Sequential Reductive Dechlorination Research Articles

Sequential Reductive Dechlorination of Triclosan by Sediment Microbiota Harboring Organohalide-Respiring Dehalococcoidia.

Aquatic ecosystems represent a prominent reservoir of xenobiotic compounds, including triclosan (TCS), a broad-spectrum biocide extensively used in pharmaceuticals and personal care products. As a biogeochemical hotspot, the potential of aquatic sediments for the degradation of TCS remains largely unexplored. Here, we demonstrated anaerobic biotransformation of TCS in a batch microcosm established with freshwater sediment. The initial 43.4 ± 2.2 μM TCS was completely dechlorinated to diclosan, followed by subsequent conversion to 5-chloro-2-phenoxyphenol, a monochlorinated TCS (MCS) congener. Analyses of community profile and population dynamics revealed substrate-specific, temporal-growth of Dehalococcoides and Dehalogenimonas, which are organohalide-respiring bacteria (OHRB) affiliated with class Dehalococcoidia. Dehalococcoides growth was linked to the formation of diclosan but not MCS, yielding 3.6 ± 0.4 × 107 cells per μmol chloride released. A significant increase in Dehalogenimonas cells, from 1.5 ± 0.4 × 104 to 1.5 ± 0.3 × 106 mL-1, only occurred during the reductive dechlorination of diclosan to MCS. Dehalococcoidia OHRB gradually disappeared following consecutive transfers, likely due to the removal of sediment materials with strong adsorption capacity that could alleviate TCS's antimicrobial toxicity. Consequently, a solid-free, functionally stable TCS-dechlorinating consortium was not obtained. Our results provide insights into the microbial determinants controlling the environmental fate of TCS.

Do CSIA data from aquifers inform on natural degradation of chlorinated ethenes in aquitards?

Back-diffusion of chlorinated ethenes (CEs) from low-permeability layers (LPLs) causes contaminant persistence long after the primary spill zones have disappeared. Naturally occurring degradation in LPLs lowers remediation time frames, but its assessment through sediment sampling is prohibitive in conventional remediation projects. Scenario simulations were performed with a reactive transport model (PHT3D in FloPy) accounting for isotope effects associated with degradation, sorption, and diffusion, to evaluate the potential of CSIA data from aquifers in assessing degradation in aquitards. The model simulated a trichloroethylene (TCE) DNAPL and its pollution plume within an aquifer-aquitard-aquifer system. Sequential reductive dechlorination to ethene and sorption were uniform in the aquitard and did not occur in the aquifer. After 10 years of loading the aquitard through diffusion from the plume, subsequent source removal triggered release of TCE by back-diffusion. In the upper aquifer, during the loading phase, δ13C-TCE was slightly enriched (up to 2‰) due to diffusion effects stimulated by degradation in the aquitard. In the upper aquifer, during the release phase, (i) source removal triggered a huge δ13C increase especially for higher CEs, (ii) moreover, downstream decreasing isotope ratios (caused by downgradient later onset of the release phase) with temporal increasing isotope ratios reflect aquitard degradation (as opposed to downstream increasing and temporally constant isotope ratios in reactive aquifers), and (iii) the carbon isotope mass balance (CIMB) enriched up to 4‰ as lower CEs (more depleted, less sorbing) have been transported deeper into the aquitard. Thus, enriched CIMB does not indicate oxidative transformation in this system. The CIMB enrichment enhanced with more sorption and lower aquitard thickness. Thin aquitards are quicker flushed from lower CEs leading to faster CIMB enrichment over time. CIMB enrichment is smaller or nearly absent when daughter products accumulate. Aquifer CSIA patterns indicative of aquitard degradation were similar in case of linear decreasing rate constants but contrasted with previous simulations assuming a thin bioactive zone. The Rayleigh equation systematically underestimates the extent of TCE degradation in aquifer samples especially during the loading phase and for conditions leading to long remediation time frames (low groundwater flow velocity, thicker aquitards, strong sorption in the aquitard). The Rayleigh equation provides a good and useful picture on aquitard degradation during the release phase throughout the sensitivity analysis. This modelling study provides a framework on how aquifer CSIA data can inform on the occurrence of aquitard degradation and its pitfalls.

