Dechlorination Of Trichloroethylene Research Articles

Biotic and Abiotic Dehalogenation of 1,1,2-Trichloro-1,2,2-trifluoroethane (CFC-113): Implications for Bacterial Detoxification of Chlorinated Ethenes.

Chlorofluorocarbons including 1,1,2-trichloro-1,2,2-trifluoroethane (CFC-113) often occur in groundwater plumes comingled with chlorinated solvents such as trichloroethene (TCE). We show that CFC-113 inhibits reductive dechlorination by Dehalococcoides mccartyi (Dhc) in a concentration-dependent manner, causing cis-1,2-dichloroethene (cis-DCE) stalls. Following a 17-day exposure of Dhc-containing consortium SDC-9 to 76 μM CFC-113, cis-DCE dechlorination activity did not recover after CFC-113 removal. River sediment microcosms demonstrated that CFC-113 was subject to microbial degradation under anoxic conditions, and chlorotrifluoroethene (CTFE) was observed as a transformation product. No degradation of CFC-113 was observed in killed controls and in incubations with reactive minerals including mackinawite, green rust, magnetite, and manganese dioxide. In vitro experiments with reduced corrinoid (i.e., vitamin B12) mediated reductive dechlorination of CFC-113 to CTFE and trifluoroethene (TFE) followed by reductive defluorination of TFE to cis-1,2-difluoroethene (cis-DFE) as an end product. This biomimetic degradation of CFC-113 to cis-DFE was also demonstrated in vivo using the corrinoid-producing homoacetogen Sporomusa ovata, suggesting the cometabolic microbial reductive dechlorination and reductive defluorination of CFC-113 to cis-DFE is feasible under anoxic in situ conditions. The CFC-113 degradation intermediates CTFE, TFE, and cis-DFE did not inhibit TCE dechlorination by Dhc, indicating that the initial reductive transformation step can overcome cis-DCE stalls.

Pilot-Scale Evaluation of a Permeable Reactive Barrier with Compost and Brown Coal to Treat Groundwater Contaminated with Trichloroethylene

This study evaluates, under field conditions, the efficiency of a permeable reactive barrier (PRB) with compost and brown coal to remove trichloroethylene (TCE) (109 µg/L) from contaminated groundwater. Three stainless steel boxes (1.2 × 0.5 × 0.5 m) with the brown coal-compost mixture at three different mixing ratios of 1:1, 1:3, and 1:5 (by volume) were installed to simulate the PRB. Groundwater from the TCE-contaminated aquifer was pumped into the system at a flow rate of 3.6 L/h. Residence times in the boxes were of: 25, 20, 10 h, respectively. Effluent samples were analyzed for TCE and its daughter products: dichloroethylene (DCE), vinyl chloride (VC) and ethane. During the 198-day experimental period TCE concentrations in groundwater decreased below ≤1.1 µg/L, i.e., much lower than groundwater and drinking water standards in Poland. After 16 days cis-1,2-DCE was monitored indicating possible reductive dechlorination of TCE. However, complete transformation of TCE into non-toxic byproducts was not evidenced during the time of experiments, indicating that reductive dechlorination slowed down or stopped at DCE, and that the designed residence times were not long enough to allow the complete dechlorination process.

Influence of different co-contaminants on trichloroethylene removal by sulfide-modified nanoscale zero-valent iron

Sulfide-modified nanoscale zero-valent iron (S-nZVI) has been widely employed to degrade various chlorinated organics due to its excellent properties. However, the influence of co-contaminants on its reactivity toward reductive degradation of chlorinated organics needs to be further investigated. In this study, S-nZVI was applied to remove trichloroethylene (TCE) in the presence of different co-contaminants (Cr6+, Cd2+, and NO3−) under acidic and alkaline conditions. The removal of TCE by S-nZVI in TCE/Cr6+ and TCE/Cd2+ mixed solution decreased significantly with the increasing concentration of Cr6+ and Cd2+. In contrast, the presence of NO3− enhanced the TCE removal by S-nZVI. The increasing initial pH from 5.61 to 9 resulted in a slight decrease of TCE removal in all reaction systems, while the increasing pH exerted negligible influence on the dechlorination of TCE. This indicated that the increasing pH only inhibited the adsorption of TCE. Simultaneously, the removal of co-contaminants was examined. S-nZVI had a poor sequestration of Cr6+, compared with that of Cd2+ and NO3−, which was due to the rapid surface passivation of S-nZVI by the products of Cr6+ reduction. SEM-EDS analysis verified that much more precipitates formed on the S-nZVI surface in the systems with Cr6+ and Cd2+ than NO3−. XPS analyses demonstrated the presence of surface layer of FeSx on S-nZVI, and the reactivity loss toward TCE degradation in TCE/Cr6+ and TCE/Cd2+ mixed solution was associated closely with the formation of Fe/Cr and Fe/Cd precipitates on the surface of S-nZVI.

