Soft X-ray spectromicroscopy of cobalt uptake by cement

Scanning transmission X-ray microscopy was used to investigate the speciation and spatial distribution of Co in a Co(II)-doped cement matrix. The aim of this study was to improve the understanding of the heavy metals immobilization process in cement on the molecular level. The Co-doped cement samples hydrated for 30 days with a Co loading of 5000 mg/kg were prepared under normal atmosphere to simulate conditions used for cement-stabilized waste packages. Co 2p(3/2) absorption edge signals were used to determine the spatial distributions of the metal species in the Co(II)-doped cement. The speciation of Co was determined by collecting near-edge X-ray absorption fine structure spectra. On the basis of the shape of the absorption spectra, it was found that Co(II) is partly oxidized to Co(III). The correlation, respectively the anticorrelation with elements such as Al, Si, and Mn, show that Co(II) is predominantly present as Co-hydroxide-like phase as well as Co-phyllosilicate, whereas Co(III) tends to be incorporated only into a CoOOH-like phase. Thus, this study suggests that thermodynamic calculations of Co(II)-immobilization by cementitious systems should take into consideration not only the solubility of Co(II)-hydroxides but also Co(III) phases.     

X-ray absorption and micro X-ray fluorescence spectroscopy investigation of copper and zinc speciation in biosolids

Despite its pivotal role in determining the risks and time frames associated with contaminant release, metal speciation remains a poorly understood aspect of biosolids chemistry. The work reported here used synchrotron-based spectroscopy techniques to investigate the speciation of copper and zinc in a range of Australian biosolids. High resolution element mapping of biosolids samples using micro X-ray fluorescence spectroscopy revealed considerable heterogeneity in key element associations, and a combination of both organic and inorganic copper and zinc binding environments. Linear combination fitting of K-edge X-ray absorption spectra indicated consistent differences in metal speciation between freshly produced and stockpiled biosolids. While sulfide minerals play a dominant role in metal binding in freshly dewatered biosolids, they are of lesser importance in dried biosolids that have been stockpiled. A degree of metal binding with iron oxide minerals was apparent but the results did not support the hypothesis that biosolids metals are chiefly associated with iron minerals. This work has potential implications for the long-term stability of metals in biosolids and their eventual fate following land application.     

Advances in the detection of as in environmental samples using low energy X-ray fluorescence in a scanning transmission X-ray microscope: arsenic immobilization by an Fe(II)-oxidizing freshwater bacteria

Speciation and quantitative mapping of elements, organic and inorganic compounds, and mineral phases in environmental samples at high spatial resolution is needed in many areas of geobiochemistry and environmental science. Scanning transmission X-ray microscopes (STXMs) provide a focused beam which can interrogate samples at a fine spatial scale. Quantitative chemical information can be extracted using the transmitted and energy-resolved X-ray fluorescence channels simultaneously. Here we compare the relative merits of transmission and low-energy X-ray fluorescence detection of X-ray absorption for speciation and quantitative analysis of the spatial distribution of arsenic(V) within cell-mineral aggregates formed by Acidovorax sp. strain BoFeN1, an anaerobic nitrate-reducing Fe(II)-oxidizing β-proteobacteria isolated from the sediments of Lake Constance. This species is noted to be highly tolerant to high levels of As(V). Related, As-tolerant Acidovorax-strains have been found in As-contaminated groundwater wells in Bangladesh and Cambodia wherein they might influence the mobility of As by providing sorption sites which might have different properties as compared to chemically formed Fe-minerals. In addition to demonstrating the lower detection limits that are achieved with X-ray fluorescence relative to transmission detection in STXM, this study helps to gain insights into the mechanisms of As immobilization by biogenic Fe-mineral formation and to further the understanding of As-resistance of anaerobic Fe(II)-oxidizing bacteria.     

