (1980) Structures of layer silicates. Pp. 1–123 in: Crystal Structures of Clay Minerals and their X-ray Identification (G.W. Brindley, and G. Brown, editors). Mineralogical Society, London.
Bauer, A., Schäfer, T., Dohrmann, R., Hoffmann, H. and Kim, J.J. (2001) Smectite stability in acid salt solutions and the fate of Eu, Th and U in solution. Clay Minerals, 36, 93–103
Becerro, A.I. (1997) Desarrollo de un sistema modelo de análisis estructural de la reactividad química de compuestos de silicio 2D y 3D aplicado a la formación de Lu2Si207. PhD thesis, University of Seville, Spain.
Borovec, Z. (1981) The adsorption of uranyl species by fine clays. Chemical Geology, 32, 45–58.
Chisholm-Brause, C., Conradson, S.D., Buscher, C.T., Eller, P.G. and Morris, D.E. (1994) Speciation of uranyl sorbed at multiple binding-sites on montmorillonite. Geochimica et Cosmochimica Acta, 58, 3625.
Cuadros, J. and Linares, J. (1996) Experimental kinetic study of the smectite-illite transformation. Geochimica et Cosmochimica Acta, 60, 439–453
Dent, A.J., Ramsay, J.D. and Swanton, S.W. (1992) An EXAFS study of uranylion in solution and sorbed onto silica and montmorillonite clay colloids. Journal of Colloid and Interface Science, 150, 45–60.
Eberl, D.D. and Srodon, J. (1988) Ostwald ripening and interparticle-diffraction effects for illite crystals. American Mineralogist, 73, 1335–1345
Eberl, D.D., Velde, B. and McCormick, T. (1993) Synthesis of illite-smectite from smectite at earth surface temperatures and high pH. Clay Minerals, 28, 49–60.
Heimann, R.B. (1993) Bronsted acidification observed during hydrothermal treatment of a calcium montmorillonite. Clays and Clay Minerals, 41, 718–725.
Herrero, C.P., Sanz, J. and Serratosa, J.M. (1985) Si, Al distribution in micas — analysis by high-resolution Si-29 NMR-spectroscopy. Journal of Physics C: Solid State Physics, 18, 13–22.
Inoue, A., Kohyama, N., Kitagawa, R. and Watanabe, T. (1987) Chemical and morphological evidence for the conversion of smectite to illite. Clays and Clay Minerals, 35, 111–120.
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.
Lippmaa, E., Magi, M., Samoson, A., Engelhardt, G. and Grimmer, A.R. (1980) Structural studies of silicates by solid-state high-resolution Si-29 NMR. Journal of the American Chemical Society, 102, 4889–4893.
Mackenzie, K.J.D. and Smith, M.E. (2002) Multinuclear Solid-State NMR of Inorganic Materials. Pergamon, Amsterdam, 215 pp.
Mackenzie, K.J.D., Brown, I.W.M., Cardile, CM. and Meinhold, R.H. (1987) The thermal reaction of muscovite studied by high-resolution solid-state 29-Si and 27-A1 NMR. Journal of Materials Science, 22, 2645–2654.
Martaza, M.G. (1989) A nuclear magnetic resonance investigation of the structure of some alkali silicates glasses. PhD thesis, University of Warwick, UK.
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.
Meunier, A., Velde, B. and Griffault, V. (1998) The reactivity of bentonites: a review. An application to clay barrier stability for nuclear waste storage. Clay Minerals, 33, 187–196.
Miller, S.E., Heath, G.R. and Gonzalez, R.D. (1982) Effects of temperature on the sorption of lanthanides by montmorillonite. Clays and Clay Minerals, 30, 111–122.
Morris, D.E., Chisholm-Brause, C.J., Barr, M.E., Conradson, S.D. and Eller, P.G. (1994) Optical spectroscopic studies of the sorption of UO2(2+) species on a reference smectite. Geochimca et Cosmochimica Acta, 58, 3613–3623.
Nadeau, P.H., Wilson, M.J., McHardy, W.J. and Tait, J.M. (1984) Interstratified clays as fundamental particles. Science, 225, 923–925.
Oades, J.M. (1984) Interactions of polycations of aluminum and iron with clays. Clays and Clay Minerals, 32, 49–57.
Perdigón, A.C. (2002) Estudio del sistema saponita/Lu(NO3)3/H2O en condiciones hidrotérmicas. PhD thesis, University of Seville, Spain.
Pérez-Maqueda, L.A., Franco, F., Avilés, M.A., Poyato, J. and Pérez-Rodriguez, J.L. (2003) Effect of sonication on particle-size distribution in natural muscovite and biotite. Clays and Clay Minerals, 51, 701–708.
Sanz, J. and Serratosa, J.M. (1984a) Si-29 and Al-27 high-resolution MAS-NMR spectra of phyllosilicates. Journal of the American Chemical Society, 106, 4790–4793.
Sanz, J. and Serratosa, J.M. (1984b) Distinction of tetrahed-rally and octahedrally coordinated Al in phyllosilicates by NMR-spectroscopy. Clay Minerals, 19, 113–115.
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.
Tsunashima, A., Brindley, G.W. and Bastovanov, M. (1981) Adsorption of uranium from solutions by montmorillonite-compositions and properties of uranyl montmorillonites. Clays and Clay Minerals, 29, 10–16.
Weiss, C.A. Jr., Altaner, S.P. and Kirkpatrick, R.J. (1987) High-resolution 29Si NMR spectroscopy of 2:1 layer silicates: Correlations among chemical shift, structural distortions, and chemical variations. American Mineralogist, 72, 935–942.
Yamada, H. and Nakazawa, H. (1993) Isothermal treatments of regularly interstratified montmorillonite-beidellite at hydro-thermal conditions. Clays and Clay Minerals, 41, 726–730.
Yau, Y.C., Peacor, D.R. and McDowell, S.D. (1987) Smectite-to-illite reactions in Saltan Sea shales: A transmission and analytical electron microscopy study. Journal of Sedimentary Petrology, 57, 335–342.
Ylagan, R.F., Altaner, S.P. and Pozzuoli, A. (2000) Reaction mechanisms of smectite illitization associated with hydro-thermal alteration from Ponza Island, Italy. Clays and Clay Minerals, 48, 610–631.
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Alba, M.D., Chain, P. Interaction Between Lu Cations And 2:1 Aluminosilicates Under Hydrothermal Treatment. Clays Clay Miner. 53, 37–44 (2005). https://doi.org/10.1346/CCMN.2005.0530105
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DOI: https://doi.org/10.1346/CCMN.2005.0530105