Constraints on microbial reduction of uranium within soils and sediments

GEOC 17

Brandy D. Stewart, stewartb@stanford.edu, GES, Stanford University, Braun Hall Building 320, Stanford, CA 94301 and Scott Fendorf, fendorf@stanford.edu, Department of Geological & Environmental Sciences, Stanford University, Braun Hall Building 320, Stanford, CA 94301.
Uranium is a redox active contaminant of concern to both human health and ecological preservation. In soils subject to anaerobic conditions, the more mobile, oxidized form of uranium (UO22+) may be reduced by dissimilatory metal reducing bacteria. Despite rapid reduction in controlled systems, various factors within soils may limit biological reduction of the uranyl ion, inclusive of competing electron acceptors such as nitrate, and complexation reactions. Here we elucidate the impact of uranyl speciation on the extent and rate of reduction with a focus on the formattion of the ternary calcium-uranyl-carbonato species. The presence of aqueous calcium greatly decreases the rate of microbial uranyl reduction by limiting the accessibility of U(VI) through changes in the conformation of the electon accepting moiety. The impact of calcium concentration is compared between systems containing ferrihydrite, an amorphous structured iron (hydr)oxide, and a more crystalline iron (hydr)oxide structure represented by goethite and hematite. A linear correlation exists between calcium concentration and decreased uranium reduction for all three iron (hydr)oxides. Uranyl reduction in these systems can be described by a first order reaction and psuedo-first order rate constants incorporating the effect of calcium are derived.