On the relationship between D(ow) and K(ow) in natural waters

The relationship between the overall octanol-water partition coefficient of a mixture of related chemical species, D(ow), and the octanol-water partition coefficients of its components, (K(ow))i, is explored. One form of the relationship (model 1) is generally applicable but relies on definition of aqueous phase speciation at equilibrium with octanol. An alternative form of the relationship (model 2) circumvents this requirement but assumes that related species are conserved during the partitioning process and is explicitly dependent on the water to octanol volume ratio, Vw/Vo. The potential applications and limitations of each model for defining the hydrophobic characteristics of chemical species in natural waters are examined in the light of experimental partition results for dissolved Cu and Pb in river waters. Given the general difficulties in accurate speciation modeling of trace metals in natural samples, model 1 was only able to estimate a K(ow) (typically in the range 0.03-0.3) for a computed organically complexed fraction of metal (generally > 90%). However, by conducting partition "isotherms" as a function of Vw/Vo and, because of the buffering capacity of natural waters, by treating a sample as two distinct hydrophilic and hydrophobic "pools", model 2 was able to estimate both the abundance and K(ow) of a more specific group of species. Parameter values derived from the latter approach indicated that river waters comprise a relatively small pool (about 4-20%) of metal whose octanol-water partitioning is in the region of 15-150. Given that the free ion activity of strongly binding metals in natural waters is extremely small, the hydrophobic fraction may, in many cases, representthe most biologically and environmentally significant component of metal. Accordingly, the experimental and modeling approaches described herein could be of great significance to an improved understanding of the fate and impacts of trace metals in the aquatic environment.     

EXAFS and XANES studies of retention of copper and lead by a lignocellulosic biomaterial

Lignocellulosic substrate (LS), which is a low cost biomaterial, has a strong complexing ability and can be used in the treatment of wastewaters as biosorbentto remove heavy metals. The speciation of copper and lead to this biomaterial has been studied by X-ray absorption spectroscopy. The copper(II) has a 6-coordinate structure with four oxygen atoms in the equatorial plane at 1.95 A and two in axial position at 2.35 A. In the case of lead a particularly low coordination number of about 3 has been obtained. The combination of extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) suggested that Cu and Pb are bound to the surface of LS through carboxylic moieties.     

Metal bioaccumulation in aquatic species: quantification of uptake and elimination rate constants using physicochemical properties of metals and physiological characteristics of species

Mechanistic bioaccumulation models are powerful tools in environmental risk assessment as they provide insight in varying accumulation patterns across species, contaminants, and conditions, and they are applicable beyond tested cases. In these models key parameters, as absorption and elimination rate constants, are predicted based on chemical specific properties and physiological characteristics. However, due to the complex environmental behavior of metals, the development of mechanistic bioaccumulation models has lagged behind that for organic chemicals. Absorption and elimination rate constants of organic substances have long been linked to their octanol-water partition coefficient, yet no equivalent quantitative relationships exist for metals. In the present study, we successfully related metal absorption rate constants to a metal specific property, the covalent index, and a species-characteristic, the ventilation rate. This quantitative relationship holds for a wide range of organisms and metals, i.e., 17 aquatic species and 10 metals, suggesting that a generic modeling approach of metal uptake kinetics is feasible for aquatic organisms. In contrast, elimination rate constants show no metal - specific character. Average, weight-corrected elimination rate constants are relatively similar among metals and species, suggesting that a single weight-corrected elimination rate constant can be used in bioaccumulation studies on aquatic species.     

