Hostname: page-component-848d4c4894-wg55d Total loading time: 0 Render date: 2024-06-03T13:07:51.347Z Has data issue: false hasContentIssue false

Characteristics of variably saturated granular bentonite after long-term storage at near-field relevant temperatures

Published online by Cambridge University Press:  09 July 2018

M. Valter*
Affiliation:
ClayLab, Institute for Geotechnical Engineering, ETH Zürich, Schafmattstrasse 6, 8093 Zürich, Switzerland
M. Plötze
Affiliation:
ClayLab, Institute for Geotechnical Engineering, ETH Zürich, Schafmattstrasse 6, 8093 Zürich, Switzerland
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Bentonite is a potential material for use in the engineered barrier of radioactive waste repositories because of its low hydraulic permeability, self-sealing capability and retention capacity. It is expected that bentonite would react at the elevated temperatures accompanying the radioactive decay in the nuclear waste. The presented study was started in order to improve understanding of the coupled influence of temperature and (pore) water on the physicochemical and mineralogical properties of bentonite during thermal treatment under near-field relevant conditions. Granular Na-bentonite MX-80 was differently saturated (Sr = 1–0.05) and stored at different temperatures (50–150°C) in a closed system. Upon dismantling after different periods of time (3 to 18 months), mineralogical characteristics, cation exchange capacity and content of leachable cations, as well as physicochemical properties such as surface area and water adsorption were investigated.

The results showed a high mineralogical stability. A slight conversion from the sodium to an earth alkali form of the bentonite was observed. However, considerable changes in the physicochemical properties of the bentonite were observed, particularly by treatment above the critical temperature of 120°C. The cation exchange capacity decreased during heating at 150°C by approximately. 10%. The specific surface area dropped by more than 50%. The water uptake capacity under free swelling conditions showed a slight tendency to lower values especially for samples heated for more than 12 months. The water vapour adsorption ability in contrast drops by 25% already within three months at T = 120°C. These changes are mostly related to the variations in the interlayer cation composition and to smectite aggregation processes. The observed alterations are rather subtle. However, temperatures ⩾ 120°C had a remarkable negative influence on different properties of MX-80.

Type
Research Article
Creative Commons
Creative Common License - CCCreative Common License - BY
Copyright © The Mineralogical Society of Great Britain and Ireland 2013 This is an Open Access article, distributed under the terms of the Creative Commons Attribution license. (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted re-use, distribution, and reproduction in any medium, provided the original work is properly cited.
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2013

