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The sequential extraction (SEP) of selenium to determine the isotopic composition of different Se pools in soils is an important tool for tracking biogeochemical cycling of Se in soils. An appropriate Se extraction method for the stable Se isotope analysis was established and tested for different Se pools in soils in terms of reproducibility and recovery. Soil samples (n = 4) from a seleniferous field site in Punjab, India and two standard reference materials were chosen because of their relatively high total Se concentration of 2 to 4.5 mg kg-1. Additionally, a soil sample with low Se content was utilized to verify the procedure and reproducibility. The isotopic mass-balance calculation gives consistent δ82Se values for the sum of the extracted pools, relative to δ82Se of the bulk soils. For instance, in one studied soil (soil-1), the sum of δ82Se of all individual Se-pools (δ82Semass-balance = 3.35‰) is in good agreement with the analysis of δ82Se of the bulk soil (δ82Sebulk of 3.56‰). We observed up to a 2‰ range in δ82Se among the different Se soil-pools (soil-3). Our Se isotopic results of Se soil pools provide more detailed observations of the Se linked processes in soils compared to bulk δ82Se. Thus, quantitative Se isotopic analysis of different Se pools can be an important tool for predicting the environmental cycling of selenium in soils or sediments. [ABSTRACT FROM AUTHOR]

At Idaho National Laboratory, Cr(VI) concentrations in a groundwater plume once exceeded regulatory limits in some monitoring wells but have generally decreased over time. This study used Cr stable isotope measurements to determine if part of this decrease resulted from removal of Cr(VI) via reduction to insoluble Cr(III). Although waters in the study area contain dissolved oxygen, the basalt host rock contains abundant Fe(II) and may contain reducing microenvironments or aerobic microbes that reduce Cr(VI). In some contaminated locations, 53Cr/52Cr ratios are close to that of the contaminant source, indicating a lack of Cr(VI) reduction. In other locations, ratios are elevated. Part of this shift may be caused by mixing with natural background Cr(VI), which is present at low concentrations but in some locations has elevated 53Cr/53Cr. Some contaminated wells have 53Cr/53Cr ratios greater than the maximum attainable by mixing between the inferred contaminant and the range of natural background observed in several uncontaminated wells, suggesting that Cr(VI) reduction has occurred. Definitive proof of reduction would require additional evidence. Depth profiles of 53Cr/53Cr suggest that reduction occurs immediately below the water table, where basalts are likely least weathered and most reactive, and is weak or nonexistent at greater depth. [ABSTRACT FROM AUTHOR]

The article presents a study which investigates the selenium stable isotope during selenium biogeochemical cycling that can be found in a lacustrine environment in Sweitzer Lake, Colorado. It stresses the importance of selenium reduction in the sediments found in the lake and its isotopic impact between surface waters and reduction sites within the sediments. Moreover, the study concludes that potential isotopes for selenium are considered as migration indicators that are found in fish tissues and phytoplankton.

Chromium stable isotope ratios show promise at indicators of Cr(VI) reduction in groundwater, but no published study has yet demonstrated that expected relationships between 53Cr/52Cr and Cr(VI) concentration, position, and time occur in an actual groundwater plume. We present an extensive data set from a point-source plume in Berkeley, CA; data extend over 5 years and 14 locations covering the entire plume. We interpret the data using a Rayleigh distillation model with an effective fractionation factor that incorporates an intrinsic fractionation factor determined from incubations of site sediments and accounts for reservoir effects in the restricted subsurface zones where Cr(VI) reduction is thought to occur. The groundwater 53Cr/52Cr and Cr(VI) concentration data are consistent with a scenario where the system has reached a steady state: Cr(VI) reduction continues, the extent of reduction at any point is constant over time, reduction proceeds to completion at the downgradient edge of the plume, and the plume is no longer advancing. The overall consistency of the results with a reasonable model for the site supports the use of Cr isotope-based estimates of reduction, hut we discuss current uncertainties and limitations of the approach as well. [ABSTRACT FROM AUTHOR]

Wetlands remove many dissolved pollutants from surface waters by various mechanisms. Stable isotope ratio measurements may provide a means of detecting and possibly quantifying certain removal processes, such as reduction of SeO42-, Cr(Vl), NO3-, and HCIO4-, that fractionate isotopes. However, the magnitude of the isotopic fractionation for a given reaction depends on the setting in which it occurs. We explore the case where isotope ratio shifts in surface waters are used to detect or quantify reactions occurring in pore waters of underlying sediments. A series of SeO42- reduction experiments reveals that the effective isotopic fractionation, observed in the water column as a result of SeO42- diffusion into underlying, Se-reducing sediments, is weaker than the intrinsic fractionation induced by the same reduction reactions in well-mixed systems in which reaction sites are not separated from measured SeO42-. An intact sediment core yielded an effective ϵ (≈ δreact — δinstantaneous prod) of 0.20‰, whereas the intrinsic ϵ was 0.61‰. These results are consistent with previously published reactive transport models. Isotopic studies of sediment-hosted reactions in wetlands and other surface water systems should use the smaller effective fractionation values, which can be estimated using the models. [ABSTRACT FROM AUTHOR]

