Redox Fluctuations and Organic Complexation Govern Uranium Redistribution from U(IV)-Phosphate Minerals in a Mining-Polluted Wetland Soil, Brittany, France

Wetlands have been proposed to naturally attenuate U transfers in the environment via U complexation by organic matter and potential U reduction. However, U mobility may depend on the identity of particulate/dissolved uranium source materials and their redox sensitivity. Here, we examined the fate of uranium in a highly contaminated wetland (up to 4500 mg·kg–1 U) impacted by former mine water discharges. Bulk U LIII-EXAFS and (micro-)­XANES combined with SEM-EDXS analyses of undisturbed soil cores show a sharp U redox boundary at the water table, together with a major U redistribution from U­(IV)-minerals to U­(VI)-organic matter complexes. Above the water table, U is fully oxidized into mono- and bidentate U­(VI)-carboxyl and monodentate U­(VI)-phosphoryl complexes. Minute amounts of U­(VI)-phosphate minerals are also observed. Below the water table, U is fully reduced and is partitioned between U­(IV)-phosphate minerals (i.e., ningyoite and a lermontovite-like phase), and bidentate U­(IV)-phosphoryl and monodentate U­(IV)-carboxyl complexes. Such a U redistribution from U-minerals inherited from mine water discharge deposits could result from redox cycling nearby the water table fluctuation zone. Oxidative dissolution of U­(IV)-phosphate minerals could have led to U­(VI)-organic matter complexation, followed by subsequent reduction into U­(IV)-organic complexes. However, uranium­(IV) minerals could have been preserved in permanently waterlogged soil.