Sustained Dechlorination of Vinyl Chloride to Ethene in Dehalococcoides-Enriched Cultures Grown without Addition of Exogenous Vitamins and at Low pH.

Trichloroethene (TCE) bioremediation has been demonstrated at field sites using microbial cultures harboring TCE-respiring Dehalococcoides whose growth is cobalamin (vitamin B12)-dependent. Bioaugmentation cultures grown ex situ with ample exogenous vitamins and at neutral pH may become vitamin-limited or inhibited by acidic pH once injected into field sites, resulting in incomplete TCE dechlorination and accumulation of vinyl chloride (VC). Here, we report growth of the Dehalococcoides-containing bioaugmentation culture KB-1 in a TCE-amended mineral medium devoid of vitamins and in a VC-amended mineral medium at low pH (6.0 and 5.5). In these cultures, Acetobacterium, which can synthesize 5,6-dimethylbenzimidazole (DMB), the lower ligand of cobalamin, and Sporomusa are dominant acetogens. At neutral pH, Acetobacterium supports complete TCE dechlorination by Dehalococcoides at millimolar levels with a substantial increase in cobalamin (∼20-fold). Sustained dechlorination of VC to ethene was achieved at pH as low as 5.5. Below pH 5.0, dechlorination was not stimulated by DMB supplementation but was restored by raising pH to neutral. Cell-extract assays revealed that vinyl chloride reductase activity declines significantly below pH 6.0 and is undetectable below pH 5.0. This study highlights the importance of cobamide-producing populations and pH in microbial dechlorinating communities for successful bioremediation at field sites.

Enhanced reductive dechlorination of trichloroethene with immobilized Clostridium butyricum in silica gel

Deteriorated environmental conditions during the bioremediation of trichloroethene (TCE)-polluted groundwater cause decreased treatment efficiencies. This study assessed the effect of applying immobilized Clostridium butyricum (a hydrogen-producing bacterium) in silica gel on enhancing the reductive dechlorination efficiency of TCE with the slow polycolloid-releasing substrate (SPRS) supplement in groundwater. The responses of microbial communities with the immobilized system (immobilized Clostridium butyricum and SPRS amendments) were also characterized by the metagenomics assay. A complete TCE removal in microcosms was obtained within 30 days with the application of this immobilized system via reductive dechlorination processes. An increase in the population of Dehalococcoides spp. was observed using the quantitative polymerase chain reaction (qPCR) analysis. Results of metagenomics assay reveal that the microbial communities in the immobilized system were distinct from those in systems with SPRS only. Bacterial communities associated with TCE biodegradation also increased in microcosms treated with the immobilized system. The immobilized system shows a great potential to promote the TCE dechlorination efficiency, and the metagenomics-based approach provides detailed insights into dechlorinating microbial community dynamics. The results would be helpful in designing an in situ immobilized system to enhance the bioremediation efficiency of TCE-contaminated groundwater.

Application of γ-PGA as the primary carbon source to bioremediate a TCE-polluted aquifer: A pilot-scale study

The effectiveness of using gamma poly-glutamic acid (γ-PGA) as the primary carbon and nitrogen sources to bioremediate trichloroethene (TCE)-contaminated groundwater was studied in this pilot-scale study. γ-PGA (40 L) solution was injected into the aquifer via the injection well (IW) for substrate supplement. Groundwater samples were collected from monitor wells and IW and analyzed for TCE and its byproducts, geochemical indicators, dechlorinating bacteria, and microbial diversity periodically. Injected γ-PGA resulted in an increase in total organic carbon (TOC) (up to 9820 mg/L in IW), and the TOC biodegradation caused the formation of anaerobic conditions. Increased ammonia concentration (because of amine release from γ-PGA) resulted in the neutral condition in groundwater, which benefited the growth of Dehalococcoides. The negative zeta potential and micro-scale diameter of γ-PGA allowed its globule to distribute evenly within soil pores. Up to 93% of TCE removal was observed (TCE dropped from 0.14 to 0.01 mg/L) after 59 days of γ-PGA injection, and TCE dechlorination byproducts were also biodegraded subsequently. Next generation sequence (NGS) analyses were applied to determine the dominant bacterial communities. γ-PGA supplement developed reductive dechlorinating conditions and caused variations in microbial diversity and dominant bacterial species. The dominant four groups of bacterial communities including dechlorinating bacteria, vinyl chloride degrading bacteria, hydrogen producing bacteria, and carbon biodegrading bacteria.

