The Effects of Changes in Water Content on Uranium(VI) Leaching in Sediment Mixtures Containing Gravel

This study is aimed at understanding the physical and chemical effects that changes in water content have on uranium leaching in sediment containing gravel. It was hypothesized that leaching will be more efficient under unsaturated conditions because flow will be restricted to the smallest pores and will have the most contact with the uranium contaminated sediment. Under saturated conditions, a large portion of the flow will bypass the < 2 mm material, and in turn not come into contact with uranium contaminated material. Batch adsorption and desorption experiments were performed on < 2 mm ERDF sediment to determine the linearity and reversibility of sorption processes and to aid in the interpretation of the leaching experiments. Results of the desorption experiments on aged, contaminated sediments show that the mass percent of sorbed U(VI) released to solution decreased as the sorbed concentration of U(VI) decreased. The opposite trend was observed on freshly contaminated sediments. This indicated that aging increased U(VI) affinity for the solid phase and was attributed to either the crystallization of calcite, which incorporated a portion of the sorbed U(VI) as it crystallized, or the presence of voids in basaltic lithic fragments accessed by diffusion. Column leaching experiments were performed at two water contents on artificially contaminated sediment collected from the Department of Energy’s (DOE) Hanford Site, Washington state. The sediment contained 81.3% gravel (> 2 mm) by mass. Non-reactive tracers were well fit with the convection-dispersion equation (CDE) at both high and low water contents indicating physical equilibrium. The column experimental data were fitted to an analytical solution to the CDE; the results of the modeling show an increase in the distribution coefficient (Kdeffective) with decreasing water content. Several potential explanations for this trend were proposed; one is based on a physical effect in which solute exposure to reactive surfaces changes as a function of water content and the others are based on results of the batch desorption experiments. This work has important implications for the Hanford Site where there is ongoing research regarding the persistence of U(VI) in the vadose zone and underlying aquifer.