Importance of Organic Matter-Uranium Biogeochemistry to Uranium Plume Persistence in the Upper Colorado River Basin

Abstract:

Recent evidence suggests that biologically driven redox reactions, fueled by sedimentary lenses enriched in detrital organic matter, play major roles in maintaining the persistent uranium groundwater plume in the subsurface at the U.S. Department of Enery’s Rifle, CO field research site. Biogeochemical cycling of C, N, Fe, and S is highly active in these organic-rich naturally reduced zones (NRZs), and uranium is present as U(IV). The speciation of these elements profoundly influences the susceptibility of uranium to be reoxidized and remobiliized and contribute to plume persistence. However, uranim speciation in particular is poorly constrained in these sytems.

To better evaluate the importance of NRZs to uranium mobility and plume persistence at the Rifle site, the DOE-BER-funded SLAC SFA team has characterized vertical concentration profiles and speciation of uranium, iron, sulfur, and NOM in well bores at high spatial resolution (4 inch intervals). Up to 95% of the sedimentary uranium pool was found to be concentrated in NRZs, where it occurs dominantly as non-crystalline forms of U(IV). Uranium accumulation and the presence of the short-lived sulfide mackinawite (FeS) at NRZ-aquifer interfaces indicate that NRZs actively exchange solutes with the surrounding aquifer. Moreover, sediment textures indicate that NRZs are likely to be abundant in riparian zones throughout the upper Colorado River basin (U.S.A.), which contains most of the contaminated DOE legacy uranium ore processing sites in the U.S. These results suggest that NRZ-uranium interactions may be important to plume persistence regionally and emphasize the importance of understanding molecular-scale processes.