Reductive dechlorination of trichloroethene under different sulfate-reducing and electron donor conditions

The effect of sulfate presence on reductive dechlorination of chlorinated ethenes has been a matter of conflict among the limited reports found in literature. This paper aims to clarify the misconceptions regarding the performance of trichloroethene biotransformation under sulfate reducing conditions by evaluating the effect of different sulfate concentrations on reductive dechlorination and to assess the influence of electron donor dose on dechlorination rate. To this end, batch experiments containing different sulfate and butyrate concentrations were conducted using trichloroethene-dechlorinating and sulfate-reducing parent cultures. Results demonstrated that if sufficient time and electron donor is provided, complete dechlorination can be achieved, even at up to 400 mg/L initial sulfate concentration. However, the rate of dichloroethene and vinyl chloride degradation is reduced as sulfide concentration increases. Moreover, the excess electron donor dose induced a slightly slower dechlorination rate. The findings of this paper present an explanatory framework for the dechlorination of TCE under sulfate reducing conditions and can contribute to the state-of-art bioremediation of contaminated sites.

Coupling membrane and Fe–Pd bimetallic nanoparticles for trichloroethene removing from water

A novel composite membrane with membrane pores loading acrylic acid microgels coated by Fe–Pd bimetallic nanoparticles (NPs) was prepared for the dechlorination of trichloroethene (TCE) in water. This membrane was prepared by firstly immobilizing acrylic acid microgels in poly (vinylidene fluoride) (PVDF) membrane pores and then in-situ synthesis of Fe–Pd bimetallic nanoparticles (NPs). The Fe–Pd NPs coupled with the porous membranes enabled dechlorination to be conducted in a cross-flow model including a penetrative flow and a tangential flow. In such a model, a large number of dechlorination occurred in penetrative flow fluid while no dechlorination occurred in tangential flow fluid. Thus, products and reactants are always timely isolated in the cross-flow dechlorination process. The composite membrane prevents Fe–Pd NPs from contamination because its nanosize surface pores stop colloids and bovine serum albumin (BSA) from entering into the membrane interior. However, these small surfaces pores cannot slow the diffusion of reactants into membrane pores, and thus make the as-formed composite membrane also show a fast dechlorination rate in a batch reaction. All in all, TCE dechlorination by the composite membrane shows many advantages including the fast dechlorination rate, the convenient operation, the timely isolation of products from reactants, and the ignorable extra steps for separation of metal NPs.

Long-term mass flux assessment of a DNAPL source area treated using bioremediation

This study assessed the long-term effectiveness of bioremediation as a remedial strategy for a chlorinated, ethene dense, non-aqueous phase liquid (DNAPL) source area, consisting of a higher- and a lower-permeability zone at Alameda Point, California. The evaluation was performed over 3.7 years after cessation of active source area bioremediation using passive flux meters (PFMs), push-pull tracer tests, and soil cores. PFMs showed that total chlorinated ethene molar discharge emanating from the source area remained relatively unchanged pre-and post-bioremediation, but molar discharge compositions shifted from trichloroethene (TCE) and cis-1,2-dichloroethene (cis-DCE) to vinyl chloride (VC) and ethene dominated during post-remedial monitoring. First-order rate constants, derived from PFM data at the edge of the source area and describing the complete dechlorination of TCE at 3.7 years following active bioremediation, were approximately 1.05 yr−1, which was over three times lower than the rate 3.6 yr−1 determined using compound stable isotope analysis (CSIA). Soil cores and push-pull tracer test data showed that DNAPL volume estimates were relatively unchanged pre- and post-bioremediation due to the remaining presence of DNAPL in the lower-permeability zone. These data suggest biotransformation processes are continuing in the higher-permeability zone, whereas DNAPL in the lower-permeability zone continues to serve as a significant source of groundwater contamination. The results suggest that it will take many years under current conditions to attain the United States Environmental Protection Agency (EPA) Maximum Contaminant Levels (MCLs) cleanup objectives.