Metal protein interactions

Proteins associated with metals serve many important biological functions. The amino acid residues provide the functional groups in a protein which are the potential ligands for a metallic cation. Metals impart various effects on protein structure and bring about overall structural stability. These effects are seen in quarternary, secondary and tertiary structures of the protein. There are varieties of approaches to study metal protein interactions. The earliest technique being the equilibrium dialysis which is still used extensibly to determine the binding strength and the number of metals bound per protein molecule. There are a number of other techniques available which provide precise information about the nature of metal binding sites. They include electron spin resonance, UV and visible spectoscopy, nuclear magnetic resonance, resonance Raman, X-ray crystallography, X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (XAFS), etc. Selected metal protein interactions are discussed in this review. Albumin is the major plasma protein in blood which transports a number of metals. Detailed studies of Cu(II) and Ni(II) binding to albumin suggests that both metals have the same specific binding site at the NH2-terminal tripeptide sequence (Asp1-Ala2-His3...) involving the Asp alpha-NH2, His3 N (1) imidazole, two deprotonated peptide nitrogens (Ala2NH and His3NH), and Asp1 COO- group. Transferrin transports Fe(III) in blood. The protein possesses two metal-binding sites, each within a domain of bilobal proteins. Presence of carbonate is an important feature of Fe(III)-binding to transferrin. The binding site has been postulated as one involving Tyr 185 and Tyr 188 and suggests that two of the three histidines His 119, His 207 and His 249 also serve as ligands. Arginine 145 is a likely anchor for the carbonate anion. Superoxide dismutase is an enzyme found in erythrocytes which catalyzes the dismutation of superoxide radical. The protein is a dimer made up of two equivalent subunits. The subunits are held together by noncovalent interactions. For optimal enzymatic activity, at least two of the protein's four metal ions must be cupric. The results of the X-ray crystal structural analysis for Cu(II) and Zn(II) containing protein have been reported. In the metal-binding region of one subunit, Cu(II) and Zn(II) are separated by approximately 6A. The Cu(II) is bound to imidazole side chains of histidines 44, 46, 61 and 118 in a distorted square planar arrangement. The imidazole ring of histidine 61 is believed to be deprotonated and to serve as a bridge between Cu(II) and Zn(II).(ABSTRACT TRUNCATED AT 400 WORDS)     

Effect of chemical speciation on toxicity of mercury to Escherichia coli biofilms and planktonic cells

While it is known that microbial uptake of mercury (Hg) by planktonic cultures is influenced by the extracellular speciation of mercury in aquatic systems, Hg uptake in biofilm cultures is understudied. We compared the importance of Hg(II) speciation in toxicity to both planktonic and biofilm cultures of the Gram-negative bacterium Escherichia coli 055. Variable chloride chemistry experiments were carried out to modify mercury speciation. Biofilms were observed to be more resistant to Hg than planktonic cells. In both planktonic and biofilm cultures, the toxicity of Hg increased and then decreased along the chloride gradient. The percent reduction in cell viability was linearly related to the concentration of HgCl2(0) when Hg-chloro complexes dominated the speciation, consistent with a passive diffusion model. However, toxicity to both planktonic cells and biofilms at low salinities could not be explained by passive diffusion alone, which suggests that microbial uptake of Hg in both planktonic cells and biofilms may occur by both passive diffusion of neutral species and facilitated uptake. The relationship between toxicity and chloride concentration was similar in the presence and absence of a biofilm, indicating that the presence of the biofilm does not drastically change the relative availability of the dominant mercury species.     

Microprobe techniques for speciation analysis and geochemical characterization of mine environments: the mercury district of Almadén in Spain

Metallurgic calcines with very high mercury and methylmercury content from the Almadén mining district were analyzed by synchrotron-based microprobe techniques. Information about mercury speciation was obtained by micro-EXAFS (microscopic extended X-ray absorption fine structure) spectroscopy, whereas elemental associations were evaluated by micro-XRF (microscopic X-ray fluorescence analysis) mapping. Complementary characterization methodologies, including X-ray diffraction (XRD), inductively coupled plasma-optical spectroscopy (ICP-OES), as well as a sequential extraction scheme (SES), were used to predict the potential availability of mercury. Analysis of total metal content revealed extremely high concentrations of mercury and iron (between 7 and 35 and 65-70 g kg(-1), respectively) and high zinc concentrations (2.2-2.5 g kg(-1)), whereas other metals such as copper, nickel, and lead were found at low concentration levels (30-300 mg kg(-1)). Micro-EXAFS results indicate that cinnabar (HgS(red)) is one of the main species within the studied mercury-rich particles (5-89% of total mercury content), together with more soluble mercury compounds such as Hg3(SO4)02 (schuetteite) and HgO (5-55% of total mercury content). Additionally, element-specific micro-XRF maps of selected mercury-rich particles in the studied samples revealed an evident correlation among Hg-Pb-Ni (and S), indicating a possible geochemical linkage of these elements. Correlations were also found among Fe-Mn and Hg, which have been attributed to sorption of mercury onto oxyhydroxides of Fe and Mn. This finding was supported by results from a sequential extraction scheme, where a significant     

