Complexation by Organic Matter Controls Uranium Mobility in Anoxic Sediments

Uranium contamination threatens the availability of safe and clean drinking water globally. This toxic element occurs both naturally and as a result of mining and ore-processing in alluvial sediments, where it accumulates as tetravalent U [U­(IV)], a form once considered largely immobile. Changing hydrologic and geochemical conditions cause U to be released into groundwater. Knowledge of the chemical form(s) of U­(IV) is essential to understand the release mechanism, yet the relevant U­(IV) species are poorly characterized. There is growing belief that natural organic matter (OM) binds U­(IV) and mediates its fate in the subsurface. In this work, we combined nanoscale imaging (nano secondary ion mass spectrometry and scanning transmission X-ray microscopy) with a density-based fractionation approach to physically and microscopically isolate organic and mineral matter from alluvial sediments contaminated with uranium. We identified two populations of U (dominantly +IV) in anoxic sediments. Uranium was retained on OM and adsorbed to particulate organic carbon, comprising both microbial and plant material. Surprisingly, U was also adsorbed to clay minerals and OM-coated clay minerals. The dominance of OM-associated U provides a framework to understand U mobility in the shallow subsurface, and, in particular, emphasizes roles for desorption and colloid formation in its mobilization.