Reductive lindane degradation with tea extracts in aqueous phase

Lindane is a persistent organochlorine pesticide (OCP) that is chemically stable, and has high lipid solubility. These characteristics allow it to bioaccumulate through the food chain, and therefore its presence in the environment is of great concern. An environment friendly chemical reductive process using tea in conjunction with Fe2+ was developed to degrade lindane in the aqueous phase. Tea containing rich polyphenols is a reducing and chelating agent. This bench-scale study investigated the potential of various tea extracts to reductively degrade lindane, and the results revealed that green tea extract (GTE) exhibited the greatest reducing power, and radical scavenging ability, compared with other tea extracts. The GTE/Fe2+ system produced polyphenol organometallic iron complexes, resulting in a highly reducing environment, and was able to completely degrade lindane within 3 h in a pH 10 (bi)carbonate buffer solution at 20 °C. Moreover, it was observed that increasing the concentration of GTE from 0.05 to 1.00 g (60 mL)−1 in a fixed 30 mM Fe2+ solution resulted in increases of initial lindane reaction rates (r0, lindane) from 1.32 to 7.80 μM h−1. However, as the Fe2+ dosage increased, with a fixed concentration of GTE, the r0, lindane decreased due to GTE deficiency and a reduced Fe2+/Fe3+ ratio in the iron complexes. Based on the lindane degradation intermediates detected by Gas Chromatography/Mass Spectrometry, the lindane degradation mechanism was postulated to be via alkaline hydrolysis and sequential reductive dechlorination.

Zerovalent iron in conjunction with surfactants to remediate sediments contaminated by polychlorinated biphenyls and nickel

Dredging and disposal is commonly used for cleanup of contaminated sediments, leaving the relocated sediments still in need of remediation. In this study, the feasibility of two approaches to using zerovalent iron (ZVI) in conjunction with surfactants to remediate sediments contaminated by polychlorinated biphenyls (PCBs) and Ni was investigated. Approach A is surfactant desorption followed by ZVI treatment and approach B is a simple mixture of ZVI and sediment in surfactant solution. Results of approach A show that 65.24% of PCBs and 2.12% of Ni were desorbed by 1% Envirosurf; however, the sequential ZVI-mediated reductive dechlorination (ZVI-RD) was ineffective due to micelle sequestration by high contents of surfactants while Ni could be almost completely removed. For approach B, less than 1% of coexisting Ni was released to aqueous solution, and 47.18%–76.31% PCBs could be dechlorinated by ZVI with the addition of 0.04% surfactants (Tween-80 and Envirosurf). Results of dechlorination kinetics and ZVI morphologies reveal that surfactants at the concentrations as low as 0.04% were able to enhance the contact of sediment-bound PCBs with ZVI, and also to alleviate ZVI passivation. The PCB mixtures in sediment were continuously desorbed and dechlorinated, yielding lower substituted homologues that are less toxic and less hydrophobic. Thus, a simple mixture of ZVI and contaminated sediments without dewatering appears to be a promising alternative to the remediation of PCBs-contaminated sediments.

Modeling 3D-CSIA data: Carbon, chlorine, and hydrogen isotope fractionation during reductive dechlorination of TCE to ethene

Reactive transport modeling of multi-element, compound-specific isotope analysis (CSIA) data has great potential to quantify sequential microbial reductive dechlorination (SRD) and alternative pathways such as oxidation, in support of remediation of chlorinated solvents in groundwater. As a key step towards this goal, a model was developed that simulates simultaneous carbon, chlorine, and hydrogen isotope fractionation during SRD of trichloroethene, via cis-1,2-dichloroethene (and trans-DCE as minor pathway), and vinyl chloride to ethene, following Monod kinetics. A simple correction term for individual isotope/isotopologue rates avoided multi-element isotopologue modeling. The model was successfully validated with data from a mixed culture Dehalococcoides microcosm. Simulation of Cl-CSIA required incorporation of secondary kinetic isotope effects (SKIEs). Assuming a limited degree of intramolecular heterogeneity of δ37Cl in TCE decreased the magnitudes of SKIEs required at the non-reacting Cl positions, without compromising the goodness of model fit, whereas a good fit of a model involving intramolecular CCl bond competition required an unlikely degree of intramolecular heterogeneity. Simulation of H-CSIA required SKIEs in H atoms originally present in the reacting compounds, especially for TCE, together with imprints of strongly depleted δ2H during protonation in the products. Scenario modeling illustrates the potential of H-CSIA for source apportionment.

