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Combined Salt and Temperature Impact on Montmorillonite Hydration

Published online by Cambridge University Press:  01 January 2024

Per Daniel Svensson  and
Staffan Hansen
Per Daniel Svensson*
Affiliation:
Swedish Nuclear Fuel and Waste Management Co, Oskarshamn, Sweden
Staffan Hansen
Affiliation:
Centre for Analysis and Synthesis, Department of Chemistry, Lund University, Sweden
*
*E-mail address of corresponding author: daniel.svensson@skb.se
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Abstract

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Bentonite is to be used as a sealing material for long-term storage of radioactive waste. During permafrost periods the buffer may freeze, causing the following: montmorillonite dehydration, ice formation, and pressure build-up that may fracture the surrounding rock. No previous study has been done on freezing of bentonite in saline water. Using small and wide angle X-ray scattering, the present study aimed to increase understanding of the combined impact of salt and temperature on the hydration (swelling) of Wyoming montmorillonite. The basal spacing of the Na-montmorillonite was very dependent on the water content, while this was not the case for the Ca-montmorillonite (after reaching 19 Å). The basal spacing of the free-swelling Na-montmorillonite (34–280 Å) was estimated successfully using simple calculations. During freezing of Na-montmorillonite in NaCl solution, both ice and hydrohalite formed (at -50 and -100ºC). At starting concentrations ≥ 1.5 M the basal spacing was not affected by freezing. During freezing of Ca-montmorillonite in CaCl2 solution, ice formed; antarcticite formed only sporadically. The basal spacing of the Ca-montmorillonite at high NaCl concentrations (>1 M) was greater at -50 and -100ºC (18 Å) than at 20ºC (16 Å). The opposite was observed at low concentrations. This change was attributed to small amounts of salts introduced into the montmorillonite interlayer, hence changing the interlayer water properties. The montmorillonite hydration was also temperature dependent; decreasing temperature increased the hydration (as long as no ice was formed) and increasing the temperature decreased the hydration. This was attributed to the temperature impact on the entropy of the hydration reaction. This observation was also reproduced in an experiment up to 90ºC. A small amount of salt in the groundwater was noted to reduce significantly the potential problem of ice formation in bentonite sealings.

Keywords

AspöBentoniteCaFreezingHydrationMontmorilloniteMX-80NaSaltSAXSSwedenSwellingWAXSXRD
Type
Article
Information
Clays and Clay Minerals , Volume 61 , Issue 4 , August 2013 , pp. 328 - 341
Copyright
Copyright © The Clay Minerals Society 2013

