Microbial Impacts on the Form, Distribution and Fate of Uranium in the Environments

Phylogenetically diverse groups of microorganisms are capable of catalyzing the reduction of highly soluble U(VI) to highly insoluble U(IV), which rapidly precipitates as uraninite (UO₂). Because uraninite is highly insoluble, microbial uranyl reduction is being intensively studied as the basis for a cost-effective in-situ bioremediation strategy. Previous studies have described UO₂ biomineralization products as amorphous or poorly crystalline. The objective of this study is to characterize the nanocrystalline uraninite in detail in order to determine the particle size, crystallinity, and size-related structural characteristics, and to examine the implications of these for reoxidation and transport.In this study, we obtained U-contaminated sediment and water from an inactive U mine and incubated them anaerobically with nutrients to stimulate reductive precipitation of UO2 by indigenous anaerobic bacteria, mainly Gram-positive spore-forming Desulfosporosinus and Clostridium spp. as revealed by RNA-based phylogenetic analysis. Desulfosporosinus sp. was isolated from the sediment and UO₂ was precipitated by this isolate from a simple solution that contains only U and electron donors. We characterized UO₂ formed in both of the experiments by high resolution-TEM (HRTEM) and X-ray absorption fine structure analysis (XAFS).The results from HRTEM showed that both the pure and the mixed cultures of microorganisms precipitated around 1.5 - 3 nm crystalline UO₂ particles. Some particles as small as around 1 nm could be imaged. Rare particles around 10 nm in diameter were also present. Particles adhere to cells and form colloidal aggregates with low fractal dimension. In some cases, coarsening by oriented attachment on {111} is evident. Our preliminary results from XAFS for the incubated U-contaminated sample also indicated an average diameter of UO₂ of 2 nm. In nanoparticles, the U-U distance obtained by XAFS was 0.373 nm, 0.012 nm smaller than found in the bulk structure of UO₂ (0.385 nm). This indicates contraction within the nanoparticles due to tensile surface stress. Microbially formed UO₂ is highly reactive, thus will be oxidized quickly as redox conditions change. Our findings support a growing number of studies that indicate that biominerals formed as the result of enzyme-mediated redox reactions are nanoparticulate. Preliminary results suggest that these particles will be readily transported through sandy aquifers, especially when conditions prevent high degrees of flocculation. Thus, despite its low (but size-dependent) solubility, UO₂ nanoparticle transport may exert a fundamental control on mobility of U in contaminated environments.