Mineralization of 2-chlorophenol by sequential electrochemical reductive dechlorination and biological processes

In this work, a novel approach was applied to obtain the mineralization of 2-chlorophenol (2-CP) in an electrochemical-biological combined system where an electrocatalytic dehydrogenation process (reductive dechlorination) was coupled to a biological denitrification process. Reductive dechlorination of 2-CP was conducted in an ECCOCEL-type reactor on a Pd-Ni/Ti electrode at a potential of −0.40V vs Ag/AgCl(s)/KCl(sat), achieving 100 percent transformation of 2-CP into phenol. The electrochemically pretreated effluent was fed to a rotating cylinder denitrifying bioreactor where the totality of phenol was mineralized by denitrification, obtaining CO2 and N2 as the end products. The total time required for 2-CP mineralization in the combined electrochemical-biological process was 7.5h. This value is close to those previously reported for electrochemical and advanced oxidation processes but in this case, an efficient process was obtained without accumulation of by-products or generation of excessive energy costs due to the selective electrochemical pretreatment. This study showed that the use of electrochemical reductive pretreatment combined with biological processes could be a promising technology for the removal of recalcitrant molecules, such as chlorophenols, from wastewaters by more efficient, rapid, and environmentally friendly processes.

Review of reactive kinetic models describing reductive dechlorination of chlorinated ethenes in soil and groundwater

Reductive dechlorination is a major degradation pathway of chlorinated ethenes in anaerobic subsurface environments, and reactive kinetic models describing the degradation process are needed in fate and transport models of these contaminants. However, reductive dechlorination is a complex biological process, where many microbial populations including dechlorinating, fermentative, methanogenic, iron and sulfate reducing, interact. In this article the modeling approaches and the experimental data needed to calibrate them are reviewed, classified, and discussed. Model approaches considered include first order kinetics, Monod kinetics to describe sequential reductive dechlorination and bacterial growth, and metabolic models which simulate fermentation and redox processes interacting with reductive dechlorination processes. The review shows that the estimated kinetic parameters reported vary over a wide range, and that experimental microbial data are scarce. Very few studies have been performed evaluating the influence of sulfate and iron reduction, and contradictory conclusions on the interaction of redox processes with reductive dechlorination have been reported. The modeling approaches for metabolic reductive dechlorination employing different descriptions of the interaction between redox and dechlorination processes and competition for hydrogen are classified. The current concepts lead to different results, suggesting a need for further investigations on the interactions between the microbial communities performing dechlorination and redox processes, including the establishment of biomarkers quantifying dechlorination, and on geochemical characterization. Finally, the relevance of laboratory data and the development of practical modeling tools for field applications are discussed.

Development and Sensitivity Analysis of a Fully Kinetic Model of Sequential Reductive Dechlorination in Groundwater

A fully kinetic biogeochemical model of sequential reductive dechlorination (SERD) occurring in conjunction with lactate and propionate fermentation, iron reduction, sulfate reduction, and methanogenesis was developed. Production and consumption of molecular hydrogen (H(2)) by microorganisms have been modeled using modified Michaelis-Menten kinetics and has been implemented in the geochemical code PHREEQC. The model have been calibrated using a Shuffled Complex Evolution Metropolis algorithm to observations of chlorinated solvents, organic acids, and H(2) concentrations in laboratory batch experiments of complete trichloroethene (TCE) degradation in natural sediments. Global sensitivity analysis was performed using the Morris method and Sobol sensitivity indices to identify the most influential model parameters. Results show that the sulfate concentration and fermentation kinetics are the most important factors influencing SERD. The sensitivity analysis also suggests that it is not possible to simplify the model description if all system behaviors are to be well described.

Carbon isotope fractionation during dechlorination of 1,2,3,4-tetrachlorodibenzo- p-dioxin by a Dehalococcoides-containing culture

