Selenite Stable Isotope Fractionation during Abiotic Reduction by Sodium Sulfide.

Reduction of Se(IV) by sulfur reducing bacteria (SRB) can remove Se from groundwater either by direct respiration or the production of H2S(g) and subsequent abiotic reduction. This study examined abiotic Se(IV) reduction by H2S(g) to determine the associated Se isotope fractionation. The extent of fractionation was compared to the results with studies of Se(IV) reduction in systems containing microorganisms to assess whether these processes could be distinguished. A solution containing Na2S was added in increasing concentrations to solutions containing Se(IV) as SeO32- to reduce and precipitate Se. Precipitates with three distinct colors were observed. Powder X-ray diffraction (PXRD) results yielded three distinct spectra for each of the three colors of precipitate, which corresponded to SenS8-n (orange) or Se(0) (red) and S(0) (yellow). The δ82Se values of the residual dissolved Se increased as the aqueous Se concentration decreased. The S/Se in solution affected the isotopic fractionation, with an 82ε of 10.1 ± 0.6‰ observed for solutions with S/Se < 1.7, and of 7.9 ± 0.3‰ for solutions with S/Se > 1.7.

A cross scale investigation of galena oxidation and controls on mobilization of lead in mine waste rock.

Galena and Pb-bearing secondary phases are the main sources of Pb in the terrestrial environment. Oxidative dissolution of galena releases aqueous Pb and SO4 to the surficial environment and commonly causes the formation of anglesite (in acidic environments) or cerussite (in alkaline environments). However, conditions prevalent in weathering environments are diverse and different reaction mechanisms reflect this variability at various scales. Here we applied complementary techniques across a range of scales, from nanometers to 10 s of meters, to study the oxidation of galena and accumulation of secondary phases that influence the release and mobilization of Pb within a sulfide-bearing waste-rock pile. Within the neutral-pH pore-water environment, the oxidation of galena releases Pb ions resulting in the formation of secondary Pb-bearing carbonate precipitates. Cerussite is the dominant phase and shannonite is a possible minor phase. Dissolved Cu from the pore water reacts at the surface of galena, forming covellite at the interface. Nanometer scale characterization suggests that secondary covellite is intergrown with secondary Pb-bearing carbonates at the interface. A small amount of the S derived from galena is sequestered with the secondary covellite, but the majority of the S is oxidized to sulfate and released to the pore water.

Real-Time XANES Measurement of Se Reduction by Zerovalent Iron in a Flow-through Cell, and Accompanying Se Isotope Measurements.

An anoxic flow-through cell experiment was conducted to examine mechanisms controlling the real-time reduction of selenate (Se(VI)) by zerovalent iron (ZVI), which is commonly used in permeable reactive barriers to treat dissolved contaminants including Se(VI). Changes in selenium (Se) isotope composition were examined by increasing the influent Se concentration over time, thus changing the proportion of Se removed from solution. At the conclusion of the experiment, an anoxic Se-free solution was pumped through the cell to assess the stability of the reaction products. At all stages, X-ray absorption data were obtained from the solid phase and Se isotope data from the aqueous phase. Reduced Se in the form of adsorbed Se(IV), Fe2SeO4, Se(0), and iron selenides accumulated on the ZVI over time. A linear regression function was fit to the δ82/76Se values of the effluent, yielding an isotopic separation of 9.6‰. A Rayleigh curve was fit to the isotope data from the effluent samples collected during the rinse stage with an effective fractionation of 2.4‰. The results from this experiment can be used to elucidate the effect of multiple concurrent mechanisms on Se isotope behavior.

Fractionation of Selenium during Selenate Reduction by Granular Zerovalent Iron.

Batch experiments were conducted using granular zerovalent iron (G-ZVI) with either ultrapure water or CaCO3 saturated simulated groundwater to assess the extent of Se isotope fractionation in solution under the anaerobic conditions characteristic of many aquifers. G-ZVI is a common remediation material in permeable reactive barriers (PRB) to treat Se-contaminated groundwater, and stable isotopes are a potential tool for assessing removal mechanisms. The solution composition, speciation of Se, and Se isotope ratios were determined during both sets of experiments. Dissolved Se concentrations decreased from 10 to <2 mg L(-1) after 3 d in the CaCO3 system and below 0.4 mg L(-1) after 2 d in the ultrapure water system. XANES analysis of the solid phase showed spectra consistent with the formation of Se(IV), Fe2(SeO3)3, FeSe, FeSe2, and Se(0) on the G-ZVI. Selenium isotope ratio measurements in solution in the CaCO3 and ultrapure water experiments showed enrichment of δ(82/76)Se values from -0.94 ± 0.07‰ and -1.93 ± 0.20‰ to maximum values of 6.85 ± 0.52‰ and 5.68 ± 0.20‰ over 72 and 36 h, respectively. The effective fractionations associated with the reduction of Se(VI) were 4.3‰ within the CaCO3 saturated water and 3.0‰ in ultrapure water.