Dechlorination Of Trichloroethylene Research Articles

Influence of microbial inoculation site on trichloroethylene degradation in electrokinetic-enhanced bioremediation of low-permeability soils

The integration of electrokinetic and bioremediation (EK-BIO) represents an innovative approach for addressing trichloroethylene (TCE) contamination in low-permeability soil. However, there remains a knowledge gap in the impact of the inoculation approach on TCE dechlorination and the microbial response with the presence of co-existing substances. In this study, four 1-dimensional columns were constructed with different inoculation treatments. Monitoring the operation conditions revealed that a stabilization period (∼40 days) was required to reduce voltage fluctuation. The group with inoculation into the soil middle (Group B) exhibited the highest TCE dechlorination efficiency, achieving a TCE removal rate of 84%, which was 1.1–3.2 fold higher compared to the others. Among degraded products in Group B, 39% was ethylene. The physicochemical properties of the post-soil at different regions illustrated that dechlorination coincided with the Fe(III) and SO42− reduction, meaning that the EK-BIO system promoted the formation of a reducing environment. Microbial community analysis demonstrated that Dehalococcoides was only detected in the treatment of injection at soil middle or near the cathode, with abundance enriched by 2.1%–7.2%. The principal components analysis indicated that the inoculation approach significantly affected the evolution of functional bacteria. Quantitative polymerase chain reaction (qPCR) analysis demonstrated that Group B exhibited at least 2.8 and 4.2-fold higher copies of functional genes (tceA, vcrA) than those of other groups. In conclusion, this study contributes to the development of effective strategies for enhancing TCE biodechlorination in the EK-BIO system, which is particularly beneficial for the remediation of low-permeability soils.

Bioremediation of trichloroethylene-contaminated groundwater using green carbon-releasing substrate with pH control capability

In this research, a sustainable substrate, termed green and long-lasting substrate (GLS), featuring a blend of emulsified substrate (ES) and modified rice husk ash (m-RHA) was devised. The primary objective was to facilitate the bioremediation of groundwater contaminated with trichloroethylene (TCE) using innovative GLS for slow carbon release and pH control. The GLS was concocted by homogenizing a mixture of soybean oil, surfactants (Simple Green™ and soya lecithin), and m-RHA, ensuring a gradual release of carbon sources. The hydrothermal synthesis was applied for the production of m-RHA production. The analyses demonstrate that m-RHA were uniform sphere-shape granules with diameters in micro-scale ranges. Results from the microcosm study show that approximately 83% of TCE could be removed (initial TCE concentration = 7.6 mg/L) with GLS supplement after 60 days of operation. Compared to other substrates without RHA addition, higher TCE removal efficiency was obtained, and higher Dehalococcoides sp. (DHC) population and hydA gene (hydrogen-producing gene) copy number were also detected in microcosms with GLS addition. Higher hydrogen concentrations enhanced the DHC growth, which corresponded to the increased DHC populations. The addition of the GLS could provide alkalinity at the initial stage to neutralize the acidified groundwater caused by the produced organic acids after substrate biodegradation, which was advantageous to DHC growth and TCE dechlorination. The addition of m-RHA reached an increased TCE removal efficiency, which was due to the fact that the m-RHA had the zeolite-like structure with a higher surface area and lower granular diameter, and thus, it resulted in a more effective initial adsorption effect. Therefore, a significant amount of TCE could be adsorbed onto the surface of m-RHA, which caused a rapid TCE removal through adsorption. The carbon substrates released from m-RHA could then enhance the subsequent dechlorination. The developed GLS is an environmentally-friendly and green substrate.