Carbon isotope fractionation was observed during dechlorination of 1,2,3,4-tetrachlorodibenzo- p-dioxin (1,2,3,4-TeCDD) by a mixed culture containing Dehalococcoides ethenogenes strain 195. Fractionation was examined when 1,2,3,4-TeCDD was added as the only chlorinated compound and when 1,2,3,4-TeCDD was added with a known growth substrate, tetrachloroethene (PCE). The 1,2,3,4-TeCDD was dechlorinated to 1,2,4-trichlorodibenzo- p-dioxin (1,2,4-TrCDD) which was enriched in 13C relative to 1,2,3,4-TeCDD with isotope separation factors, ε C, of 1.3 ± 0.2‰ and 1.7 ± 0.4‰ (average ± 95% confidence interval (CI)) in cultures with and without PCE, respectively. The 1,2,4-TrCDD was further dechlorinated to 1,3-dichlorodibenzo- p-dioxin (1,3-DCDD) which was depleted in 13C relative to 1,2,4-TrCDD with ε C of −2.4 ± 0.4‰ and −2.9 ± 0.8‰ (average ± 95% CI) in cultures with and without PCE, respectively. This demonstrates carbon isotope fractionation during sequential reductive dechlorination of PCDDs, where isotope fractionation during dechlorination of the intermediate was substantial and a 13C depleted lightly chlorinated PCDD congener was ultimately formed during dechlorination of more highly chlorinated PCDD congeners. Despite reproducible, statistically significant differences between isotope compositions of the parent, 1,2,3,4-TeCDD and daughter, 1,2,4-TrCDD and 1,3-DCDD congeners in triplicate bottles of both treatments, fractionation factors for 1,2,3,4-TeCDD could not be determined for all replicates by regression analysis of the plot of the Rayleigh equation. It is possible that dissolution of 1,2,3,4-TeCDD imposed a kinetic limitation on dechlorination, thus masking isotope fractionation during its dechlorination.

Theoretical investigation of the sequential reductive dechlorination pathways of chlorobenzenes and chloroanilines

The distribution of product isomers during the sequential reductive dechlorination of pentachloroaniline (PCA) and pentachlorobenzene (PeCB) was examined based on calculated thermodynamic, chromatographic, and electronic properties and then compared to the product distribution achieved by enrichment cultures. The dechlorination pathway analysis based on free energy considerations matched 78% and 67% of the experimental results for the sequential reductive dechlorination of chlorobenzenes (CBs) and chloroanilines (CAs), respectively. Chromatographic properties of CBs and CAs were able to explain some but not all of the reactions in the observed dechlorination pathways. Correlations between the observed dechlorination pattern and electronic properties of the parent compounds were able to explain most of the formation of the observed products. Experimentally observed sequential reductive dechlorination of CBs and CAs were similar to predicted dechlorination pathways based on the charge differential values calculated for the carbon-chloride bonds. Chlorine atoms were removed from the carbon atom that has the highest charge differential or the second highest charge differential. However, although thermodynamic, electronic as well as chromatographic properties of the CBs and CAs are certainly important factors, they may not be sufficient to completely describe the sequential microbial reductive dechlorination. Enzymatic specificity, as well as other factors (i.e., culture acclimation, environmental factors) should be considered for the interpretation of observed sequential reductive dehalogenation pathways of haloorganic compounds. This work provides the most comprehensive analysis to date of theoretical factors that control the sequential reductive chlorination of two homologous series of single-ring chloroaromatic species.

A process for the purification of organochlorine contaminated activated carbon: Sequential solvent purging and reductive dechlorination

A system for the purification of organochlorine contaminated activated carbon is described. The system involves a continuous flow of aqueous ethanol to purge organochlorines from activated carbon. The organochlorine laden solvent is simultaneously treated with zero valent zinc as the bulk electron source, water as the proton source and the electron shuttle cyanocobalamin as a catalyst for reductive dechlorination. The system was characterised by performing batch reactions and extractions before being applied in a continuous flow system. In particular the ratio of water to ethanol in the system needed to be optimised. Water is needed for the reductive dechlorination reaction whilst it is not conducive to the extraction process. An 80% ethanolic solution was found to give optimal reductive dechlorination rates without compromising extraction of organochlorines from activated carbon. Of three electron shuttles evaluated cyanocobalamin was discovered to be the most relevant to the system with respect to reductive dechlorination rates and its ability to avoid absorption to activated carbon.

