Uranium Isotope Fractionation during the Anoxic Mobilization of Noncrystalline U(IV) by Ligand Complexation

Uranium (U) isotopes are suggested as a tool to trace U reduction. However, noncrystalline U­(IV), formed predominantly in near-surface environments, may be complexed and remobilized using ligands under anoxic conditions. This may cause additional U isotope fractionation and alter the signatures generated by U reduction. Here, we investigate the efficacy of noncrystalline U­(IV) mobilization by ligand complexation and the associated U isotope fractionation. Noncrystalline U­(IV) was produced via the reduction of U­(VI) (400 μM) by Shewanella oneidensis MR-1 and was subsequently mobilized with EDTA (1 mM), citrate (1 mM), or bicarbonate (500 mM) in batch experiments. Complexation with all investigated ligands resulted in significant mobilization of U­(IV) and led to an enrichment of ²³⁸U in the mobilized fraction (δ²³⁸U = 0.4–0.7 ‰ for EDTA; 0.3 ‰ for citrate; 0.2–0.3 ‰ for bicarbonate). For mobilization with bicarbonate, a Rayleigh approach was the most suitable isotope fractionation model, yielding a fractionation factor α of 1.00026–1.00036. Mobilization with EDTA could be modeled with equilibrium isotope fractionation (α: 1.00039–1.00049). The results show that U isotope fractionation associated with U­(IV) mobilization under anoxic conditions is significant and needs to be considered when applying U isotopes in remediation monitoring or as a paleo-redox proxy.