Arsenic Release and Attenuation Processes in a Groundwater Aquifer During Anaerobic Remediation of TCE with Biostimulation

AbstractArsenic in groundwater in excess of the drinking water limit is usually from natural sources. The release of As, however, can be amplified by anthropogenic inputs of carbon, including those associated with the remediation of chlorinated solvents such as trichloroethylene (TCE). Large laboratory columns (15.2 cm diameter, 183 cm long) packed with aquifer solids from a TCE contaminated site near Hill Air Force Base (Utah) were fed with groundwater containing TCE and were biostimulated, bioaugmented, and monitored for TCE dechlorination over 7.5 years. This is a basin‐fill aquifer with As bearing geologic features. The objective of this study was to evaluate the biogeochemical changes that affect As solubilization that occurred after 7.5 years of feeding the columns with either whey or two formulations of Newman Zone® emulsified oil, and a no carbon addition control. The columns were analyzed in 10.16 cm sections for pore water and sediment quality parameters, parameters descriptive of redox conditions, and As geochemistry. The whey treatment resulted in 52.9% (±1.36%) (average ± standard deviation) of the total As in the solids leaching from the columns. The oil treatments promoted loss of 20.9% (±6.40%) of the total As. Arsenic solubility was associated with strongly reducing conditions developed with whey addition, leading to dissolution of crystalline Fe oxides and release of As. Arsenic was attenuated within the oil treated columns with As associated with carbonates in the lower layers. A consequence of adding whey, resulting in the desired full dechlorination of TCE in this aquifer, is the mobilization of As in groundwater.

High-energy ball milling enhancing the reactivity of microscale zero-valent aluminum toward the activation of persulfate and the degradation of trichloroethylene

Microscale zero-valent aluminum (mZVAl), an excellent electron donor, presents great potential in the field of water treatment. However, surface inherent oxide film impedes its development and application. High-energy ball milling is a promising approach to enhance the reactivity of mZVAl. In this study, taking nontoxic and biodegradable stearic acid (SA) as the process control agent (PCA), ball milled mZVAl (termed as mZVAlbm) was prepared and employed to activate persulfate (PS) for the degradation of trichloroethylene (TCE). Firstly, the role of ball milling on the surface morphology, structure and reactivity of mZVAl was revealed by SEM, BET, XRD, XPS characterizations and H2 evolution experiments. The results demonstrated that high-energy ball milling, as a severe plastic deformation method, can partially break the native oxide film on mZVAl surface and expose fresh surfaces, thereby appreciably increasing its reactivity. Secondly, the underlying mechanisms of mZVAlbm excelling pristine mZVAl in activating PS were evaluated through TCE degradation process. In mZVAlbm/PS system, complete degradation and dechlorination of TCE were achieved and corresponding rate (kobs,TCE) increased by 96 times, while traces of TCE were removed in pristine mZVAl/PS system due to the hindrance of surface oxide film. Additionally, sulfate radical (SO4−) and hydroxyl radical (OH) were identified as the predominant active species. Finally, mZVAlbm surface corrosion mechanism in the presence of PS was also deeply clarified. After reaction, the corrosion products, namely Al-(hydr)oxide, precipitated on mZVAlbm surface, decreasing its reactivity, but ball milling again can easily regenerate mZVAlbm. In a word, high-energy ball milling as a pretreatment method can remarkably enhance the reactivity of mZVAl toward PS activation, achieving the rapid and efficient removal of contaminants from water.