Measurements of selenium (Se) isotope fractionation began about 1960, with work by Roy Krouse and Harry Thode on Se reduction. Se isotope research to date has confirmed these measurements, developed new measurement techniques, and investigated Se isotope fractionation during several other critical processes. As the geochemistry of Se is complex, current understanding of Se isotope systematics involves studies of many reactions, and synthesis of these results. Fractionation during dissimilatory Se reduction by pure bacterial cultures varies according to experimental conditions, but bacterial reduction in sediment slurries from three wetlands induces consistent 80Se/76Se fractionations of about 2.8‰ and 5.6‰ for Se(VI) reduction and Se(IV) reduction, respectively. Assimilation by higher plants, Se(IV) oxidation, sorption, and biological volatilization induce little or no isotopic fractionation. Preliminary experiments suggest that fractionation of about 1.0‰ accompanies assimilation of Se by algae. Thus, significant fractionation occurs in only a few reactions and if fractionation is observed in nature, it provides evidence that those reactions occur.Understanding of the systematics of other “heavy stable isotopes”, including those of calcium, iron, copper, molybdenum, chromium, and zinc, is currently being developed. Mass-dependent fractionation of these and other elements should provide a new set of tools for low-temperature biogeochemical applications, such as detecting redox reactions or distinguishing between potential contaminant sources. Some general conclusions from the Se isotopes work can be extended to the other heavy stable isotopes to aid in developing them and assessing their likely geochemical applicability. [Copyright &y& Elsevier]

The mobility and bioavailability of Se depend on its redox state, and reduction of Se oxyanions to less mobile, reduced species controls transport of this potentially toxic element in the environment. Stable isotope fractionation of Se is currently being developed as an indicator of Se immobilization through reduction. In this study, Se isotope fractionation resulting from reduction of Se(VI) and Se(IV) oxyanions by natural microbial consortia was measured in sediment slurry experiments under nearly natural conditions, with no substrate added. Experiments were conducted with a wide range of initial Se concentrations and with sediment and water from three locations with contrasting environmental settings. The products of Se(VI) and Se(IV) reduction were enriched in the lighter isotopes relative to the reactants. Shifts of −2.6‰ to −3.1‰ and −5.5‰ to −5.7‰, respectively, were observed in the 80Se/76Se ratio. These isotopic fractionations did not depend significantly on initial Se concentrations, which were varied from 22 μg/l to 8 mg/l, or on geochemical differences among the sediments. These results provide estimates of Se isotope fractionation in organic-rich wetland environments but may not be appropriate for substrate-poor aquifers and marine sediments. [Copyright &y& Elsevier]

Selenium stable isotope ratios are known to shift in predictable ways during various microbial, chemical, and biological processes, and can be used to better understand Se cycling in contaminated environments. In this study we used Se stable isotopes to discern the mechanisms controlling the transformation of oxidized, aqueous forms of Se to reduced, insoluble forms in sediments of Se‐affected environments. We measured 80Se/76Se in surface waters, shallow ground waters, evaporites, digested plants and sediments, and sequential extracts from several sites where agricultural drainage water is processed in the San Joaquin Valley of California. Selenium isotope analyses of samples obtained from the Tulare Lake Drainage District flow‐through wetland reveal small isotopic contrasts (mean difference 0.7‰) between surface water and reduced Se species in the underlying sediments. Selenium in aquatic macrophytes was very similar isotopically to the NaOH and Na2SO3 sediment extracts designed to recover soluble organic Se and Se(0), respectively. For the integrated on‐farm drainage management sites, evaporite salts were slightly (approximately 0.6‰) enriched in the heavier isotope relative to the inferred parent waters, whereas surface soils were slightly (approximately 1.4‰) depleted. Bacterial or chemical reduction of Se(VI) or Se(IV) may be occurring at these sites, but the small isotopic contrasts suggest that other, less isotopically fractionating mechanisms are responsible for accumulation of reduced forms in the sediments. These findings provide evidence that Se assimilation by plants and algae followed by deposition and mineralization is the dominant transformation pathway responsible for accumulation of reduced forms of Se in the wetland sediments. [ABSTRACT FROM AUTHOR]

