Combining U speciation and U isotope fractionation to evaluate the importance of naturally reduced sediments in controlling the mobility of uranium in the upper Colorado River Basin

Abstract:

Long-term persistence of uranium (U) in groundwater at legacy ore-processing sites in the upper Colorado River Basin (CRB) is a major concern for DOE, stakeholders, and local property owners. In the past year, we have investigated U distributions in contaminated floodplains at Grand Junction, Naturita, and Rifle (CO), Riverton (WY), and Shiprock (NM). We find that U is retained at all locations in fine-grained, organic-rich sulfidic sediments, referred to as naturally reduced zones (NRZs). The retention mechanisms (e.g., complexation, precipitation or adsorption) and the processes responsible for U accumulation in NRZs will directly determine the capacity of the sediments to prevent U mobilization. However, these processes remain poorly understood at local and regional scales yet they are critical to management and remediation of these sites.

We have used U L_III/II-edge XANES to systematically characterize U oxidation states, and EXAFS and bicarbonate extractions to characterize U local structure and reactivity in order to distinguish the forms of U. We are measuring U isotopic signatures (δ^238/235U) to better understand uranium sources and processes of accumulation in NRZs. We have found that high U concentrations correspond to reduced and relatively insoluble U forms, mainly non-crystalline U(IV), and co-occur with ferrous iron and sulfides. This suggests that reduction processes, fueled by the high organic matter content and constrained to the diffusion-limited environment in the fine-grained NRZs, are important for the retention of U in these sediments. We also observe a strong correlation between the U concentrations in the NRZs and the extent of isotopic fractionation, with up to +1.8 ‰ difference between uranium-enriched and low concentration zones. In some locations the δ^238/235U values are within the range of values typical of the mine tailings, whereas at other sites the more positive δ^238/235U values suggest that redox cycling and/or partial reduction of uranium are occurring. These results suggest that organic-rich reduced sediments play important roles governing uranium mobility in contaminated floodplains regionally within the upper CRB and other locations where organic sediments occur