Bacterial community analysis of shallow groundwater undergoing sequential anaerobic and aerobic chloroethene biotransformation

At Department of Energy Site 300, beneficial hydrocarbon cocontaminants and favorable subsurface conditions facilitate sequential reductive dechlorination of trichloroethene (TCE) and rapid oxidation of the resultant cis-dichloroethene (cis-DCE) upon periodic oxygen influx. We assessed the geochemistry and microbial community of groundwater from across the site. Removal of cis-DCE was shown to coincide with oxygen influx in hydrocarbon-containing groundwater near the source area. Principal component analysis of contaminants and inorganic compounds showed that monitoring wells could be differentiated based upon concentrations of TCE, cis-DCE, and nitrate. Structurally similar communities were detected in groundwater from wells containing cis-DCE, high TCE, and low nitrate levels. Bacteria identified by sequencing 16S rRNA genes belonged to seven phylogenetic groups, including Alpha-, Beta-, Gamma- and Deltaproteobacteria, Nitrospira, Firmicutes and Cytophaga-Flexibacter-Bacteroidetes (CFB). Whereas members of the Burkholderiales and CFB group were abundant in all wells (10(4)-10(9) 16S rRNA gene copies L(-1)), quantitative PCR showed that Alphaproteobacteria were elevated (>10(6) L(-1)) only in wells containing hydrocarbon cocontaminants. The study shows that bacterial community structure is related to groundwater geochemistry and that Alphaproteobacteria are enriched in locales where cis-DCE removal occurs.

Evaluation of Isotopic Enrichment Factors for the Biodegradation of Chlorinated Ethenes Using a Parameter Estimation Model: Toward an Improved Quantification of Biodegradation

A model was developed to predict the concentrations of chlorinated ethenes and ethene during sequential reductive dechlorination of tetrachloroethene (PCE) from stable carbon isotope values using Rayleigh model principles and specified isotopic enrichment factors for each step of dechlorination. The model was tested using three separate datasets of concentration and isotope values measured during three experiments involving the degradation of PCE to vinyl chloride (VC), trichloroethene (TCE) to ethene, and cis-1,2-dichloroethene (cDCE) to ethene. The model was then coupled to a parameter estimation method to estimate values for the isotopic enrichment factors of TCE, cDCE, and VC when they are intermediates in the dechlorination to ethene. The enrichment factors estimated for TCE and cDCE when they were intermediates in biodegradation experiments were close to or within the published range of enrichment factors determined from experiments where TCE or cDCE were the initial substrates. In contrast, the enrichment factors determined by parameter estimation for experiments in which VC was an intermediate in biodegradation experiments were consistently more negative (by approximately 10 per thousandth) than the most negative published enrichment factor determined from experiments where VC was the initial substrate. This finding suggests that the range of enrichment factors for VC dechlorination may not be as narrow as previously suggested (-21.5 per thousandth to -26.6 per thousandth) and that fractionation during VC dechlorination when VC is an intermediate compound may be significantly larger than when VC is the initial substrate. These findings have important implications both for the current practice of extrapolating laboratory-derived isotopic enrichment factors to quantify biodegradation of chlorinated ethenes in the field and for understanding the details of enzymatic reductive dechlorination.

Sequential Reductive Dechlorination of meta -Chlorinated Polychlorinated Biphenyl Congeners in Sediment Microcosms by Two Different Chloroflexi Phylotypes

Sequential Reductive Dechlorination of <i>meta</i> -Chlorinated Polychlorinated Biphenyl Congeners in Sediment Microcosms by Two Different <i>Chloroflexi</i> Phylotypes

Sequential reductive dechlorination of meta-chlorinated polychlorinated biphenyl congeners in sediment microcosms by two different Chloroflexi phylotypes.

Three species within a deeply branching cluster of the Chloroflexi are the only microorganisms currently known to anaerobically transform polychlorinated biphenyls (PCBs) by the mechanism of reductive dechlorination. A selective PCR primer set was designed that amplifies the 16S rRNA genes of a monophyletic group within the Chloroflexi including Dehalococcoides spp. and the o-17/DF-1 group. Assays for both qualitative and quantitative analyses by denaturing gradient gel electrophoresis and most probable number-PCR, respectively, were developed to assess sediment microcosm enrichments that reductively dechlorinated PCBs 101 (2,2',4,5,5'-CB) and 132 (2,2',3,3',4,6'-CB). PCB 101 was reductively dechlorinated at the para-flanked meta position to PCB 49 (2,2',4,5'-CB) by phylotype DEH10, which belongs to the Dehalococcoides group. This same species reductively dechlorinated the para- and ortho-flanked meta-chlorine of PCB 132 to PCB 91 (2,2',3',4,6'-CB). However, another phylotype designated SF1, which is more closely related to the o-17/DF-1 group, was responsible for the subsequent dechlorination of PCB 91 to PCB 51 (2,2',4,6'-CB). Using the selective primer set, an increase in 16S rRNA gene copies was observed only with actively dechlorinating cultures, indicating that PCB-dechlorinating activities by both phylotype DEH10 and SF1 were linked to growth. The results suggest that individual species within the Chloroflexi exhibit a limited range of congener specificities and that a relatively diverse community of species within a deeply branching group of Chloroflexi with complementary congener specificities is likely required for the reductive dechlorination of different PCBs congeners in the environment.