References

Bérend, I., Cases, J.M., François, M., Uriot, J.P., Michot, L., Masion, A. & Thomas, F. (1995) Mechanism of adsorption and desorption of water vapor by homoionic montmorillonites: 2. The Li+, Na+, K+, Rb+ and Cs+-exchanged forms. Clays and Clay Minerals, 43, 324–336.10.1346/CCMN.1995.0430307CrossRefGoogle Scholar
Bergmann, J. & Kleeberg, R. (1998) Rietveld analysis of disordered layer silicates. Materials Science Forum, 278–281, 300–305.Google Scholar
Brindley, G.W. & Brown, G. (1980) X-ray diffraction procedures for clay mineral identification. Pp. 305–359 in: Crystal Structures of Clays Minerals and their X-ray Identification (Brindley, G.W. & Brown, G., editors). Monograph 5, Mineralogical Society, London.CrossRefGoogle Scholar
Brunauer, S., Emmet, P.S. & Teller, E. (1938) Adsorption of gases in multimolecular layers. Journal of American Chemical Society, 60, 309–319.10.1021/ja01269a023CrossRefGoogle Scholar
Cases, J.M., Bérend, I., François, M., Uriot, J.P., Michot, L.J. & Thomas, F. (1997) Mechanism of adsorption and desorption of water vapor by homoionic montmorillonite: 3. The Mg2+, Ca2+, Sr2+ and Ba2+ exchanged forms. Clays and Clay Minerals, 45, 8–22.10.1346/CCMN.1997.0450102CrossRefGoogle Scholar
Chamley, H. (1989) Clay Sedimentology, 411–414. Springer-Verlag, Berlin.10.1007/978-3-642-85916-8CrossRefGoogle Scholar
Couture, R.A. (1985) Steam rapidly reduces the swelling capacity of bentonite. Letters to Nature, 318, 50–52.10.1038/318050a0CrossRefGoogle Scholar
DIN 18132 (1995) Determination of Water Absorption. DIN Deutsches Institut fü r Normung, Berlin.Google Scholar
DIN ISO 11465 (1996) Determination of Dry Matter and Water Content on a Mass Basis. DIN Deutsches Institut fü r Normung, Berlin.Google Scholar
Dohrmann, R. & Kaufhold, S. (2010) Determination of exchangeable calcium of calcareous and gypsiferous bentonites. Clays and Clay Minerals, 58, 79–88.10.1346/CCMN.2010.0580108CrossRefGoogle Scholar
Emmerich, K. (2011) Thermal analysis in the characterization and processing of industrial minerals. Pp. 129–170 in: Advances in the Characterization of Industrial Minerals (Christidis, G.E., editor). European Mineralogical Union and the Mineralogical Society of Great Britain & Ireland, London.Google Scholar
enresa (2000) FEBEX project, Full-scale engineered barriers experiment for a deep geological repository for high level radioactive waste in crystalline host rock. Final report. enresa, Madrid.Google Scholar
Galán, E. (2006) Genesis of clay minerals. Pp. 1129–1162 in: Handbook of Clay Science (Bergaya, F., Theng, B. & Lagaly, G., editors). Elsevier, Amsterdam.Google Scholar
Gaucheré, .C., Blanc, P., Bardot, F., Braibant, G., Buschaert, S., Crouzet, C., Gautier, A., Girard, J.P., Jacquot, E., Lassin, A., Negrel, G., Tournassat, C., Vinsot, A. & Altmann, S. (2006) Modelling the porewater chemistry of the Callovian–Oxfordian formation at a regional scale. Comptes Rendus Geoscience, 338, 917–930.Google Scholar
Göbel, I., Alheid, H.J., Jockwer, N., Mayor, J.C., García-Siñeriz, J.L., Alonso, E., Weber, H., Plötze, M., Klubertanz, G. & Rothpletz, C.A. (2006) Heater Experiment: Rock and bentonite Thermo-Hydro-Mechanical (THM) processes in the near-field of a thermal source for development of deep underground high level radioactive waste repositories. Euratom.Google Scholar
Gómez-Espina, R. & Villar, M. V. (2010) Geochemical and mineralogical changes in compacted MX-80 bentonite submitted to heat and water gradients. Applied Clay Science, 47, 400–408.10.1016/j.clay.2009.12.004CrossRefGoogle Scholar
Herbert, H.J., Kasbohm, J., Sprenger, H., Frenández, A.M. & Reichelt, C. (2008) Swelling pressures of MX-80 bentonite in solutions of different ionic strength. Physics and Chemistry of the Earth, 33, S327–S342.CrossRefGoogle Scholar
Itälä, A. & Olin, M. (2011) Chemical evolution of bentonite buffer in a final repository of spent nuclear fuel during the thermal phase. Nuclear Technology, 174, 342–352.10.13182/NT11-A11744CrossRefGoogle Scholar
Kahr, G. & Müller Vonmoos, M.(1982) Wärmeleitfähigkeit von Bentonit MX80 und von Montigel nach der Heizdrahtmethode. Nagra Technical Report NTB 82–06. Nagra, Baden.Google Scholar