Spatial and temporal variation of watertype-specific no-effect concentrations and risks of Cu, Ni, and Zn

Geographical and temporal variations in metal speciation were calculated and water-type specific sensitivities were derived for a range of aquatic species, using surveillance water chemistry data that cover almost all surface water types in The Netherlands. Biotic ligand models for Cu, Zn, and Ni were used to normalize chronic no-effect concentrations (NOEC) determined in test media toward site-specific NOEC for 372 sites sampled repeatedly over 2007-2010. Site-specific species sensitivity distributions were constructed accounting for chemical speciation. Sensitivity of species as well as predicted risks shifted among species over space and time, due to changes in metal concentrations, speciation, and biotic ligand binding. Sensitivity of individual species (NOEC) and of the ecosystem (HC5) for Cu, Ni, and Zn showed a spatial variation up to 2 orders of magnitude. Seasonality of risks was shown, with an average ratio between lowest and highest risk of 1.3, 2.0, and 3.6 for Cu, Ni, and Zn, respectively. Maximum risks of Cu, Ni, and Zn to ecosystems were predicted in February and minimum risks in September. A risk assessment using space-time specific HC5 of Cu and Zn resulted in a reduction of sites at risk, whereas for Ni the number of sites at risks increased.     

Evidence for biogenic pyromorphite formation by the nematode Caenorhabditis elegans

The determination of chemical speciation and spatial distribution is a prerequisite for a mechanistic understanding of contaminant bioavailability and toxicity to an organism. We have employed synchrotron X-ray techniques to study Cu and Pb speciation and spatial distribution in the soil nematode Caenorhabditis elegans. Nematodes were exposed to each metal ion singly or simultaneously in solution for 24 h and were then rinsed thoroughly and preserved in formalin for transportation to the National Synchrotron Light Source. Experiments were conducted at the microprobe beamline X26A employing a focused beam of approximately 10 microm in diameter. Nematodes were mounted in agar gel on Kapton tape. Two-dimensional elemental maps for Cu- and Pb-exposed nematodes were collected in fluorescence mode. Copper was homogeneously distributed throughout the body of the nematode, but Pb exhibited a high degree of localization in the nematode, exclusively in the anterior pharynx region. Detectable localized concentrations of Pb in C. elegans occurred at aqueous exposure concentrations of 2.4 microM. Micro X-ray diffraction of these Pb hotspots gave a diffraction pattern indicating a crystalline Pb solid that was consistent with the Pb phosphate, pyromorphite. Biogenic inorganic phosphate granule formation is relatively common in soil invertebrates; however, these phosphates are typically amorphous, and we believe that this is the first report of crystalline pyromorphite formed internally in an organism.     

Copper stabilization by zeolite synthesis in polluted soils treated with coal fly ash

This study deals with the process of zeolite formation in an agricultural soil artificially polluted by high amounts of Cu (15 mg of Cu/g of soil dry weight) and treated with fused coal fly ash at 30 and 60 degrees C and how this process affects the mobility and availability of the metal. As a consequence of the treatment, the amount of dissolved Cu, and thus its mobility, was strongly reduced, and the percentage of the metal stabilized in the solid phase increased over time, reaching values of 30% at 30 degrees C and 40% at 60 degrees C. The physicochemical phenomena responsible for Cu stabilization in the solid phase have been evaluated by EDTA sequential extractions and synchrotron radiation based X-ray microanalytical techniques. These techniques were used for the visualization of the spatial distribution and the speciation of Cu in and/or on the neo-formed zeolite particles. In particular, micro XRF (X-ray fluorescence) tomography showed direct evidence that Cu can be entrapped as clusters inside the porous zeolitic structures while mu-XANES (X-ray absorption near edge structure) spectroscopy determinations revealed Cu to be present mainly as Cu(ll) hydroxide and Cu(ll) oxide. The reported results could be useful as a basic knowledge for planning new technologies for the on site physicochemical stabilization of heavy metals in heavily polluted soils.     