Anaerobic biodegradability of Tween surfactants used as a carbon source for the microbial reductive dechlorination of hexachlorobenzene

Three structurally-related, nonionic, polysorbate surfactants (Tween 60, 61, and 65) were used as the sole carbon source to sustain the microbial, sequential reductive dechlorination of hexachlorobenzene (HCB) in a mixed, methanogenic culture derived from a contaminated estuarine sediment. The surfactants were partially degraded and fermented to methane with no measurable accumulation of volatile fatty acids, indicating that methanogenesis was rapid relative to the rates of hydrolysis and acidogenesis. Addition of the methanogenesis inhibitor 2-bromoethanesulfonic acid resulted in acetate accumulation without impact on the sequential dechlorination of HCB. An anaerobic biodegradability assay was performed and the following data were obtained for the Tween 60, 61, and 65, respectively: 53, 62, and 62% COD destruction; 35, 57, and 48% COD to methane conversion; and 38, 38, and 45% COD to acetate conversion. These data suggest that the hydrophobic moiety (stearate) of the surfactants was preferentially degraded, most likely through beta-oxidation, to acetate and ultimately to methane and carbon dioxide. Between 38 and 47% of the initial surfactant COD remained after 46 d incubation, which most likely corresponds to the hydrophilic polyoxyethylene moiety. An anaerobic biodegradation pathway of the Tween surfactants is proposed.

Formulation of the CBC-Model for Modelling the Contaminants and Footprints in Natural Attenuation of BTEX

The Refuse Hideaway Landfill (23-acre) received municipal, commercial, and industrial waste between 1974 and 1988. It was designed as a "natural attenuation" landfill and no provision was made to collect and treat contaminated water. Natural biological degradation through sequential reductive dechlorination had been an important mechanism for natural attenuation at the site. We used the concentration of hydrogen to forecast whether reductive dechlorination would continue over time at particular locations in the plume. Based on published literature, reductive dechlorination and natural attenuation of PCE, TCE, and cis-DCE can be expected in the aquifer if the concentration of molecular hydrogen in monitoring wells are adequate (> 1 nanomolar). Reductive dechlorination can be expected to continue as the ground water moves down gradient. Natural attenuation through reductive dechlorination is not expected in flow paths that originate at down gradient monitoring wells with low concentrations of molecular hydrogen (< 1 nanomolar). In three monitoring wells at the margin of the landfill and in five monitoring wells down gradient of the landfill, ground water maintained a molecular hydrogen concentration, ranging from 1.30 to 9.17 nanomolar, that is adequate for reductive dechlorination. In three of the monitoring wells far down gradient of the landfill, the concentration of molecular hydrogen (0.33 to 0.83 nanomolar) was not adequate to support reductive dechlorination. In wells with adequate concentrations of hydrogen, the concentrations of chlorinated volatile organic compounds were attenuated over time, or concentrations of chlorinated volatile organics were below the detection limit. In wells with inadequate concentrations of hydrogen, the concentrations of chlorinated organic compounds attenuated at a slower rate over time. In wells with adequate hydrogen the first order rate of attenuation of PCE, TCE, cis-DCE and total chlorinated volatile organic compounds varies from 0.38 to 0.18 per year. In wells without adequate hydrogen the rate varies from 0.015 to 0.006 per year.

Reductive dechlorination of carbon tetrachloride and tetrachloroethylene by zerovalent silicon-iron reductants.

