The Rifle alluvial aquifer along the Colorado River in west central Colorado contains finegrained, diffusionlimited sediment lenses that are substantially enriched in organic carbon and sulfides, as well as uranium, from previous milling operations. These naturally reduced zones (NRZs) coincide spatially with a persistent uranium groundwater plume. There is concern that uranium release from NRZs is contributing to plume persistence or will do so in the future. To better define the physical extent, heterogeneity and biogeochemistry of these NRZs, we investigated sediment cores from five neighboring wells. The main NRZ body exhibited uranium concentrations up to 100 mg/kg U as U(IV) and contains ca. 286 g of U in total. Uranium accumulated only in areas where organic carbon and reduced sulfur (as iron sulfides) were present, emphasizing the importance of sulfatereducing conditions to uranium retention and the essential role of organic matter. NRZs further exhibited centimeterscale variations in both redox status and particle size. Mackinawite, greigite, pyrite and sulfate coexist in the sediments, indicating that dynamic redox cycling occurs within NRZs and that their internal portions can be seasonally oxidized. We show that oxidative U(VI) release to the aquifer has the potential to sustain a groundwater contaminant plume for centuries. NRZs, known to exist in other uraniumcontaminated aquifers, may be regionally important to uranium persistence.

No abstract

Chromium(VI) produced from the oxidation of indigenous Cr(III) minerals is increasingly being recognized as a threat to groundwater quality. A critical determinant of Cr(VI) generation within soils and sediments is the necessary interaction of two low-solubility phases-Cr(III) silicates or (hydr)oxides and Mn(III/IV) oxides-that lead to its production. Here we investigate the potential for Cr(III) oxidation by Mn oxides within fixed solid matrices common to soils and sediments. Artificial aggregates were constructed from Cr(OH)- and CrFe(OH)-coated quartz grains and either mixed with synthetic birnessite or inoculated with the Mn(II)-oxidizing bacterium Leptothrix cholodnii. In aggregates simulating low organic carbon environments, we observe Cr(VI) concentrations within advecting solutes at levels more than twenty-times the California drinking water standard. Chromium(VI) production is highly dependent on Cr-mineral solubility; increasing Fe-substitution (x = 0 to x = 0.75) decreases the solubility of the solid and concomitantly decreases total Cr(VI) generation by 37%. In environments with high organic carbon, reducing conditions within aggregate cores (microbially) generate sufficient Fe(II) to suppress Cr(VI) efflux. Our results illustrate Cr(VI) generation from reaction with Mn oxides within structured media simulating soils and sediments and provide insight into how fluctuating hydrologic and redox conditions impact coupled processes controlling Cr and Mn cycling.

Groundwater resources in California represent a confluence of high-risk factors for hexavalent chromium contamination as a result of industrial activities, natural geology, and, potentially, land use. Here, we examine state-wide links in California between groundwater Cr(VI) concentrations and chemicals that provide signatures for source attribution. In environmental monitoring wells, Cr(VI) had the highest co-occurrence and also clustered with 1,4-dioxane and several chlorinated hydrocarbons indicative of the metal plating industry. Additionally, hotspots of Cr(VI) co-occurring with bromoform result from volatile organic compound remediation using in situ chemical oxidation that inadvertently oxidizes naturally occurring Cr(III). In groundwater supply wells, which are typically free of industrial inputs, Cr(VI) correlates with dichlorodiphenyldichloroethylene (DDE), vanadium, and ammonia and clusters with nitrate and dissolved oxygen, suggesting potential links between agricultural activities and Cr(VI). Specific controls on Cr(VI) vary substantially by region: from the metal plating industry around Los Angeles and the San Francisco Bay areas to natural redox conditions along flow paths in the Mojave Desert and to correlations with agricultural practices in the Central Valley of California. While industrial uses of Cr lead to the most acute cases of groundwater Cr(VI) contamination, oxidation of naturally occurring Cr affects a larger area, more wells, and a greater number of people throughout California.

Proton activity is the master variable in many biogeochemical reactions. To control pH, laboratory studies involving redox-sensitive minerals like manganese (Mn) oxides frequently use organic buffers (typically Good’s buffers); however, two Good’s buffers, HEPES and MES, have been shown to reduce Mn(IV) to Mn(III). Because Mn(III) strongly controls mineral reactivity, avoiding experimental artefacts that increase Mn(III) content is critical to avoid confounding results. Here, we quantified the extent of Mn reduction upon reaction between Mn oxides and several Good’s buffers (MES, pKa = 6.10; PIPES, pKa = 6.76; MOPS, pKa = 7.28; HEPES, pKa = 7.48) and TRIS (pKa = 8.1) buffer. For δ-MnO2, Mn reduction was rapid, with up to 35% solid-phase Mn(III) generated within 1 h of reaction with Good’s buffers; aqueous Mn was minimal in all Good’s buffers experiments except those where pH was one unit below the buffer pKa and the reaction proceeded for 24 h. Additionally, the extent of Mn reduction after 24 h increased in the order MES < MOPS < PIPES < HEPES << TRIS. Of the variables tested, the initial Mn(II,III) content had the greatest effect on susceptibility to reduction, such that Mn reduction scaled inversely with the initial average oxidation number (AMON) of the oxide. For biogenic Mn oxides, which consist of a mixture of Mn oxides, bacterial cells and extracelluar polymeric substances, the extent of Mn reduction was lower than predicted from experiments using abiotic analogs and may result from biotic re-oxidation of reduced Mn or a difference in the reducibility of abiotic versus biogenic oxides. The results from this study show that organic buffers, including morpholinic and piperazinic Good’s buffers and TRIS, should be avoided for pH control in Mn oxide systems due to their ability to transfer electrons to Mn, which modifies the composition and reactivity of these redox-active minerals.