Kasbohm, J., Pusch, R., Nguyen-Thanh, L. & Hoang-Ming, T. (2012) Lab-scale performance of selected expandable clays under HLW repository conditions. Environmental Earth Sciences. DOI 10.1007/ s12665-012-2085-1Google Scholar
Kaufhold, S. & Dohrmann, R. (2009) Stability of bentonites in salt solutions I. Sodium chloride. Applied Clay Science, 45, 171–177.10.1016/j.clay.2009.04.011CrossRefGoogle Scholar
Kaufhold, S. & Dohrmann, R. (2010) Stability of bentonites in salt solutions II. Potassium chloride solution – Initial step of illitization? Applied Clay Science, 49, 98–107.Google Scholar
Kaufhold, S. & Dohrmann, R. (2011) Stability of bentonites in salt solutions III. Calcium hydroxide. Applied Clay Science, 51, 300–307.10.1016/j.clay.2010.12.004CrossRefGoogle Scholar
Kaufhold, S., Dohrmann, R. & Klinkenberg, M. (2010a) Water uptake capacity of bentonites. Clays and Clay Minerals, 58, 37–43.Google Scholar
Kaufhold, S., Dohrmann, R., Klinkenberg, M., Siegesmund, S. & Ufer, K. (2010b) N2-BET specific surface area of bentonites. Journal of Colloid and Interface Science, 349, 275–282.10.1016/j.jcis.2010.05.018CrossRefGoogle Scholar
Keeling, P.S., Kirby, E.C. & Robertson, R.H. (1980) Moisture adsorption and specific surface area. Transactions and Journal of the British Ceramic Society, 79, 36–40.Google Scholar
Lagaly, G. (1994) Layer charge determination by alkylammonium ions. Pp. 1–46 in: Layer Charge Characteristics of 2:1 Silicate Clay Minerals (Mermut, A.R., editor). The Clay Minerals Society, Boulder, Colorado, USA.Google Scholar
Lagaly, G. & Weiss, A. (1969) Determination of the layer charge in mica-type layer silicates. Pp. 61–80 in: Proceedings of the International Clay Conference, Vol. 1 (Heller, L., editor). Israel Universities Press, Tokyo.Google Scholar
Laine, H. & Karttunen, P. (2010) Long-Term Stability of Bentonite, Working Report 2010-53. Posiva Oy, Eurajoki.Google Scholar
Laird, D.A. (1999) Layer charge influences on the hydration of expandable 2:1 phyllosilicates. Clays and Clay Minerals, 47, 630–636.10.1346/CCMN.1999.0470509CrossRefGoogle Scholar
MacEwan, D.M.C. & Wilson, M.J. (1980) Interlayer and intercalation complexes of clay minerals. Pp. 197–248 in: Crystal Structures of Clay Minerals and their X-ray identification (Brindley, G.W. & Brown, G., editors). Mineralogical Society, London.Google Scholar
Madejová, J., Balan, E. & Petit, S. (2011) Application of vibrational spectroscopy to the characterization of phyllosilicates and other industrial minerals. Pp. 171–226 in: Advances in the Characterization of Industrial Minerals (Christidis, G.E., editor). European Mineralogical Union and the Mineralogical Society of Great Britain & Ireland, London.Google Scholar
Mäder, U.K. (2009) Reference pore water for the Opalinus clay and “Brown Dogger” for the provisional safety-analysis in the framework of the sectorial plan – interim results (SGT-ZE). Nagra Work Report NAB 09-14. Nagra, Wettingen.Google Scholar
Madsen, F.T. & Kahr, G. (1992) Wasserdampfadsorption und spezifische Oberfläche von Tonen. Pp. 165–179 in: Contributions to Annual Meeting Hannover (Graf, H. Reichenbach, v.). DTTG, Hannover, Germany.Google Scholar
Marty, N.C.M., Fritz, B., Clément, A. & Michau, N. (2010) Modelling the long term alteration of the engineered bentonite barrier in an underground radioactive waste repository. Applied Clay Science, 47, 82–90.10.1016/j.clay.2008.10.002CrossRefGoogle Scholar
Meier, L.P. & Kahr, G. (1999) Determination of the cation exchange capacity (CEC) of clay minerals using the complexes of Copper (II) ion with Triethylenetetramine and Tetraethylenepentamine. Clays and Clay Minerals, 47, 386–388.10.1346/CCMN.1999.0470315CrossRefGoogle Scholar
Montes-H, G. & Geraud, Y. (2004) Sorption kinetic of water vapour of MX80 bentonite submitted to different physical–chemical and mechanical conditions. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 235, 17–23.10.1016/j.colsurfa.2004.01.013CrossRefGoogle Scholar
Montes-H, G., Fritz, B., Clement, A. & Michau, N. (2005) Modelling of geochemical reactions and experimental cation exchange in MX80 bentonite. Journal of environmental management, 77, 35–46.10.1016/j.jenvman.2005.03.003CrossRefGoogle Scholar