Microbially-catalyzed reductive immobilization of aqueous uranium (U) as a solid phase has been proposed as a U remediation technique. Both laboratory and field experiments have demonstrated that this reduction reaction alters the 238U/235U ratio, producing a 238U-enriched U(IV) solid. In contrast, other major U reactive transport processes fractionate these isotopes much less. This suggests the potential to quantify the extent of bioreduction occurring in groundwater containing U using the 238U/235U ratio, which would substantially improve upon current practices largely relying on U concentration measurements alone. Current reactive transport models for uranium dynamics include only concentration measurements, which are strongly influenced by highly coupled reactive transformation and aqueous transport processes. The complex physical and chemical behavior of U potentially compromises such quantitative analysis of U storage and release. Here we report the first numerical reactive transport model which explicitly incorporates variations in the 238U/235U ratio of U and demonstrates improved interpretation of the principal chemical reactions and groundwater transport processes affecting the subsurface mobility and distribution of this widespread contaminant. Recent U bioreduction studies performed in a contaminated aquifer in Rifle, Colorado, USA applied Rayleigh distillation models to interpret U stable isotope fractionation observed as a result of acetate amendment. These simplified models were unable to resolve the spatiotemporal pattern of U isotope fractionation recorded in the aqueous solutes. Here, we employ the multi-component, isotope-enabled CrunchTope reactive transport software to interpret these measured U isotope ratios, and demonstrate accurate reproduction of observed trends in both geochemistry and 238U/235U ratios for two consecutive years of field experiments. Our results indicate that accurately modeling both the U concentration and isotope ratio distributions greatly constrains the parameter space of the model. We find that the transport properties of U in the Rifle aquifer are governed by the presence of low-permeability regions, which the isotopes are uniquely sensitive to. When U reduction is spatially constrained by these low-permeability regions, the shift in the 238U/235U ratio becomes more muted. Accurate modeling of observed U isotope ratios thus provides a powerful means to better understand bioremediation, and the current study serves to advance the application of this novel method. [ABSTRACT FROM AUTHOR]

Abstract: Sorption and reduction are important processes influencing the environmental mobility and cycling of Se. In this study, we determined the rates of reaction and isotopic fractionations of Se(IV) and Se(VI) during sorption to iron oxides (2-line ferrihydrite, hematite and goethite) and iron sulfides (mackinawite and pyrite) at pH7 and room temperature (22±2°C). More than 80% of aqueous Se(IV) was removed from solution in the presence of the mineral phases, except for hematite where only 40% of aqueous Se(IV) was sorbed. In contrast, less than 20% of aqueous Se(VI) was removed in the mineral suspensions, except for 2-line ferrihydrite where approximately 50% removal was observed. While XANES spectra revealed no change in Se oxidation state when Se(IV) and Se(VI) sorbed to iron oxides, they showed evidence of reduction in the presence of iron sulfides. Selenium isotopic fractionations, expressed as ε82/76Se, were always less than 1‰ in the experiments with iron oxides (mean ε82/76Se: 0.2‰). Fractionations were significantly higher in the experiments with iron sulfides, with ε82/76Se values of up to ~10‰ in the Se(IV)-pyrite system, and a mean ε82/76Se value of 2.3‰ for all sorption experiments with iron sulfides combined. The larger fractionations in the experiments with iron sulfides reflect the chemical reduction of Se(IV) and Se(VI). The highest isotope fractionation observed in the Se(IV)–FeS2 system (9.7‰) is comparable to that previously reported for Se(VI) reduction by green rust (11.1‰). [Copyright &y& Elsevier]

The recent widespread adoption of compact fluorescent lamps (CFL) has increased their importance as a source of environmental Hg. Stable isotope analysis can identify the sources of environmental Hg, but the isotopic composition of Hg from CFL is not yet known. Results from analyses of CFL with a range of hours of use show that the Hg they contain is isotopically fractionated in a unique pattern during normal CFL operation. This fractionation is large by comparison to other known fractionating processes for Hg and has a distinctive, mass-independent signature, such that CFL Hg could be uniquely identified from other sources. The fractionation process described here may also explain anomalous fractionation of Hg isotopes in precipitation. [ABSTRACT FROM AUTHOR]