Transport and release of electron donors and alkalinity during reductive dechlorination by combined emulsified vegetable oil and colloidal Mg(OH)2: Laboratory sand column and microcosm tests

Emulsified vegetable oil combined with colloidal Mg(OH)2 (EVO-CM) can slowly release electron donors and OH– into groundwater and is therefore regarded as a promising amendment for enhanced in situ treatment of chlorinated solvents, such as tetrachloroethene (PCE) and trichloroethene (TCE). However, its migration ability in different porous media and the simultaneous release of electron donor and pH buffer during enhanced reductive dechlorination (ERD) have never been evaluated in detail. In this study, EVO-CM with uniform drop size and desirable stability was prepared. Laboratory-scale column tests were conducted to investigate the transport and spatial distribution of the EVO-CM in different porous media. Batch microcosm experiments were carried out to study the dechlorination efficiency under different EVO:Mg(OH)2 ratios. Experimental results indicate that prepared EVO-CM emulsions can be transported effectively through different porous media with grain size ranging from 0.1–1.0 mm. The emulsified vegetable oil (EVO) and colloidal Mg(OH)2 showed synchronous movement through the porous media column systems, providing both electron donor and alkalinity at the same location. The retention degree of EVO-CM is greater in the finer grained media and decreases with increasing distance from the inlet. The injection of EVO-CM lead to a significant mobilization of TCE in the column. The reductive dechlorination of TCE in the microcosms was remarkably enhanced in the presence of EVO-CM. The coaddition of sufficient colloidal Mg(OH)2 effectively limits the deleterious pH decline caused by acid release. The microcosm achieves an optimum dechlorination efficiency when the EVO:Mg(OH)2 ratio is 1:1.

Application of a Pd-TiO2 nanotube/Ti electrode prepared by atomic layer deposition to reductive dechlorination of trichloroethylene

Trichloroethylene (TCE) is a toxic carcinogen. Electrocatalytic hydrodechlorination is a very effective and safe method for degrading TCE and does not produce any secondary pollution. In this communication, a new cathode, fabricated by loading catalytic palladium (Pd) particles by atomic layer deposition (ALD) onto titanium dioxide nanotubes (TiO2NTs), is used in the dechlorination of TCE. With 60 mA current at pH = 5, the efficiency of TCE (40 mg/L) reduction was as high as 95.0%. Pd-TiO2NT/Ti cathodes thus demonstrate very good performance in TCE dechlorination. The cathodes prepared by ALD have greater efficiency and longer lifetimes than cathodes prepared by electrodeposition.

Structural dynamics and transcriptomic analysis of Dehalococcoides mccartyi within a TCE-Dechlorinating community in a completely mixed flow reactor

A trichloroethene (TCE)-dechlorinating community (CANAS) maintained in a completely mixed flow reactor was established from a semi-batch enrichment culture (ANAS) and was monitored for 400 days at a low solids retention time (SRT) under electron acceptor limitation. Around 85% of TCE supplied to CANAS (0.13 mmol d−1) was converted to ethene at a rate of 0.1 mmol d−1, with detection of low production rates of vinyl chloride (6.8 × 10−3 mmol d−1) and cis-dichloroethene (2.3 × 10−3 mmol d−1). Two distinct Dehalococcoides mccartyi strains (ANAS1 and ANAS2) were stably maintained at 6.2 ± 2.8 × 108 cells mL−1 and 5.8 ± 1.2 × 108 cells mL−1, respectively. Electron balance analysis showed 107% electron recovery, in which 6.1% were involved in dechlorination. 16 S rRNA amplicon sequencing revealed a structural regime shift between ANAS and CANAS while maintaining robust TCE dechlorination due to similar relative abundances of D. mccartyi and functional redundancy among each functional guild supporting D. mccartyi activity. D. mccartyi transcriptomic analysis identified the genes encoding for ribosomal RNA and the reductive dehalogenases tceA and vcrA as the most expressed genes in CANAS, while hup and vhu were the most critical hydrogenases utilized by D. mccartyi in the community.

Mechanistic Dichotomy in Bacterial Trichloroethene Dechlorination Revealed by Carbon and Chlorine Isotope Effects.