Reductive dechlorination of carbon tetrachloride (CT) and tetrachloroethylene (PCE) by zerovalent silicon (ZVS, Si0) and the combination of Si0 with metal iron (Fe0) was investigated as potential reductants for chlorinated hydrocarbons. The X-ray photoelectron spectroscopy (XPS) was used to identify the surface characteristics of Si0. CT and PCE can be completely degraded via sequential reductive dechlorination to form lesser chlorinated homologues by Si0. Productions of chloroform (CF) and trichloroethylene (TCE) accounted for 80% of CT and 65% of PCE dechlorination, respectively. The degradation of CT and PCE by Si0 at pH 8.3 followed pseudo-first-order kinetics, and the normalized surface rate constants (k(sa)) were 0.288 and 0.003 L m(-2) h(-1), respectively, which react more efficiently than zerovalent iron in CT and PCE dechlorination. A linear relationship was also established between pH and the k(sa) value. The XPS results showed that the hydrogenated silicon surface and silicon oxides on the silicon surface were removed during the dechlorination processes, thus providing a relatively clean silicon surface for dechlorination reactions. The combination of zerovalent silicon with iron influences both the dechlorination rate and the distribution of products. Sequential reductive dechlorination was still the main reaction for CT dechlorination by Si0/Fe0, while reductive dechlorination and beta-elimination were the dominant reaction pathways for PCE dechlorination with ethane and ethene as the major end products. Also, the combination of silicon and iron constitutes a buffer system to maintain the pH at a stable value. A 0.3 unit of pH changed upon increasing the amount of Fe by a factor of 35 was observed, depicting that Si0 serves as a pH buffer in Si0/Fe0 system during dechlorination processes.

Potential and Limitations of Microbial Reductive Dechlorination for Bioremediation Applications

Current knowledge and recent advances in the area of microbial reductive dechlorination of polychlorinated organic compounds are summarized. Factors which may limit the efficacy of the dechlorination process for the in situ bioremediation of contaminated soil and sediment systems are identified. Results of recent studies on the anaerobic biotransformation of soil-sorbed chlorinated ethenes and sediment-sorbed chlorinated benzenes are provided to illustrate how low contaminant bioavailability may control the rate and extent of dechlorination in subsurface systems, especially those with long-term contamination. Use of nonionic, polysorbate surfactants as the sole electron donors of a mixed, methanogenic culture supported the microbial sequential reductive dechlorination of either free or sediment-bound hexachlorobenzene (HCB) to primarily 1,3-dichlorobenzene, but did not enhance the bioavailability of sediment-bound HCB as compared to microcosms, which used glucose. Because current knowledge on the interactions of dechlorinating populations with other microbial populations in the presence of alternative terminal electron acceptors (e.g., nitrate, Fe3+ , Mn4+) is limited, such interactions and their effect on the dechlorination process in subsurface systems need to be further explored to improve our understanding of the reductive dechlorination process in complex environmental systems and lead to the development of more efficient in situ bioremediation technologies and strategies.

Carbon isotopes as a tool to evaluate the origin and fate of vinyl chloride: laboratory experiments and modeling of isotope evolution.

Accumulation of vinyl chloride (VC) is often a main concern at sites contaminated with chlorinated ethenes and ethanes due to its high toxicity. Since there can be several possible sources of VC and ethene at such sites, assessing the origin and fate of VC can be complicated. Aim of this study was to evaluate carbon isotope fractionation associated with various anaerobic processes that lead to the production of VC and ethene in view of using isotopes to evaluate the origin and fate of these compounds in groundwater. Microcosms were constructed using sediments and groundwater from a contaminated site and amended with potential precursors for VC and ethene production. In the microcosms with dichloroethene isomers, sequential reductive dechlorination was observed, and isotopic enrichmentfactors of -19.9 +/- 1.5 per thousand for cis-1,2-dichloroethene, -30.3 +/- 1.9 per thousand for trans-1,2-dichloroethene, and -7.3 +/- 0.4 per thousand for 1,1-dichloroethene were obtained. In microcosms with chlorinated ethanes, 1,2-dichloroethane (1,2-DCA) and 1,1,2-trichloroethane (1,1,2-TCA) were predominantly transformed by dichloroelimination to ethene and VC, respectively, and enrichmentfactors of -32.1 +/- 1.1 per thousand for 1,2OCA and -2.0 +/- 0.2 per thousand for 1,1,2-TCA were observed. Except for 1,1,2-TCA, a strong 13C enrichment in each of the potential precursor of VC was observed, which opens the possibility to trace the origin of VC based on the isotope ratio of potential precursors. Furthermore, it was possible to model the isotope evolution of VC present as substrate or intermediate product as a function of time. The study demonstrates that carbon isotope ratios can potentially be used for qualitative and possibly quantitative evaluation of the origin and fate of VC at sites with complex contaminant mixtures.