Mercury stable isotope abundances were used to trace transport of Hg-impacted river sediment near a coal ash spill at Harriman, Tennessee, USA. δ202Hg values for Kingston coal ash released into the Emory River in 2008 are significantly negative (-1.78 ± 0.35‰), whereas sediments of the Clinch River, into which the Emory River flows, are contaminated by an additional Hg source (potentially from the Y-12 complex near Oak Ridge, Tennessee) with near-zero values (-0.23 ± 0.16‰). Nominally uncontaminated Emory River sediments (12 miles upstream from the Emory-Clinch confluence) have intermediate values (-1.17 ± 0.13‰) and contain lower Hg concentrations. Emory River mile 10 sediments, possibly impacted by an old paper mill has δ202Hg values of -0.47 ± 0.04‰. A mixing model, using δ202Hg values and Hg concentrations, yielded estimates of the relative contributions of coal ash, Clinch River, and Emory River sediments for a suite of 71 sediment samples taken over a 30 month time period from 13 locations. Emory River samples, with two exceptions, are unaffected by Clinch River sediment, despite occasional upstream flow from the Clinch River. As expected, Clinch River sediment below its confluence with the Emory River are affected by Kingston coal ash; however, the relative contribution of the coal ash varies among sampling sites [ABSTRACT FROM AUTHOR]

Abstract: León valley, located in the Mexican state of Guanajuato, has a long history (35+ a) of Cr contamination of groundwater and surface water. Here data are presented for Cr, major ion and trace element concentrations and Cr stable isotope measurements of groundwater in a heavily contaminated aquifer in Buenavista, where Cr ore processing residue piles (COPRPs) located in a chromate production factory are the main source of Cr. The aquifer directly beneath the factory still retains very high Cr(VI) concentrations (∼121mg/L). Ongoing pump and treat remediation is keeping the high concentration plume confined to the factory area and immediate vicinity, though Cr is also detected at some distance away. Chromium isotope data of the aquifer directly under the factory show only a small increase in δ53Cr (+0.33‰ to +0.81‰) and indicates minimal reduction of Cr(VI) to Cr(III). Very high Cr(VI) concentrations have possibly overwhelmed natural reductants and furthermore fresh Cr(VI) was being leached into the groundwater from the COPRP. From just one year of Cr isotope data it is clear that more aggressive remediation techniques will be necessary to reduce or eliminate the contamination. The fringes of the Cr plume have substantially lower concentrations and can be partially explained by transport of the main plume or mixing between waters from the nearby landfill and highly contaminated waters from QC. While the source of Cr at the fringes of the plume could be attributed to a source from the nearby landfill instead of the main plume from the factory, the Cr stable isotope data show enrichment in the heavier isotopes and point to varying amounts of reduction. Isotopic enrichment seen between 2007 and 2008 along the fringe may indicate either reduction or less unreacted Cr(VI) is being transported to the fringes. In either case some potential for natural attenuation of Cr(VI) exists at the western margin of the plume with the landfill playing a role. [Copyright &y& Elsevier]

Abstract: Selenium (Se) is an essential trace element, which, with multiple oxidation states and six stable isotopes, has been suggested as a potentially powerful paleoenvironmental proxy. In this study, bulk Se concentrations and isotopic compositions were analyzed in a suite of about 120 samples of fine-grained marine sedimentary rocks and sediments spanning the entire Phanerozoic. While the Se concentrations vary greatly (0.22–72ppm), the δ82/76Se values fall in a fairly narrow range from −1 to +1‰ (relative to NIST SRM3149), with the exception of laminated black shales from the New Albany Shale formation (Late Devonian), which have δ82/76Se values of up to +2.20‰. Black Sea sediments (Holocene) and sedimentary rocks from the Alum Shale formation (Late Cambrian) have Se to total organic carbon ratios (Se/TOC) and δ82/76Se values close to those found in modern marine plankton (1.72±0.15×10−6 mol/mol and 0.42±0.22‰). For the other sedimentary sequences and sediments, the Se/TOC ratios show Se enrichment relative to modern marine plankton. Additional input of isotopically light terrigenous Se may explain the Se/TOC and δ82/76Se data measured in recent Arabian Sea sediments (Pleistocene). The very high Se concentrations in sedimentary sequences that include the Cenomanian–Turonian Oceanic Anoxic Event (OAE) 2 may reflect an enhanced input of volcanogenic Se to the oceans. As the latter has an isotopic composition not greatly different from marine plankton, the volcanogenic source does not impart a distinct signature to the sedimentary Se isotope record. The lowest average δ82/76Se values are observed in the OAE2 samples from Demerara Rise and Cape Verde Basin cores (δ82/76Se=−0.14±0.45‰) and could reflect fractionation associated with microbial or chemical reduction of Se oxyanions in the euxinic water column. In contrast, a limiting availability of seawater Se during periods of increased organic matter production and burial may be responsible for the elevated δ82/76Se values and low Se/TOC ratios in the black shales of the New Albany Shale formation. Overall, our results indicate that to unlock the full proxy potential of marine sedimentary Se records, we need to gain a much more detailed understanding of the sources, chemical speciation, isotopic fractionations and cycling of Se in the marine environment. [Copyright &y& Elsevier]