Speciation of hepatic Zn in trout exposed to elevated waterborne Zn using X-ray absorption spectroscopy

The long-term impacts of chronic metal exposure for aquatic biota are not well understood, partly due to a lack of understanding of metal speciation within tissues. The objective of this study was to determine hepatic Zn speciation of rainbow trout (Oncorhnychus mykiss) exposed to Zn-enriched water in relation to unexposed (control) fish,through direct analysis of freeze-dried liver samples using synchrotron X-ray absorption spectroscopy (XAS). Juvenile rainbow trout (n=30) were exposed to Zn in a two-step process, 200 microg L(-1) for 14 days, followed by 370 microg L(-1) for 23 days. Thirty other trout were grown in a control treatment (10 microg Zn L(-1)). At the end of the experiment, three liver samples per treatment were collected, freeze-dried, ground, and mixed homogeneously. Although Zn concentration was higher in the Zn-exposed livers than in the control livers (22.32 vs 13.73 mg kg(-1), respectively; p < 0.05), Zn speciation was similar for both groups. Extended X-ray absorption fine structure (EXAFS) spectroscopy indicated that Zn was coordinated to 4 sulfur atoms with an average Zn-S bond distance of 2.31 +/- 0.02 A. Sulfur K-XANES analysis confirmed that S was predominantly in reduced organic form analogous to cysteine. Our results are consistent with previous evidence for Zn(II) bonding to S in metallothionein proteins. These results suggest that the mechanisms for dealing with the extra load of bioaccumulated Zn in high exposure conditions were the same as in the control group.     

Modeling of the solid-solution partitioning of heavy metals and arsenic in embanked flood plain soils of the rivers Rhine and Meuse

The aim of this study is to predict the solid-solution partitioning of heavy metals in river flood plain soils. We compared mechanistic geochemical modeling with a statistical approach. To characterize the heavy metal contamination of embanked river flood plain soils in The Netherlands, we collected 194 soil samples at 133 sites distributed in the Dutch part of the Rhine and Meuse river systems. We measured the total amounts of As, Cd, Cr, Cu, Ni, Pb, and Zn in the soil samples and the metal fraction extractable by 2.5 mM CaCl2. We found a strong correlation between heavy metal contamination and organic matter content, which was almost identical for both river systems. Speciation calculations by a fully parametrized model showed the strengths and weaknesses of the mechanistic approach. Cu and Cd concentrations were predicted within one log scale, whereas modeling of Zn and Pb needs adjustment of some model parameters. The statistical fitting approach produced better results but is limited with regard to the understanding it provides. The log RMSE for this approach varied between 0.2 and 0.32 for the different metals. The careful modeling of speciation and adsorption processes is a useful tool for the investigation and understanding of metal availability in river flood plain soils.     

Spatial distributions of copper in microbial biofilms by scanning electrochemical microscopy

The spatial distribution of Cu was determined in Escherichia coli PHL628 biofilms using a scanning electrochemical microscope (SECM) consisting of a microelectrode in conjunction with a piezoelectric micropositioning system. Aqueous labile copper species were determined using voltametric stripping after reductive deposition of Cu for 4 min on the microelectrode at -0.7 V (vs Ag/AgCl). The position of the bulk solution-biofilm interface was determined from the change in current produced by 0.4 mM hydroxymethyl ferrocene that was added as a redox indicator. After a 2 h exposure to 0.2 mM copper, Cu was located in the upper region of the biofilm with a penetration depth less than 150 microm. A one-dimensional diffusive transport model adequately described the spatial distribution of copper in the biofilm, but the Cu retardation factor in the biofilm was more than 6-fold larger than that calculated from the isotherm for Cu binding to suspensions of E. coli PHL628 cells. There are several possible reasons for this difference, including an increase in the amount of extracellular polymer per cell within the biofilm and/or tortuosity that might hinder Cu transport into biofilms. The SECM technique in combination with model calculations provides direct evidence in support of the concept that formation of a biofilm may confer resistance to transient spikes in the bulk solution concentration of toxic metal species by retarding metal diffusion and reducing the metal exposure of cells within the biofilm.     