Tetrachloroethene (PCE) and trichloroethene (TCE) are significant groundwater contaminants. Microbial reductive dehalogenation at contaminated sites can produce nontoxic ethene but often stops at toxic cis-1,2-dichloroethene ( cis-DCE) or vinyl chloride (VC). The magnitude of carbon relative to chlorine isotope effects (as expressed by ΛC/Cl, the slope of δ13C versus δ37Cl regressions) was recently recognized to reveal different reduction mechanisms with vitamin B12 as a model reactant for reductive dehalogenase activity. Large ΛC/Cl values for cis-DCE reflected cob(I)alamin addition followed by protonation, whereas smaller ΛC/Cl values for PCE evidenced cob(I)alamin addition followed by Cl- elimination. This study addressed dehalogenation in actual microorganisms and observed identical large ΛC/Cl values for cis-DCE (ΛC/Cl = 10.0 to 17.8) that contrasted with identical smaller ΛC/Cl for TCE and PCE (ΛC/Cl = 2.3 to 3.8). For TCE, the trend of small ΛC/Cl could even be reversed when mixed cultures were precultivated on VC or DCEs and subsequently confronted with TCE (ΛC/Cl = 9.0 to 18.2). This observation provides explicit evidence that substrate adaptation must have selected for reductive dehalogenases with different mechanistic motifs. The patterns of ΛC/Cl are consistent with practically all studies published to date, while the difference in reaction mechanisms offers a potential answer to the long-standing question of why bioremediation frequently stalls at cis-DCE.

Enhanced reductive dechlorination of trichloroethene in an acidic DNAPL impacted aquifer

A field pilot test was conducted using an emulsified vegetable oil (EVO) and colloidal magnesium hydroxide [Mg(OH)2] formulation to enhance reductive dechlorination of dense non-aqueous phase liquid (DNAPL) trichloroethene (TCE) in an acidic (pH < 4), heterogeneous aquifer. The field test consisted of i) a single well injection test to evaluate Mg(OH)2 distribution and ii) installation of two EVO-Mg(OH)2 permeable reactive barriers (PRBs; PRB-1 & PRB-2) at varying distances downgradient of the DNAPL source area. Distribution of Mg(OH)2 was observed up to 2.3 m away from the injection point within a permeable coarse sand layer; however, Mg(OH)2 transport in the overlying clayey-silty sand was minimal. Downgradient of the PRBs, colloidal Mg(OH)2 increased the pH of the coarse sand to levels appropriate for biological reductive dechlorination (pH >∼5); however, some settling of Mg(OH)2 in the injection wells generated persistent high pH (∼9–10) within the PRBs. A redesigned suspension of colloidal Mg(OH)2 was tested and proved to be more effective at raising aquifer pH without an excessive rise in pH within the PRBs. At PRB-1 (located closest to the DNAPL source area), limited TCE biodegradation was observed due to the influx of high TCE concentrations (up to 400 mg/L) and inhibition of dechlorinating bacteria. At PRB-2 (located 25 m downgradient of the DNAPL source area), TCE concentrations were much lower (13–26 mg/L) and production of cis-1,2-dichloroethene (cDCE) and some vinyl chloride (VC) was observed. Subsequent bioaugmentation with a commercial dechlorinating culture at PRB-2 improved conversion of cDCE to VC and ethene at downgradient monitoring wells over the duration of the study. These results emphasize the importance of PRB location (relative to the DNAPL source), base selection for pH adjustment, source strength, and local heterogeneities for the design and long-term performance of ERD in acidic DNAPL-impacted aquifers.

Estimating bioaugmentation efficacy of TCE dechlorination using long-term field well-to-well tests in a highly recharged and TCE-contaminated aquifer

This study demonstrates a combined field method accurately assessing the extent of trichloroethylene (TCE) reductive dechlorination activity and the mass fraction of its by-products. A combined method of injecting a known concentration of 1,1,2-trichloro-2-fluoroethene (TCFE) as a TCE bio-surrogate and a data processing technique of forced mass balance (FMB), considering the sorption effect on the mass fraction of chloroethene was evaluated by performing soil column and field bioaugmentation tests. In the soil column test, the FMB resulted in the mass fraction of 6% TCE, 48.3% cis-1,2-dichloroethene, 18.5% vinyl chloride and 27.2% ethylene. In the field bioaugmentation test, TCFE showed equivalent dechlorination pathways of TCE. The mass fractions estimated by FMB were very similar to those observed in the soil column bioaugmentation tests: 4.5% TCFE, 57.1% 1,2-dichloro-1-fluoroethene, 12% 1-chloro-1-fluoroethene and 26.4% fluoroethene (FE). The FMB method gave ∼50% higher mass fraction for more chlorinated ethenes (i.e., TCFE) and ∼10% lower mass fraction of less chlorinated ethenes (i.e., FE) than those considering only the aqueous concentrations of chlorofluoroethenes. A combined method of TCFE and FMB that could accurately estimate both the extent of dechlorination activities and mass distribution of TCE reductive dechlorination would be highly useful.

