Effect of iron and carbonation on the diffusion of iodine and rhenium in waste encasement concrete and soil fill material under hydraulically unsaturated conditions

Assessing long-term performance of Category 3 cement wasteforms and accurate prediction for radionuclide encasement requires knowledge of the radionuclide–cement interactions and mechanisms of retention (i.e. sorption or precipitation). A set of sediment-concrete half-cell diffusion experiments was conducted under unsaturated conditions (4% and 7% by weight moisture content) using carbonated and non-carbonated concrete–soil half cells. Results indicate the behavior of Re and I release was comparable within a given half-cell test. Diffusivity in soil is a function of moisture content; a 3% increase in moisture content affords a one to two order of magnitude increase in diffusivity. Release of I and Re was 1–3 orders of magnitude less from non-carbonated, relative to carbonated, concrete monoliths. Inclusion of Fe in non-carbonate monoliths resulted in the lowest concrete diffusivity values for both I and Re. This suggests that in the presence of Fe, I and Re are converted to reduced species, which are less soluble and better retained within the concrete monolith. The release of I and Re was greatest from Fe-bearing, carbonated concrete monoliths, suggesting carbonation negates the effect of Fe on the retention of I and Re within concrete monoliths. This is likely due to enhanced formation of microcracks in the presence of Fe, which provide preferential paths for contaminant migration. Although the release of I and Re were greatest from carbonated concrete monoliths containing Fe, the migration of I and Re within a given half cell is dependent on the moisture content, soil diffusivity, and diffusing species.