Metal compartmentation and speciation in a soil sentinel: the earthworm, Dendrodrilus rubidus

Earthworms are well-studied organisms in ecotoxicology because of their keystone ecological status and metal-accumulating capacity. However, the direct estimation of the bioreactive fractions of accumulated metal burdens remains technically elusive. In this study we exploited two physical techniques, electron probe X-ray microanalysis (EPXMA) and X-ray absorption spectroscopy (XAS), to improve understanding of the subcellular spatial distributions, ligand affinities, and coordination chemistries of Cd, Pb and Zn in a field population of the epigeic earthworm, Dendrodrilus rubidus. EPXMA and XAS analyses were performed on cryopreparations to maintain compositional fidelity; EPXMA data were analyzed by multivariate statistics. XAS provided whole-worm insights; EPXMA provided in situ, subcellular data from the major metal-sequestering tissue, the chloragog. Both techniques showed that Cd is coordinated with S; the measured Cd-S bond distance in XAS suggests a metallothionein-type ligand. The mean Cd:S molar ratio (EPXMA) of 0.36 is higher than the ratio of 0.29 estimated from published biochemical data. EPXMA and XAS data also found that Ca, Pb, and Zn are predominantly bound to one or more O-donating, probably phosphate-rich, ligands. X-ray distribution maps (EPXMA) of the hepatocyte-resembling chloragocytes revealed that the O-seeking (Ca, Pb, Zn) metals and S-seeking Cd bioaccumulate in distinct organelles. Extended X-ray absorption fine structure showed that the Pb complex is not biogenic pyromorphite, although X-ray absorption near edge structure did not eliminate the possibility. XAS provided no evidence of Pb spillage from the "sequestration compartment" within D. rubidus. However, the correspondence of Pb with Ca and P in EPXMA is not as strong as that of Zn. This is indicative either of spillover or of a second, hitherto unidentified, sequestered-Pb pool. By exploiting the complimentary techniques of EPXMA and XAS,we are closer to describing the mechanistic link between equilibrated body burdens and biomarker responses in earthworms.     

Geochemical weathering increases lead bioaccessibility in semi-arid mine tailings

Mine tailings can host elevated concentrations of toxic metal(loid)s that represent a significant hazard to surrounding communities and ecosystems. Eolian transport, capable of translocating small (micrometer-sized) particles, can be the dominant mechanism of toxic metal dispersion in arid or semiarid landscapes. Human exposure to metals can then occur via direct inhalation or ingestion of particulates. The fact that measured doses of total lead (Pb) in geomedia correlate poorly with blood Pb levels highlights a need to better resolve the precise distribution of molecularly speciated metal-bearing phases in the complex particle mixtures. Species distribution controls bioaccessibility, thereby directly impacting health risk. This study seeks to correlate Pb-containing particle size and mineral composition with lability and bioaccessibility in mine tailings subjected to weathering in a semiarid environment. We employed X-ray absorption spectroscopy (XAS) and X-ray fluorescence (XRF), coupled with sequential chemical extractions, to study Pb speciation in tailings from the semiarid Arizona Klondyke State Superfund Site. Representative samples ranging in pH from 2.6 to 5.4 were selected for in-depth study of Pb solid-phase speciation. The principle lead-bearing phase was plumbojarosite (PbFe(6)(SO(4))(4)(OH)(12)), but anglesite (PbSO(4)) and iron oxide-sorbed Pb were also observed. Anglesite, the most bioavailable mineral species of lead identified in this study, was enriched in surficial tailings samples, where Pb concentrations in the clay size fraction were 2-3 times higher by mass relative to bulk. A mobile and bioaccessible Pb phase accumulates in surficial tailings, with a corresponding increase in risk of human exposure to atmospheric particles.     

