Uranium(VI) Diffusion in Sodium-Montmorillonite at Alkaline pH
Abstract
Diffusive transport of uranium(VI) in montmorillonite clay and bentonite has important implications for uranium(VI) mobility in engineered barrier systems or host rocks in high level radioactive waste repositories, and clay-rich soils and sediments in the environment. The prediction of uranium(VI) adsorption and diffusion in clay-rich media, however, is complicated by (1) the complexity of the mineralogical structure of montmorillonite, in terms of its pore-size distributions and available surface site types, and (2) the complex uranium(VI) solution speciation, which can include cationic, uncharged, and anionic complexes, depending on solution conditions. For instance, a partial or full exclusion of anions from negatively charged clay interlayer spaces could change the effective 'anion-accessible' porosity and decrease the diffusive flux of these solutes under steady state conditions. In contrast, weak cation exchange reactions can result in 'surface diffusion' of adsorbed cations, such as UO2OH+, in addition to diffusion in the liquid phase, resulting in greater diffusive fluxes at steady state. In order to investigate these complex interactions, we performed two, lab-scale uranium(VI) through-diffusion experiments in lightly compacted Na-montmorillonite at slightly different, alkaline pH conditions (average pH values of 8.69 and 8.87). Observed uranium(VI) diffusive fluxes were decreased by approximately an order of magnitude in comparison to a tritium tracer. This indicates a relevance of 'anion exclusion' effects, the full or partial exclusion of anionic U(VI)-carbonato species from clay interlayer spaces. In addition, uranium(VI) sorption reactions were shown to be relevant in the diffusion experiments, even at alkaline pH values of around 8.7 and 8.9, where uranium(VI) sorption is low compared to other pH conditions. Despite the similarity of pH conditions, different degrees of uranium(VI) retardation were determined for the two systems. Additionally, we observed apparent kinetic limitations for uranium(VI) sorption as a function of pH, which was indicated by different varying times required to reach steady-state conditions for diffusive fluxes.