Enhancing trichloroethylene dechlorination capacity by utilizing granular ceramic material derived from Fe0-carbon-kaolin nanocomposite as substrate filter

In this study, we present a novel approach to fabricate a granular ceramic material utilizing a composite of nano zero-valent iron (nZVI), carbon, and kaolin. The optimal mass ratio of the prepared material was kaolin, nZVI, activated carbon, and appropriate additives = 40%:40%:10%:10%. The resulting composite demonstrated microelectrolysis effects, enhancing its reactivity for pollutant removal. Activated carbon within the composite significantly increased the interlayer spacing of kaolin, and improved material performance. Furthermore, the addition of activated carbon proved effective in preventing the agglomeration of nZVI, and ensuring a stable and efficient pollutant removal process. The results of 40-day column experiments showed that nano iron-carbon-kaolin micro-electrolysis particles (NIMP) consistently demonstrated stable trichloroethane (TCE) removal with an average removal rate of 88.15 ± 3.24%. Batch experiments confirmed that the synthesized material can achieve complete dechlorination of TCE, which was consistent with density functional theory calculations. The developed material exhibited a robust soil structure and high reactivity for pollutant reduction, making it a promising substrate filler for efficiently degrading refractory organic pollutants. It holds great potential for applications in areas such as water treatment and soil remediation.

Mechanochemical nitridation of micron zero-valent iron for enhanced dechlorination of trichloroethylene: Mechanistic insights into nitrogen sources and ball milling conditions

The performance optimization of zero-valent iron (ZVI) based materials for reductive dechlorination remains challenging. After extensive research on sulfidation modification, the doping of heteroatom nitrogen (N) into ZVI for reductive dechlorination of chlorinated hydrocarbons (CHCs) becomes a new promising trend. In this study, surface modification of microscale ZVI (mZVI) was carried out by a facile ball milling method, and Fe–N(C) coated mZVI (abbreviated as N(C)-mZVIbm) synthesized from different N sources of dimethylimidazole, urea and melamine were characterized. The effects of nitrogen-to-iron ratios (N/Fe), ball milling time and speed on the reductive dechlorination of trichloroethylene (TCE) were further investigated. A series of characterization and mechanistic analysis showed that the high reactivity of N(C)-mZVIbm with melamine as nitrogen source (abbreviated as N(C)-mZVIbm(M)) was attributed to the properties and thickness of its particle passivation layer, and faster electron transfer from the reduced iron species to the surface layer. In addition, N(C)-mZVIbm(M) exhibited great performance for dechlorination at a wide pH range of 3 to 11, due to alleviated passivation of the Fe0 core under alkaline conditions by Fe–N(C). This study presents new ideas and evidences for the environmentally friendly synthesis of N-modified ZVI materials and their practical application in groundwater remediation.

Unravelling the bifunctional role of biochar in promoting nZVI/Ni towards complete dechlorination of trichloroethylene: Not only a carbonouces support

Trichloroethylene (TCE) is a widely recognized persistent groundwater pollutant, and the majority of dechlorination processes for its reduction yield hazardous by-products with low levels of chlorination. Herein, highly reactive catalysts (BCs@FN) were developed using bifunctional biochar (BC) loaded with nZVI/Ni (FN) nanoparticles for the complete dechlorination of trichloroethylene (TCE). BC plays bifunctional roles in promoting TCE dechlorination by facilitating FN dispersion and enhancing the conductivity of bimetallic FN, thereby promoting the production of dominant reactive atomic hydrogen. Moreover, both the reaction rate constant (kobs) of dechlorination and the amount of essential reduction species of atomic hydrogen exhibited a positive correlation with the conductivities of BCs@FN. Specifically, BC900@FN achieved complete dechlorination of 20 mg/L TCE within 3 h at a kobs value of 1.4 h−1. Analysis regarding carbon balance and Cl existence form disclosed all C-Cl bonds could be broken and 100 % TCE was transformed into ethylene (4.1 %) and ethane (95.9 %). Furthermore, the proposed BC900@FN catalyst demonstrates remarkable TCE degradation efficiencies ranging from 71.2 % to 91.8 % in tap water, municipal water and groundwater samples. These findings highlight the potential application of bifunctional BCs in synthesizing bimetallic catalysts and their practical use for remediating chlorinated contaminants.

