Uranium sorption to organic matter and long-term accumulation in a pristine alpine wetland

Understanding the controls on uranium (U) mobility in the environment is key to improve the management of sites contaminated by U mining activities. Previous research has shown that natural or engineered wetlands are particularly able to scavenge high amounts of U(VI) and U(IV) under noncrystalline forms. However, questions remain on the respective roles of sorption and reduction processes in the removal of U from running waters in wetlands, as well as on the long-term stability of U storage. Here, we performed a series of geochemical, isotopic (delta U-238, (U-234/U-238)), microscopic (SEM-EDXS, EPMA) and spectroscopic (mu-XRF, mu-XAS, XANES and EXAFS at the U L-3 and M-4-edges and Fe K-edge) investigations to determine the modes of U accumulation and assess U mobility in a natural exceptionally U-enriched (up to 5000 mu g/g) wetland on the shore of Lake Negre (Mediterranean Alps, France). Uranium (VI) was largely dominant in the two studied soil cores, except a few samples containing as much as similar to 50 % U(IV). At the particle scale, U is associated to a variety of organic constituents of the soil matrix with a homogenous oxidation state. Bulk EXAFS spectroscopy at the U L-3-edge shows that U is mostly mononuclear, with dominant monodentate binding to organic moieties (C neighbors at similar to 3.45 angstrom). An additional minor fraction of U under polymeric forms is inferred from wavelet (CCWT) analysis of the EXAFS data. These observations are reinforced by 1 M bicarbonate extractions that result in the dissolution of 82-96 % of total U, including putative polymeric species. At the wetland scale, similar or slightly fractionated isotopic ratios (delta U-238) between the wetland-feeding creek waters and the wetland soils are observed, supporting the idea that U(VI) sorption on organic matter is the primary U scavenging mechanism. Furthermore, it indicates that partial U(VI) reduction to U(IV) occurs as a second step, after sorption. Analysis of U decay chain disequilibria in the cores as a function of depth suggests that U accumulation in this wetland has lasted for several thousand years. We propose that the wetland acts as an active reactor where U has been massively accumulating for similar to 14500 years, especially as U(VI) forms associated to organic matter, and is further partly exported to the lake through soil erosion. (C) 2022 Elsevier Ltd. All rights reserved.