Oxygenic photosynthesis fundamentally transformed all major biogeochemical cycles and increased the size and complexity of Earth's biosphere. However, there is still debate about when this metabolism evolved. As oxygenic photosynthesis is the only significant source of O 2 at Earth's surface, O 2-sensitive trace element enrichments and isotopic signatures in Archean sedimentary rocks can potentially be used to determine the onset of oxygenic photosynthesis by tracking shifts in the oxidative capacity of Earth's surface environment. Here, we present an extensive new Archean U isotope record from iron formations, organic-rich shales, and paleosols. Variability in  238 U values gradually increased from Archean to Phanerozoic, consistent with current view of gradual oxidation of Earth's surface. In addition, statistical analysis on available  238 U data indicates a turning point of  238 U variability at roughly 3.0 billon years ago. We suggest that such a turning point in  238 U variability indicates the initiation of relatively large-scale oxidative weathering of U(IV)-bearing minerals, implying that oxygenic photosynthesis may have evolved before 3.0 billion years ago.

Uranium groundwater contamination due to U mining and processing affects numerous sites globally. Bioreduction of soluble, mobile U(VI) to U(IV)-bearing solids is potentially a very effective remediation strategy. Uranium isotopes (U/U) have been utilized to track the progress of microbial reduction, with laboratory and field studies finding a ∼1‰ isotopic fractionation, with the U(IV) product enriched in U. However, the isotopic fractionation produced by adsorption may complicate the use ofU/U to trace microbial reduction. A previous study found that adsorption of U(VI) onto Mn oxides produced a -0.2‰ fractionation with the adsorbed U(VI) depleted in U. In this study, adsorption to quartz, goethite, birnessite, illite, and aquifer sediments induced an average isotopic fractionation of -0.15‰ with the adsorbed U(VI) isotopically lighter than coexisting aqueous U(VI). In bicarbonate-bearing matrices, the fractionation depended little on the nature of the sorbent, with only birnessite producing an atypically large fractionation. In the case of solutions with ionic strengths much lower than those of typical groundwater, less isotopic fractionation was produced than U(VI) solutions with greater ionic strength. Studies using U isotope data to assess U(VI) reduction must consider adsorption as a lesser, but significant isotope fractionation process.

Biostimulation to induce reduction of soluble U(VI) to relatively immobile U(IV) is an effective strategy for decreasing aqueous U(VI) concentrations in contaminated groundwater systems. If oxidation of U(IV) occurs following the biostimulation phase, U(VI) concentrations increase, challenging the long-term effectiveness of this technique. However, detecting U(IV) oxidation through dissolved U concentrations alone can prove difficult in locations with few groundwater wells to track the addition of U to a mass of groundwater. We propose the U/U ratio of aqueous U as an independent, reliable tracer of U(IV) remobilization via oxidation or mobilization of colloids. Reduction of U(VI) produces U-enriched U(IV), whereas remobilization of solid U(IV) should not induce isotopic fractionation. The incorporation of remobilized U(IV) with a highU/U ratio into the aqueous U(VI) pool produces an increase in U/U of aqueous U(VI). During several injections of nitrate to induce U(IV) oxidation, U/U consistently increased, suggesting U/U is broadly applicable for detecting mobilization of U(IV).

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Uranium (U) groundwater contamination is a major concern at numerous former mining and milling sites across the Upper Colorado River Basin (UCRB), USA, where U(IV)-bearing solids have accumulated within naturally reduced zones (NRZs). Understanding the processes governing U reduction and oxidation within NRZs is critical for assessing the persistence of U in groundwater. To evaluate the redox cycling of uranium, we measured the U concentrations and isotopic compositions (δ 238 U) of sediments and pore waters from four study sites across the UCRB that span a gradient in sediment texture and composition. We observe that U accumulation occurs primarily within fine-grained (low-permeability) NRZs that show active redox variations. Low-permeability NRZs display high accumulation and low export of U, with internal redox cycling of U. In contrast, within high-permeability NRZs, U is remobilized under oxidative conditions, possibly without any fractionation, and transported outside the NRZs. The low δ 238 U of sediments outside of defined NRZs suggests that these reduced zones act as additional U sources. Collectively, our results indicate that fine-grained NRZs have a greater potential to retain uranium, whereas NRZs with higher permeability may constitute a more-persistent but dilute U source.

Mining uranium by in situ recovery (ISR) typically involves injecting an oxidant and a complexing agent to mobilize and extract uranium in a saturated ore zone. This strategy involves less infrastructure and invasive techniques than traditional mining, but ISR often results in persistently elevated concentrations of U and other contaminants of concern in groundwater after mining. These concentrations may remain elevated for an extended period without remediation. Here, we describe a field experiment at an ISR facility in which both a chemical reductant (sodium dithionite) and a biostimulant (sodium acetate) were sequentially introduced into a previously mined ore zone in an attempt to establish reducing geochemical conditions that, in principle, should decrease and stabilize aqueous U concentrations. While several lines of evidence indicated that reducing conditions were established, U concentrations did not decrease, and in fact increased after the amendment deployments. We discuss likely reasons for this behavior, and we also discuss how the results provide insights into improvements that could be made to the restoration process to benefit from the seemingly detrimental behavior.

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