RESUMEN
Potential adverse ecological effects of expanded uranium (U) mining within the Grand Canyon region motivated studies to better understand U exposure and risk to endemic species. This study documents U exposures and analyzes geochemical and biological factors affecting U bioaccumulation at spring-fed systems within the Grand Canyon region. The principal objective was to determine if aqueous U was broadly indicative of U accumulated by insect larvae, a dominate fauna. Analyses focused on three widely distributed taxa: Argia sp. (a predatory damselfly), Culicidae (suspension feeding mosquitos), and Limnephilus sp. (a detritivorous caddisfly). The study showed that U accumulated by aquatic insects (and periphyton) generally correlated positively with total dissolved U, although correlations were strongest when based on modeled concentrations of the U-dicarbonato complex, UO2(CO3)2-2, and UO2(OH)2. Sediment metal concentration was a redundant indicator of U bioaccumulation. Neither insect size or U in the gut content of Limnephilus sp. substantially affected correlations between aqueous U and whole-body U concentrations. However, in Limnephilus sp., the gut and its content contained large quantities of U. Estimates of the sediment burden in the gut indicated that sediment was a minor source of U mass but contributed substantially to the total insect weight. As a result, whole-body U concentration would tend to vary inversely with the sediment burden of the gut. The correlations between aqueous U and bioaccumulated U provide an initial relational baseline against which newly acquired data could be evaluated for changes in U exposure during and after mining operations.
Asunto(s)
Uranio , Animales , Uranio/análisis , Insectos , Factores Biológicos , Monitoreo del Ambiente , Agua/análisisRESUMEN
The fate and transport of inorganic nitrogen (N) is a critically important issue for human and aquatic ecosystem health because discharging N-contaminated groundwater can foul drinking water and cause algal blooms. Factors controlling N-processing were examined in sediments at three sites with contrasting hydrologic regimes at a lake on Cape Cod, MA. These factors included water chemistry, seepage rates and direction of groundwater flow, and the abundance and potential rates of activity of N-cycling microbial communities. Genes coding for denitrification, anaerobic ammonium oxidation (anammox), and nitrification were identified at all sites regardless of flow direction or groundwater dissolved oxygen concentrations. Flow direction was, however, a controlling factor in the potential for N-attenuation via denitrification in the sediments. Potential rates of denitrification varied from 6 to 4500 pmol N/g/h from the inflow to the outflow side of the lake, owing to fundamental differences in the supply of labile organic matter. The results of laboratory incubations suggested that when anoxia and limiting labile organic matter prevailed, the potential existed for concomitant anammox and denitrification. Where oxic lake water was downwelling, potential rates of nitrification at shallow depths were substantial (1640 pmol N/g/h). Rates of anammox, denitrification, and nitrification may be linked to rates of organic N-mineralization, serving to increase N-mobility and transport downgradient.
Asunto(s)
Sedimentos Geológicos/microbiología , Lagos , Consorcios Microbianos/genética , Ciclo del Nitrógeno , Desnitrificación , Agua Subterránea , Hidrología/métodos , Lagos/química , Massachusetts , NitrificaciónRESUMEN
BACKGROUND: Previously described methods to separate dissolved U(IV) from dissolved U(VI) under acidic anoxic conditions prior to laboratory analysis were ineffective with materials currently available commercially. Three strong anion exchange resins were examined for their efficiency in separating, recovering, and preserving both redox states during separation. RESULTS: Under oxic conditions, recovery of U(VI) from three exchange resins (Bio-Rad AG® 1x8 Poly-Prep® prefilled columns, Bio-Rad AG® 1x8 powder, and Dowex® 1x8 powder) ranged from 72% to 100% depending on the dosed mass, eluent volume, and resin selected. Dowex® 1x8 resin was the only resin found to provide 100% recovery of U(VI) with fewer than 5 bed volumes of eluent. Under anoxic conditions, all three resins oxidized U(IV) in aqueous solutions with relatively low U(IV) concentrations (<3x10-6 M). Resin-induced oxidation was observed visually using a leuco dye, safranin-o. Oxidants associated with the resin were irreversibly reduced by the addition of Ti(III). After anoxic resin pre-treatment, a series of U(IV)/U(VI) mixtures at micro-molar levels were prepared and separated using the Dowex® 1x8 resin with 100% recovery of both U(IV) and U(VI) with no resin-induced changes in oxidation state. CONCLUSIONS: Currently available anion exchange resins with apparently identical physical properties were found to have significantly different recoveries for hexavalent uranium at micro-molar concentrations. A novel qualitative technique was developed to visually assess oxidative capacities of anion exchange resins under acidic anoxic conditions. A protocol was developed for pre-treatment and use of currently available anion exchange resins to achieve quantitative separation of U(IV) and U(VI) in aqueous solutions with low U(IV) concentrations. This method can be applied to future work to quantitatively assess dissolved U(IV) and U(VI) concentrations in both laboratory and field samples.
RESUMEN
Extraction techniques utilizing high pH and (bi)carbonate concentrations were evaluated for their efficacy in determining the oxidation state of uranium (U) in reduced sediments collected from Rifle, CO. Differences in dissolved concentrations between oxic and anoxic extractions have been proposed as a means to quantify the U(VI) and U(IV) content of sediments. An additional step was added to anoxic extractions using a strong anion exchange resin to separate dissolved U(IV) and U(VI). X-ray spectroscopy showed that U(IV) in the sediments was present as polymerized precipitates similar to uraninite and/or less ordered U(IV), referred to as non-uraninite U(IV) species associated with biomass (NUSAB). Extractions of sediment containing both uraninite and NUSAB displayed higher dissolved uranium concentrations under oxic than anoxic conditions while extractions of sediment dominated by NUSAB resulted in identical dissolved U concentrations. Dissolved U(IV) was rapidly oxidized under anoxic conditions in all experiments. Uraninite reacted minimally under anoxic conditions but thermodynamic calculations show that its propensity to oxidize is sensitive to solution chemistry and sediment mineralogy. A universal method for quantification of U(IV) and U(VI) in sediments has not yet been developed but the chemical extractions, when combined with solid-phase characterization, have a narrow range of applicability for sediments without U(VI).
Asunto(s)
Sedimentos Geológicos/química , Compuestos de Uranio/análisis , Uranio/análisis , Resinas de Intercambio Aniónico/química , Colorado , Agua Subterránea , Residuos Industriales/análisis , Oxidación-Reducción , Espectroscopía de Absorción de Rayos XRESUMEN
Uranium adsorption-desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500-1000 h although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A nonelectrostatic surface complexation reaction, >SOH + UO2²âº + 2CO3²â» = >SOUO2(CO3HCO3)²â», provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logK(c)) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logK(c) values. Using this approach, logK(c) values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (< 0.063 mm) of another could be demonstrated despite the fines requiring a different reaction stoichiometry. Estimates of logK(c) uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors.