Alteration experiments have been performed using RTT7 and synthetic basaltic glasses in MgCl2−CaCl2 salt solution at 190°C. The duration of experiments ranged from 0.25 to 463 days. The alteration products were studied by Scanning Electron Microscope (SEM), Scanning Transmission Electron Microscope (STEM), X-ray diffraction (XRD) and Electron Spectrometry for Chemical Analysis (ESCA). For both glasses, the early alteration product is a hydrotalcite-like compound [Mg6Al2CO3(OH)16·4H2O] in which HPO42−, SO42− and Cl− substitutes for CO32−. The measured basal spacing is 7.68 Å for the hydrotalcite formed from R7T7 glass and 7.62 Å for the hydrotalcite formed from basaltic glass which reflect the high Al/Al + Mg ratios x (0.34 ≤ x ≤ 0.46). The chemical microanalyses show that the hydrotalcite is subsequently covered by a silica-rich gel which evolves into saponite after a few months. These results support the use of basaltic glasses alteration patterns in Mg-rich solution, to understand the long-term behavior of R7T7 nuclear waste glass.

Steady-state dissolution rates of basaltic glass were measured in mixed-flow reactors at 50ºC at pH 3 and 4 as a function of aqueous sulphate concentration. Dissolution rates in the presence of 0.1 moles/kg SO42- were found to be ~3 times greater than those in corresponding SO42- free solutions. This rate increase is found to be approximately consistent with that calculated using a rate equation previously proposed by Gislason and Oelkers (2003). These results suggest that the addition of sulphate to injected CO2 may facilitate CO2 sequestration in basalts by accelerating basaltic glass dissolution rates thus more rapidly releasing aqueous Ca and Mg to solution.

Short-range order in the oxygen co-ordination shell of the Ca ion in a glass of composition Ca3Mg4Al2Si7O24 is investigated by analysis of the extended X-ray absorption fine structure. The estimate of disorder in the short-range oxygen co-ordination is no greater than that for crystalline samples of diopside and bytownite. An estimate of the oxygen environment of calcium in the particular glass is included.

Far-from-equilibrium dissolution experiments with diopside and basaltic glass in mixed-flow reactors at 70°C and pH 8.2 show that solute concentrations do not reach steady state over the experimental duration of 45—60 days. Chemical modelling indicates that during the dissolution experiments, solutions have become supersaturated with respect to carbonates in the case of diopside, and carbonates, clay minerals and zeolites in the case of the basaltic glass. Decreasing dissolution is therefore interpreted as a result of secondary surface precipitates blocking the reactive surface area. Calcite formation was supported in both experiments by a significant increase in Ca (and Sr) concentrations as pH was abruptly lowered from 8.2 to 7 because this change increased carbonate solubility and caused all potential carbonate precipitates to re-dissolve. The reduction in pH also led to an increase in Si concentration for diopside and a decrease in Si concentration for basaltic glass. This observation is in accordance with previous experiments on the pH-dependent dissolution rates of pyroxenes and basaltic glass.