Abstract
The maximum dose of ionizing radiation from the geological disposal of TRU wastes will likely be controlled by poorly sorbing soluble radionuclides, such as I-129. Proposed repository designs for the geological disposal of TRU wastes envisage the use of an engineered barrier composed of a bentonite buffer to limit the migration of such radionuclides by impeding groundwater flow. Cementitious materials will inevitably be used for waste packaging, in filling and adding structural integrity to the repository. Using cementitious materials, however, is problematic because they produce highly alkaline leachates which have the potential to cause a complex series of coupled changes in the porewater chemistry, mineralogy and, ultimately, the mass transport properties of the bentonite buffer. To elucidate the consequences of these coupled changes, reactive-transport model analyses have been conducted for bentonite alteration test cases with the use of different combinations of secondary minerals that will likely form in the bentonite buffer. A dissolution rate equation of smectite (a key component of bentonite) applicable to pH 7-13 and 25-80 ℃ was proposed and used in the reactive-transport model analyses. It was found that the amount of dissolved smectite at the center of the bentonite buffer was smaller and those in the vicinity of the cement interface was larger when thermodynamically metastable secondary minerals mainly precipitated as compared with the precipitation of stable phases. The calculated temporal and spatial changes of kinetic smectite dissolution were interpreted as a consequence of the changes in Gibbs free energy and porewater chemistry. Furthermore, the bentonite porewater chemistry was also affected by the stoichiometry and thermodynamic stability of the secondary minerals and the kinetics of smectite dissolution. Except in the close proximity of the cement interface, it was found that regardless of the choice of secondary minerals, the effective diffusion coefficient and hydraulic conductivity remained largely unchanged after 100,000 years.