Zinc sorption by a bacterial biofilm

Microbial biofilms are present in soils, sediments, and natural waters. They contain bioorganic metal-complexing functional groups and are thought to play an important role in metal cycling in natural and contaminated environments. In this study, the metal-complexing functional groups present within a suspension of bacterial cell aggregates embedded in extracellular polymeric substances (EPS) were identified in Zn adsorption experiments conducted at pH 6.9 with the freshwater and soil bacterium Pseudomonas putida. The adsorption data were fit with the van Bemmelen-Freundlich model. The molecular speciation of Zn within the biofilm was examined with Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The Zn EXAFS data were analyzed by shell-by-shell fitting and linear least-squares fitting with reference spectra. Zinc sorption to the biofilm was attributed to predominantly Zn--phosphoryl (85 +/- 10 mol %) complexes, with a smaller contribution to sorption from carboxyl-type complexes (23 +/- 10 mol %). The results of this study spectroscopically confirm the importance of phosphoryl functional groups in Zn sorption by a bacterial biofilm at neutral pH.     

Effects of Ag(I), Au(III), and Cu(II) on the reductive dechlorination of carbon tetrachloride by green rust

Green rusts (GRs), mixed iron(II)/iron(III) hydroxide minerals found in many suboxic environments, have been shown to reduce a range of organic and inorganic contaminants, including several chlorinated hydrocarbons. Many studies have demonstrated the catalytic activity of transition metal species in the reduction of chlorinated hydrocarbons, suggesting the potential for enhanced reduction by GR in the presence of an appropriate transition metal catalyst. Reductive dechlorination of carbon tetrachloride (CT) was examined in aqueous suspensions of GR amended with Ag(I), Au(III), or Cu(II). The CT reduction rates were greatly increased for systems amended with Cu(II), Au(III), and Ag(I) (listed in order of increasing rates) relative to GR alone. Observed intermediates and products included chloroform, dichloromethane, chloromethane, methane, acetylene, ethene, ethane, carbon monoxide, tetrachloroethene, and various nonchlorinated C3 and C4 compounds. Product distributions for the reductive dechlorination of CT were highly dependent on the transition metal used. A reaction pathway scheme is proposed in which CT is reduced primarily to methane and other nonchlorinated end products, largely through a series of one-electron reductions forming radicals and carbenes/carbenoids. Recently, X-ray absorption fine structure analysis of aqueous GR suspensions amended with Ag(I), Au(III), or Cu(II) showed that the metals were reduced to their zerovalent forms. A possible mechanism for CT reduction is the formation of a galvanic couple involving the zerovalent metal and GR, with reduction of CT occurring on the surface of the metal and GR serving as the bulk electron source. The enhanced reduction of CT by GR suspensions amended with Ag(I), Au(III), or Cu(II) may prove useful in the development of improved materials for remediation of chlorinated organic contaminants.     

XANES-EXAFS analysis of se solid-phase reaction products formed upon contacting Se(IV) with FeS2 and FeS

The solid-phase Se speciation after short-term (3 weeks) contact of selenite [Se(IV)] oxyanions with pyrite (FeS2) and troilite (FeS) was investigated using X-ray absorption spectroscopy (XAS; X-ray absorption near-edge spectroscopy-extended X-ray absorption fine structure (XANES-EXAFS)). It was found that the nature of the sulfide mineral dictates the final speciation since respectively Se(0) and FeSe(x) were formed, meaning that the reaction mechanism is different and that these phases cannot be regarded as geochemically similar. The experimental results support the previously proposed sorption/ reduction mechanism for the reaction of selenite with pyrite. In the presence of troilite the reduction proceeds through the intermediate formation of Se(0) by reduction of selenite with dissolved sulfide. XAS data recorded for the FeS2 and FeS were compared with different Se reference phases, ranging in oxidation state from -II to +IV, used for validation of the XAS analysis methodology. This methodology can in principle be used to analyze Se phases formed in "in situ" geochemical conditions such as high-level radioactive waste disposal facilities.