Pentavalent U Reactivity Impacts U Isotopic Fractionation during Reduction by Magnetite.

Meaningful interpretation of U isotope measurements relies on unraveling the impact of reduction mechanisms on the isotopic fractionation. Here, the isotope fractionation of hexavalent U [U(VI)] was investigated during its reductive mineralization by magnetite to intermediate pentavalent U [U(V)] and ultimately tetravalent U [U(IV)]. As the reaction proceeded, the remaining aqueous phase U [containing U(VI) and U(V)] systematically carried light isotopes, whereas in the bicarbonate-extracted solution [containing U(VI) and U(V)], the δ238U values varied, especially when C/C0 approached 0. This variation was interpreted as reflecting the variable relative contribution of unreduced U(VI) (δ238U < 0‰) and bicarbonate-extractable U(V) (δ238U > 0‰). The solid remaining after bicarbonate extraction included unextractable U(V) and U(IV), for which the δ238U values consistently followed the same trend that started at 0.3-0.5‰ and decreased to ∼0‰. The impact of PIPES buffer on isotopic fractionation was attributed to the variable abundance of U(V) in the aqueous phase. A few extremely heavy bicarbonate-extracted δ238U values were due to mass-dependent fractionation resulting from several hypothesized mechanisms. The results suggest the preferential accumulation of the heavy isotope in the reduced species and the significant influence of U(V) on the overall isotopic fractionation, providing insight into the U isotope fractionation behavior during its abiotic reduction process.

Persistence of the Isotopic Signature of Pentavalent Uranium in Magnetite.

Uranium isotopic signatures can be harnessed to monitor the reductive remediation of subsurface contamination or to reconstruct paleo-redox environments. However, the mechanistic underpinnings of the isotope fractionation associated with U reduction remain poorly understood. Here, we present a coprecipitation study, in which hexavalent U (U(VI)) was reduced during the synthesis of magnetite and pentavalent U (U(V)) was the dominant species. The measured δ238U values for unreduced U(VI) (∼-1.0‰), incorporated U (96 ± 2% U(V), ∼-0.1‰), and extracted surface U (mostly U(IV), ∼0.3‰) suggested the preferential accumulation of the heavy isotope in reduced species. Upon exposure of the U-magnetite coprecipitate to air, U(V) was partially reoxidized to U(VI) with no significant change in the δ238U value. In contrast, anoxic amendment of a heavy isotope-doped U(VI) solution resulted in an increase in the δ238U of the incorporated U species over time, suggesting an exchange between incorporated and surface/aqueous U. Overall, the results support the presence of persistent U(V) with a light isotope signature and suggest that the mineral dynamics of iron oxides may allow overprinting of the isotopic signature of incorporated U species. This work furthers the understanding of the isotope fractionation of U associated with iron oxides in both modern and paleo-environments.

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.

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits.

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U(VI)) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U(IV) generated through biologically mediated U(VI) reduction is the predominant U(IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority (∼58-89%) of U is bound as U(IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U(VI) represent only minor components. The uranium deposit exhibited mostly 238U-enriched isotope signatures, consistent with largely biotic reduction of U(VI) to U(IV). This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U(IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.

Mechanism of Uranium Reduction and Immobilization in Desulfovibrio vulgaris Biofilms.

The prevalent formation of noncrystalline U(IV) species in the subsurface and their enhanced susceptibility to reoxidation and remobilization, as compared to crystalline uraninite, raise concerns about the long-term sustainability of the bioremediation of U-contaminated sites. The main goal of this study was to resolve the remaining uncertainty concerning the formation mechanism of noncrystalline U(IV) in the environment. Controlled laboratory biofilm systems (biotic, abiotic, and mixed biotic-abiotic) were probed using a combination of U isotope fractionation and X-ray absorption spectroscopy (XAS). Regardless of the mechanism of U reduction, the presence of a biofilm resulted in the formation of noncrystalline U(IV). Our results also show that biotic U reduction is the most effective way to immobilize and reduce U. However, the mixed biotic-abiotic system resembled more closely an abiotic system: (i) the U(IV) solid phase lacked a typically biotic isotope signature and (ii) elemental sulfur was detected, which indicates the oxidation of sulfide coupled to U(VI) reduction. The predominance of abiotic U reduction in our systems is due to the lack of available aqueous U(VI) species for direct enzymatic reduction. In contrast, in cases where bicarbonate is present at a higher concentration, aqueous U(VI) species dominate, allowing biotic U reduction to outcompete the abiotic processes.