Experimentally determined swelling pressures and geochemical interactions of compacted Wyoming bentonite with highly alkaline solutions

The estimated quantity of cement for construction and sealing purposes is around 9E5 kg in the planned Swedish KBS3 repository for nuclear waste. The highly alkaline cement pore fluid (pH > 12) may affect other components in the repository, and especially the bentonite buffer is of concern. In this study, we simulated possible interactions between cement and bentonite by contacting highly compacted bentonite with high molar hydroxide solutions in a series of laboratory experiments. Wyoming bentonite (MX-80) and purified homo-ionic Na- and Ca-montmorillonite were used for tests with 0.1, 0.3 and 1.0 M NaOH and saturated Ca(OH)2 solutions. Pressure cells with permeable filters were loaded with compacted discs of bentonite at the proposed buffer density (2000 kg/m(3) at full water saturation). A hydroxide solution was circulated on one side of the cell and an isotonic chloride solution on the other during a minimum of 45 days. Swelling pressure and solution pH were monitored during the tests and the change in the solution composition and bentonite mineralogy were determined after completed tests. No effect on swelling pressure was observed in tests with 0.1 M NaOH (pH 12.9) or saturated Ca(OH)2 solutions (pH 12.4) and the mineralogical/chemical changes of the clay were minimal. The bentonite swelling pressure was significantly reduced in the tests with 0.3 (pH 13.3) and 1.0 M (pH 13.8) NaOH solutions. The reduction seems to be due to an instant osmotic effect, and to a continuous dissolution of silica minerals, resulting in mass loss and, consequently, a decrease in density. At these high pH, the release of silica was dominating and the CEC of the clay increased by 20-25%. The structural formula of the smectite and X-ray diffraction tests for nonexpandability (Greene-Kelly test) provided strong evidence that the dissolution of montmorillonite proceeds incongruently through an initial step of beidellitization. The calculated rate of silica release from montmorillonite is 1.6E-9 g g(-1) clay s(-1) for 1.0 M and 5E-10 g g-1 clay s-1 for 0.3 M NaOH solutions. The Si release rate is, however, not a straightforward measure of the montmorillonite dissolution rate due to the non-stoichiometric dissolution. Upon contact between bentonite and NaCl solutions, ion-equilibrium is established between the external solution and the exchangeable cations of the clay. A similar initial pressure response on exposure of bentonite to NaOH solutions indicates that such equilibrium may establish also with an external NaOH solution. If so, the OH-concentration of the clay pore water will be lower than that of the external solution, which would explain that dissolution rates in our experiments with highly compacted bentonite are lower than those reported for batch experiments with hydroxide solutions of the same concentration. (C) 2006 Published by Elsevier Ltd.