Moore, D.M. & Reynolds, R.C. (1997) X-Ray Diffraction and the Identification and Analysis of Clay Minerals, 2nd edition. Oxford University Press, Oxford.Google Scholar
Nagra, (2002) Project Opalinus Clay – Demonstration of disposal feasibility for spent fuel, vitrified highlevel waste and long-lived intermediate-level waste (proof of waste disposal). Nagra Technical Report NTB 02-05. Nagra, Wettingen.Google Scholar
Nagra, (2011) Alternative Buffer Material, Status Report. Nagra Technical Report NAB 11-19. Nagra, Wettingen.Google Scholar
Olsson, S. & Karnland, O. (2011) Mineralogical and chemical characteristics of the bentonite in the A2 test parcel of the LOT field experiments at ä spö HRL, Sweden. Physics and Chemistry of the Earth, 36, 1545–1553.Google Scholar
Perdrial, J.N. & Warr, L.N. (2011) Hydration behavior of MX80 bentonite in a confined-volume system: Implications for backfill design. Clays and Clay Minerals, 59, 640–653.10.1346/CCMN.2011.0590609CrossRefGoogle Scholar
Plötze, M. & Kahr, G. (2003) Swelling pressure and suction of clays. Pp. 479–483 in: Geotechnics of Soft Soils (Vermeer, P.A., Schweiger, H.F., Karstunen, M. & M. Cudny, editors). VGE, Essen.Google Scholar
Plötze, M. & Weber, H.P. (2007) ESDRED: Emplacement tests with granular bentonite MX-80. Laboratory results from ETH Zürich. Nagra Work Report NAB 07-24. Nagra, Wettingen.Google Scholar
Plötze, M., Kahr, G., Dohrmann, R. & Weber, H. (2007) Hydro-mechanical, geochemical and mineralogical characteristics of the bentonite buffer in a heater experiment: The HE-B project at the Mont Terri Rock Laboratory. Physics and Chemistry of the Earth, 32, 730–740.Google Scholar
Olis, A.C., Malla, P.B. & Douglas, L.A. (1990) The rapid estimation of the layer charges of 2:1 expanding clays from a single alkylammonium ion expansion. Clay Minerals, 25, 39–50.10.1180/claymin.1990.025.1.05CrossRefGoogle Scholar
Pusch, R. (2000) On the effect of hot water vapor on MX-80 clay. SKB Technical Report TR-00-16. SKB, Stockholm.Google Scholar
Pusch, R. (2001) The buffer and backfill handbook, Part 2: Materials and techniques. SKB Technical Report TR-02-12. SKB, Stockholm.Google Scholar
Pusch, R. (2006) Clays and nuclear waste management. Pp. 703–716 in: Handbook of Clay Science (Bergaya, F., Theng, B.K.G. & Lagal, G.y, editors). Elsevier, Amsterdam.Google Scholar
Russell, S. & Facella, J. A. (2006) Progress towards longterm management of used nuclear fuel in Canada. Pp. 39–54 in: Geological Challenges in Radioactive Waste Isolation, Fourth Worldwide Review (Witherspoon, P.A. & Bodvarsson, G.S., editors). University of California, Berkeley, California, USA.Google Scholar
Sato, R., Sasaki, T., Ando, K., Smith, P.A. & Schneider, J.W. (1998) Calculations of the temperature evolution of a repository for spent fuel in crystalline and sedimentary rocks. Nagra Technical Report NTR 97- 02. Nagra, Wettingen, Switzerland.Google Scholar
Senger, R. & Ewing, J.J. (2008) Evolution of temperature and water content in bentonite buffer: Detailed modelling of two phase flow processes associated with the early closure period. Nagra Work Report NAB 08-32. Nagra, Wettingen.Google Scholar
Svensson, D., Dueck, A., Nilsson, U., Olsson, S., Sandén, T., Lydmark, S., Jägerwall, S., Pedersen, K. & Hansen, S. (2011) Alternative buffer material – Status of the ongoing laboratory investigation of reference materials and test package 1. SKB Technical Report TR- 11-06. SKB, Stockholm.Google Scholar
Valter, M. & Plötze, M. (2010) New observations in behaviour of clays after their long-term thermal treatment. Pp. 515 in: Clays in Natural & Engineered Barriers for Radioactive Waste Confinement, Abstracts. Andra, Nantes.Google Scholar
Villar, M.V. & Lloret, A. (2007) Dismantling of the first section of the FEBEX in situ test: THM laboratory tests on the bentonite blocks retrieved. Physics and Chemistry of the Earth, 32, 716–729.Google Scholar
Zhang, G., Germaine, J.T., Torrence Martin, R. & Whittle, A.J. (2003) A simple sample-mounting method for random powder X-ray diffraction. Clays and Clay Minerals, 51, 218–225.10.1346/CCMN.2003.0510212CrossRefGoogle Scholar