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Smectite-rich clays are to be used in nuclear repositories for sealing in the radioactive waste. As the radioactive decay produces heat it may affect the chemical, physical and hydromechanical properties of the clay components in the repository. An ‘alternative buffer material’ (ABM) experiment is a Svensk Kärnbränslehantering AB (SKB)-led in situ heating test placed in boreholes in the Äspö tunnel (Sweden). The 2nd ABM package was dismantled in April 2013, after 6.5 y of equilibration with Äspö groundwater and 5 y of heating. The objective was to investigate the long-term effects of the iron heater and Äspö groundwater on four of 31 compacted blocks made of MX-80, Deponit CaN and Friedland clays.Compared to the starting materials, major changes in the exchangeable cation populations were observed. Within horizontal profiles, water-soluble sulfate, Ca, K and Mg increased; poorly crystalline Fe oxide contents decreased; total Mg, Ca and S increased; and a decrease in the amounts of total Na and K away from the host rock towards the heater was observed. At the boundary with the heater, an increase in the total Fe content, decreases in total Si and Al contents, precipitation of gypsum and anhydrite, dissolution of cristobalite and feldspars, and indications of the formation of trioctahedral clay minerals were observed. A decrease in swelling pressure for the Friedland clay (in drill-cored samples) was recorded which was recovered after grinding and recompaction. No effects of hydraulic conductivity were found, after 6.5 y of reaction time, in the subsurface of any of materials studied.

The Swedish and Finnish nuclear waste repository design, KBS-3H, foresees horizontal emplacement of copper canisters-bentonite modules surrounded by a titanium shell. The interaction of titanium with bentonite was studied here using a combination of wet chemistry and a spectroscopic approach to evaluate the potential impact of Ti corrosion on the clay. For natural analogue clays with high Ti contents, spectroscopic investigations showed that titanium occurs as crystalline TiO2. In contrast, the Ti in the MX-80 bentonite occurs in the clay structure, presumably in the octahedral sheet. Hydrothermal tests conducted at 200°C using synthetic montmorillonite showed little if any change in the montmorillonite structure at near-neutral and acidic conditions. Under alkaline conditions, limited alteration was observed, including the formation of trioctahedral clay minerals and zeolite. These changes, however, occurred independently of the addition of Ti. In the batch tests conducted at 80°C, Ti did not occur as separate TiO2particles. The comparison of experimental data with spectroscopic simulations provides sound evidence that Ti was incorporated in a neoformed phyllosilicate structure.

The interaction of two different bulk bentonites (Na- and Ca-types) with three types of simulated cement waters (pH 9.7, 11.3 and 12.0) and one saline groundwater simulate (pH 8.3) as a reference, was studied in batch reactors at 25°C. The solution pH was monitored in order to keep the pH as steady as possible by replacing the leaching solution with fresh one when needed. After 554 days, one set of parallel samples was removed from the experiment in order to investigate the possible changes in the bentonite materials.The buffering capacity of bentonite was clearly observed, especially at the beginning of the high-pH experiments, as the pH of the leaching solutions decreased quite dramatically due to interaction with bentonite. The solution chemistry results showed a decrease of Ca content in all leachate samples, but especially in pH 12.0 experiments. Small amounts of silica were released throughout the experiment. Both bentonites in pH 12.0 experiments also released detectable amounts of Al, while in the lower pH experiments the levels were below detection limit. These observations were also supported by chemical analyses of the bentonite materials. Only minor changes were detected in the mineralogy, and they were mainly concentrated on experiments at pH 11.3 and pH 12.0. The measured swelling pressure showed an increase in pH 12.0 experiments. The results obtained in this research may facilitate modelling of bentonite interaction with high-pH solutions.