References

Ahlrichs, J.L. and White, J.L., 1962 Freezing and lyophilizing alters the structure of bentonite gels Science, New Series 136 1116–1118.Google Scholar
Amorim, C.L.G. Lopes, R.T. Barroso, R.C. Queiroz, J.C. Alves, D.B. Perez, C.A. and Schelin, H.R., 2007 Effect of clay—water interactions on clay swelling by X-ray diffraction Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment 580 768–770.CrossRefGoogle Scholar
Anderson, D.M. and Hoekstra, P., 1965 Migration of interlamellar water during freezing and thawing of Wyoming bentonite Soil Science Society of America Journal 29 498–504.CrossRefGoogle Scholar
Birgersson, M. and Karnland, O., 2009 Ion equilibrium between montmorillonite interlayer space and an external solution — consequences for diffusional transport Geochimica et Cosmochimica Acta 73 1908–1923.CrossRefGoogle Scholar
Birgersson, M. Karnland, O. and Nilsson, U., 2008.Freezing in saturated bentonite — A thermodynamic approach Physics and Chemistry of the EarthCrossRefGoogle Scholar
Birgersson, M. Börgesson, L. Hedström, M. Karnland, O. and Nilsson, U., 2009.Bentonite erosion—final reportGoogle Scholar
Bradley, W.F. Grim, R.E. and Clark, W.I., 1937 A study of the behavior of montmorillonite upon wetting Zeitschrift für Kristallographie 97 216–222.Google Scholar
Brindley, G.W. and Brown, G., 1980 Crystal Structures of Clay Minerals and their X-ray Identification London Mineralogical Society.CrossRefGoogle Scholar
Cerenius, Y. Stahl, K. Svensson, L.A. Ursby, T. Oskarsson, Albertsson, J. and Liljas, A., 2000 The crystallography beamline I711 at MAX II Journal of Synchrotron Radiation 7 203–208.CrossRefGoogle ScholarPubMed
Handbook, C.R.C., 1972 Handbook of Chemistry and Physics 53rd.Google Scholar
Eagleson, M., 1993 Concise Encyclopedia of Chemistry Berlin Walter de Gruyter.Google Scholar
Ferrage, E. Tournassat, C. Rinnert, E. Charlet, L. and Lanson, B., 2005 Experimental evidence for Ca-chloride ion pairs in the interlayer of montmorillonite. An XRD profile modelling approach Clays and Clay Minerals 53 348–360.CrossRefGoogle Scholar
Ferrage, E. Lanson, B. Sakharov, B.A. and Drits, V.A., 2005 Investigation of smectite hydration properties by modeling experimental X-ray diffraction patterns. Part I. Montmorillonite hydration properties American Mineralogist 90 1358–1374.CrossRefGoogle Scholar
Fukushima, Y., 1984 X-ray diffraction study of aqueous montmorillonite emulsions Clays and Clay Minerals 32 320–326.CrossRefGoogle Scholar
Hedström, M. and Karnland, O., 2011 Donnan equilibrium in Na-montmorillonite from a molecular dynamics perspective Geochimica et Cosmochimica Acta 77 266–274.CrossRefGoogle Scholar
Holmboe, M. Wold, S. and Jonsson, M., 2012 Porosity investigation of compacted bentonite using XRD profile modeling Journal of Contaminant Hydrology 128 19–32.CrossRefGoogle ScholarPubMed
Huang, T.C. Toraya, H. Blanton, T.N. and Wu, Y., 1993 X-ray-powder diffraction analysis of silver behenate. A possible low-angle diffraction standard Journal of Applied Crystallography 26 180–184.CrossRefGoogle Scholar
Karnland, O. Muurinen, A. Karlsson, F., Alonso, E.E. and Ledesma, A., 2005 Bentonite swelling pressure in NaCl solutions Experimentally Determined Data and Model Calculations. Advances in Understanding Engineered Clay Barriers London Taylor & Francis Group 241–256.Google Scholar
Karnland, O. Olsson, S. and Nilsson, U., 2006.Mineralogy and sealing properties of various bentonites and smectite-rich clay materialGoogle Scholar
Kjellander, R. Marčelja, S. Pashley, R.M. and Quirk, J.P., 1988 Double-layer ion correlation forces restrict calcium-clay swelling Journal of Physical Chemistry 92 6489–6492.CrossRefGoogle Scholar
Light, B., Brandt, R.E., and Warren, S.G. (2009) Hydrohalite in cold sea ice: Laboratory observations of single crystals, surface accumulations, and migration rates under a temperature gradient, with application to “Snowball Earth”. Journal of Geophysical Research, 114, C07018.CrossRefGoogle Scholar
Low, P.F. Anderson, M. and Hoekstra, P., 1968 Some thermodynamic relationships for solids at or below the freezing point. 1. Freezing point depression and heat capacity Water Resources Research 4 379–394.CrossRefGoogle Scholar
Mammen, C.B., Ursby, T., Cerenius, Y., Thunnissen, M., Als-Nielsen, J., Larsen, S., and Liljas, A. (2002) Design of a 5-station macromolecular crystallography beamline at MAX-1ab. Acta Physica Polonica A, 101, 595.CrossRefGoogle Scholar
Mammen, C.B. Ursby, T. Cerenius, Y. Thunnissen, M. and Als-Nielsen, J., 2004 Bent diamond crystals and multilayer based optics at the new 5-station protein crystallography beamline ‘Cassiopeia’ at MAX-lab AIP Conference Proceedings 705 808–811.CrossRefGoogle Scholar
Morillon, V. Debeaufort, F. Jose, J. Tharrault, J.F. Capelle, M. Blond, G. and Voilley, A., 1999 Water vapour pressure above saturated salt solutions at low temperatures Fluid Phase Equilibria 155 297–309.CrossRefGoogle Scholar
Norrish, K., 1954 The swelling of montmorillonite Discussions of the Faraday Society 18 120–134.CrossRefGoogle Scholar
Norrish, K. and Rausell-Colom, J., 1962 Effect of freezing on the swelling of clay minerals Clay Minerals Bulletin 5 9–16.CrossRefGoogle Scholar
Roberts, W.L. Rapp, G.R. and Weber, J., 1974 Encyclopedia of Minerals New York Van Nostrand Reinhold Company.Google Scholar
Schnewberger, R. Voilley, A. and Weisser, H., 1978 Activity of water in frozen systems International Journal of Refrigeration 1 201–206.CrossRefGoogle Scholar
Segad, M. Jönsson, B. Akesson, T. and Cabane, B., 2010 Ca/ Na montmorillonite: Structure, forces and swelling properties Langmuir 26 5782–5790.CrossRefGoogle ScholarPubMed
Slade, P.G. Quirk, J.P. and Norrish, K., 1991 Crystalline swelling of smectite samples in concentrated NaCl solutions in relation to layer charge Clays and Clay Minerals 39 234–238.CrossRefGoogle Scholar
Sposito, G. Holtzclaw, K.M. Charlet, L. Jouany, C. and Page, A.L., 1983 Sodium-calcium and sodium-magnesium exchange on Wyoming bentonite in perchlorate and chloride ionic media Soil Science Society of America Journal 47 51–56.CrossRefGoogle Scholar
SKB, 2006 Climate and climate-related issues for the safety assessment SR-Can Stockholm Svensk Kärnbränslehantering AB.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.CrossRefGoogle Scholar
Svensson, P.D. and Hansen, S., 2010 Freezing and thawing of montmorillonite—a time-resolved synchrotron X-ray diffraction study Applied Clay Science 49 127–134.CrossRefGoogle Scholar
Strunz, H., 1970 Mineralogische Tabellen 5th Germany Geest & Portig Akademische Verlagsgesellschaft, Leipzig.Google Scholar
Tambach, T.J. Hensen, E.J.M. and Smit, B., 2004 Molecular simulations of swelling clay minerals Journal of Physical Chemistry B 108 7586–7596.CrossRefGoogle Scholar
Torii, T. and Ossaka, J., 1965 Antarcticite: a new mineral, calcium chloride hexahydrate, dicovered in Antarctica Science 149 975–977.CrossRefGoogle Scholar
Zavitsas, A.A., 2005 Aqueous solutions of calcium ions: Hydration numbers and the effect of temperature The Journal of Physical Chemistry B 109 20636–20640.CrossRefGoogle ScholarPubMed