Atomistic simulations were performed to study the diffusion and adsorption of Ca 2 UO 2 (CO 3 ) 3 and of some of its constituent species, i.e., UO 2 2+ , CO 3 2− , and UO 2 CO 3 , in feldspar nanosized fractures. Feldspar is important to uranium remediation efforts at the U.S. Department of Energy Hanford site as it has been found in recent studies to host contaminants within its intragrain fractures. In addition, uranyl carbonate species are known to dominate U(VI) speciation in conditions relevant to the Hanford site. Molecular dynamics (MD) simulations showed that the presence of the feldspar surface diminishes the diffusion coefficients of all of the species considered in this work and that the diffusion coefficients do not reach their bulk aqueous solution values in the center of a 2.5 nm fracture. Moreover, the MD simulations showed that the rate of decrease in the diffusion coefficients with decreasing distance from the surface is greater for larger adsorbing species. Free energy profiles of the same species adsorbing on the feldspar surface revealed a large favorable free energy of adsorption for UO 2 2+ and UO 2 CO 3 , which are able to adsorb to the surface with their uranium atom directly bonded to a surface hydroxyl oxygen, whereas adsorption of CO 3 2− and Ca 2 UO 2 (CO 3 ) 3 , which attach to the surface via hydrogen bonding from a surface hydroxyl group to a carbonate oxygen, was calculated to be either only slightly favorable or unfavorable.
■ INTRODUCTIONUranium is a major radionuclide contaminant in groundwater systems at sites where nuclear materials were processed and stored. 1 Consequently, one of the main challenges for uranium remediation at nuclear facilities is to develop a comprehensive understanding of the reactivity and stability of uranium in order to predict its fate in subsurface environments. Uranium has been found predominantly in microscopic intragrain domains in contaminated sediments such as from the US Department of Energy (DOE) Hanford Site. 2,3 In addition, ion diffusion has been shown to be a major process contributing to the preferential uranium concentration in these sediments and is predicted to control the future release of uranium from the sediments. 2,4,5 One important limitation in studies of uranium diffusion is the lack of self-diffusion coefficients for uranyl species in groundwater, 6 which has led to the development of diffusion models, referred to here as apparent diffusion models, whereby the total dissolved U(VI) concentration is considered as a single chemical species. Recently, the self-diffusion coefficients of alkaline-earth uranyl carbonate species were determined using molecular dynamics (MD) simulations. 7 This allowed for the development of a species-based diffusion model 6 that explicitly treats the variations in mass, charge, and diffusion coefficient of aqueous uranyl species, which proportions can be determined from speciation reactions. In test cases, the species-based diffusion model was shown to give a good description of the uranyl release fro...