Role of groundwater oxidation potential and radiolysis on waste glass performance in crystalline repository environments

Laboratory experiments have shown that groundwater conditions in a granite repository will be as reducing as those in a basalt repository. Chemical analysis of the reduced groundwaters confirmed that the Fe2+/Fe3+ couple controls the oxidation potential (Eh). The reducing groundwater conditions were found to decrease the time-dependent release of soluble elements (Li and B) from the waste glass. However, due to the lower solubility of multivalent elements released from the glass when the groundwaters are reducing, these elements have significantly lower concentrations in the leachates. Gamma radiolysis reduced the oxidation potential of both granitic and basaltic groundwater in the absence of both waste glass and oxygen. This occurred in tests at atmospheric pressure where H2 could have escaped from the solution. The mechanism for this decrease in Eh is under investigation but appears related to the reactive amorphous precipitate in both groundwaters. The results of these tests suggest that radiolysis may not cause the groundwaters to become oxidizing in a crystalline repository when abundant Fe2+ species are present