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Effects of Chemical Structure on the Stability of Smectites in Short-Term Alteration Experiments

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—Because of their isolating capacity, smectite-rich clays have been proposed as buffer and backfill materials in high-level radioactive waste repositories. These repositories have to guarantee long-term safety for ∼1 million years. Thermodynamics and kinetics of possible alteration processes of bentonite determine its long-term performance as a barrier material. Smectites in 25 different clays and bentonites were investigated in order to identify possible differences in their rates of alteration. These samples were saturated for 30 days in 1 M NaCl solution and deionized water, and then overhead rotated at speeds of 20 rpm and 60 rpm. Depending on the octahedral and interlayer composition, each of the smectites studied had specific rate of alteration, a so-called specific dissolution potential of smectite. The bentonites were classed as 'slow-reacting bentonite', 'moderate-reacting bentonite', or 'fast-reacting bentonite' corresponding to a relatively low (ΔP–specific dissolution potential – < –5%), moderate (–5% < ΔP < –20%), or high specific dissolution potential (ΔP > –20%), respectively. The larger the amount of octahedral Fe and Mg compared to octahedral Al, the greater the specific dissolution potential. The present study found that the interlayer composition has a discernible impact on the rate of alteration. In experiments with rotation speeds of 60 rpm and a 1 M NaCl solution, Na+ was found to be the stabilizing cation in the interlayers of all the smectites. The Na-stabilizing mechanism was identified in only some of the smectites (type A) in experiments with 20 rpm (1 M NaCl solution). A second stabilization mechanism (by interlayer cations; Ca and Mg) was identified for other smectites (type B). Each bentonite has a specific rate of alteration. 'Slow-reacting bentonite' and clay with smectite-illite interstratifications are recommended as potential clay barriers in HLW repositories. The experimental and analytical procedures described here could be applied to potential barrier materials to identify 'slow-reacting bentonite'.
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Keywords: BENTONITES; CLAY STABILITY; INTERLAYER COMPOSITION; OCTAHEDRAL SHEET COMPOSITION; OVERHEAD ROTATING; SHORT-TERM ALTERATION; SMECTITE; SPECIFIC DISSOLUTION POTENTIAL

Document Type: Research Article

Publication date: 01 October 2014

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  • The JOURNAL publishes articles of interest to the international community of clay scientists, including but not limited to areas in mineralogy, crystallography, geology, geochemistry, sedimentology, soil science, agronomy, physical chemistry, colloid chemistry, ceramics, petroleum engineering, foundry engineering, and soil mechanics. Clays and Clay Minerals exists to disseminate to its worldwide readership the most recent developments in all of these aspects of clay materials. Manuscripts are welcome from all countries.

    Clays and Clay Minerals is the official publication of The Clay Minerals Society.

    The Editor-in-Chief is Professor Joseph W. Stucki [email protected]

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