Uranium geochemistry in estuarine sediments: Controls on removal and release processes

Porewater uranium profiles from Long Island Sound (LIS) and Amazon shelf sediments and LIS sediment incubation experiments indicate that both removal and release processes control U geochemistry in estuarine sediments. Release of U from sediments occurs in association with Fe reduction. A correlation between U and Fe (and Mn) observed in sediment incubation experiments suggests that there is release of U from Fe-Mn-oxides as they are reduced, consistent with data from the Amazon shelf. In both sediment porewater profiles (LIS and Amazon) and sediment incubation experiments (LIS), there is removal of U from porewater under conditions of sulfate reduction. Sediment incubation experiments indicate that the removal rate is first-order with respect to U concentration, and the rate constant is linearly correlated to sulfate reduction rates. The link between U removal and sulfate reduction (a measure of diagenetic microbial activity) is consistent with a microbial mediation of U reduction. The diffusional flux of U into LIS sediments is estimated from porewater profiles. The inclusion of this estuarine removal term in the oceanic U balance increases the importance of the sediment sink.