Strategy for the Rapid Dechlorination of Polychlorinated Biphenyls (PCBs) by Dehalococcoides mccartyi Strains.

Anaerobic bacteria play critical roles in the environmental bioremediation of polychlorinated biphenyls (PCBs). However, in situ applications of PCB dechlorinating anaerobes have been largely impeded by difficulties in growing PCB dechlorinators to a high cell abundance in short time periods. Here, we report the accelerated onset of PCB dechlorination by pre-cultivating Dehalococcoides mccartyi strains on chloroethenes as alternative electron acceptors. The extensive dechlorination of Aroclor 1260 was achieved within 1 week by D. mccartyi CG4 pregrown on trichloroethene (TCE) or tetrachloroethene (PCE). Compared to control cultures fed solely with Aroclor 1260, the PCB dechlorination rate was up to 30 times greater in cultures pre-cultivated with chloroethenes. However, when CG4 was simultaneously exposed to multiple potential substrates (PCE, TCE, and PCBs), PCB dechlorination was not observed until PCE was completely depleted. The expression of the bifunctional PCE and PCBs reductive dehalogenase (RDase) gene pcbA4 was inhibited by the presence of both substrates. Furthermore, in the presence of >0.3 mM TCE (produced as an intermediate from PCE dechlorination), the PCB dechlorination rate was an order of magnitude lower than in cultures amended with Aroclor 1260 after the complete depletion of TCE. This reduced PCB dechlorination rate corresponded with a sharp decrease in pcbA4 transcripts in the presence of both TCE and PCBs. The utilization of chloroethenes and PCBs as substrates by CG4 was found to be largely sequential rather than concurrent, suggesting that PCE and TCE are preferred substrates for the RDase responsible for PCE, TCE, and PCB dechlorination.

Nitrogen-Doped Carbon Materials as Metal-Free Catalyst for the Dechlorination of Trichloroethylene by Sulfide.

A new method for trichloroethylene (TCE) dechlorination is proposed using sulfide (HS- and S2-) as reductant under the mediation of nitrogen-doped carbon materials (NCMs). About 99% of the TCE was converted to acetylene after 200 h using this method. Dechlorination of TCE in the NCMs-sulfide system (NCSS) followed pseudo-first-order kinetics. Pyridinic N (N6) on surface of the NCMs appeared to play a critical role in NCSS as shown by the good linear relationship between the surface content of N6 and kobs. Nucleophilic substitution was suggested as the first step in TCE dechlorination, and the nucleophilic reagent was identified as a sulfur intermediate with C-S-S-H as the functional group. The generation of C-S-S-H could be ascribed to the interaction between positively charged carbon atoms in N6 and negative charged sulfide. This work is the first to demonstrate that sulfide combined with NCMs can produce active substances that are effective in TCE dechlorination and the findings will assist in the development of strategies that use natural sulfide as reductant for detoxicating organic chloroethene contaminants.

Diffusion-Coupled Degradation of Chlorinated Ethenes in Sandstone: An Intact Core Microcosm Study.

Matrix diffusion must be considered when assessing natural attenuation and remediation of chlorinated ethenes in fractured porous bedrock aquifers. In this study, intact sandstone rock and groundwater from a trichloroethene (TCE)-contaminated site were used in microcosms (maintained for approximately 600 days) to simulate a single fracture-matrix system with a chamber at the top of the core allowing advection to represent fracture flow. Diffusion-coupled degradation with and without biostimulation were evaluated and compared to crushed-rock, batch microcosms. In the diffusion-transport microcosms, lactate stimulated reductive dechlorination of TCE to cis-1,2-dichloroethene (cDCE) and sulfate reduction. Reduction of TCE to cDCE led to a higher rate of chlorinated ethene removal from the cores, likely due to higher concentration gradients, along with lower sorption and a higher diffusion coefficient for cDCE relative to TCE. Reduction of cDCE to vinyl chloride or ethene did not occur as in crushed rock microcosms, inferring an absence of Dehalococcoides in the intact cores. Abiotic transformation was evident in the core microcosms based on the appearance of acetylene and enrichment in δ13C-TCE and δ13C-cDCE. Core microcosms permit a more realistic representation of the behavior of chlorinated ethenes in water-saturated fractured porous rock by incorporating the combined influence of fracture flow and matrix diffusion on transport and transformation.