Molybdenum disulfide modified microscale zero-valent iron (MoS-mZVI) for enhanced trichloroethylene dechlorination

The potential of microscale zero-valent iron (ZVI) for dechlorinating chlorinated hydrocarbons holds promise in pollution remediation. However, Fe0 passivation presents a challenge, leading to slow dechlorination and the buildup of hazardous incomplete dechlorinated intermediates. To address these concerns, we introduce molybdenum disulfide (MoS2)-modified microscale ZVI (MoS-mZVI). Our study demonstrates the significant enhancement of trichloroethylene (TCE) dechlorination by MoS-mZVI compared to standard mZVI. Remarkably, the optimal Fe/MoS2 molar ratio of 20 in MoS-mZVI achieves a remarkable 26.8-fold acceleration in TCE removal compared to mZVI. Acetylene emerges as the primary intermediate in TCE dechlorination by MoS-mZVI, peaking at 38%, accompanied by major end products including ethene (45%) and ethane (31%). Importantly, the MoS-mZVI-20 system avoids toxic byproducts, diverging from the dichloroethylene accumulation observed in the mZVI system. Notably, electron utilization efficiency shows significant improvement, with MoS-mZVI reaching 65.6% compared to mZVI's 7.2%. Furthermore, MoS2′s selective OH- adsorption triggers pH reduction, mitigating mZVI passivation and optimizing its reactivity. This innovative approach highlights the effectiveness of MoS2-modified microscale ZVI as an environmentally friendly solution for enhancing TCE dechlorination processes.

Relationship Between Sulfidated Nano Zero Valent Iron and a Reductive Dechlorinating Microbial Culture - Synergistic or Antagonistic? 

Sulfidated nano zerovalent iron (S-nZVI) has garnered significant attention from researchers due to its potential for effective in-situ remediation applications. Compared to bare nZVI, sulfidation process enhances its reactivity towards chlorinated volatile organic compounds (cVOCs) and improves its longevity (Nunez Garcia et al. 2021). Stabilizing the particles with a polymer, like carboxymethyl cellulose (CMC), can further improve the performance of S-nZVI by imparting higher stability, less toxicity towards microbial cells, and a potential biostimulatory effect, making CMC-S-nZVI a promising in-situ remediation technology (Nunez Garcia et al. 2021). Recently, CMC-S-nZVI has also been applied for field-scale remediation (Nunez Garcia et al. 2020;Brumovský et al. 2021). The contaminated sites usually have multiple pollutants and not all can be degraded by CMC-S-nZVI, thus, leaving some recalcitrant cVOCs untreated (Zhang et al. 2021). Biodegradation of cVOCs by dechlorinating microbial cultures may generate highly toxic intermediates like vinyl chloride (Kocur et al. 2016). However, coupling the two treatments may be able to compensate for each other’s drawbacks, resulting in higher efficiency, longer effectiveness, non-accumulation of intermediates, and degradation of a wider range of target contaminants. However, interacting effects of CMC-S-nZVI on dechlorinating microbial cultures have not been studied yet. This research investigates the potential of combining CMC-S-nZVI and a reductive dechlorinating microbial culture (KB-1) to degrade trichloroethylene (TCE) and 1,2-dichloroethane (1,2-DCA). CMC-S-nZVI was synthesized by a two-step method: (1) CMC-nZVI was first synthesized by reducing ferrous sulfate-CMC solution with dropwise addition of sodium borohydride solution with continuous mixing and (2) then sodium dithionite solution was added as a sulfidation agent to the freshly-synthesized CMC-nZVI (Nunez Garcia et al. 2020). Effects of different sulfur-iron ratios (S/Fe), iron, and CMC concentrations on TCE degradation were studied to obtain an effective CMC-S-nZVI formulation. Results showed a successful TCE removal by the CMC-S-nZVI but 1,2-DCA was not degraded. TCE degradation by CMC-S-nZVI fitted the first-order kinetic model, with the highest degradation rate constant (0.35 h-1) achieved at S/Fe = 0.1 with iron and CMC concentrations of 1 gL-1 and 0.4 wt%, respectively. This CMC-S-nZVI formulation was further tested to examine its interaction with KB-1 in terms of cVOCs dechlorination and microbial population responses. A four-day aged CMC-S-nZVI was also tested to study the effect of aging. Degradation pathways for TCE and 1,2-DCA were proposed, based on the formation of degradation products. For the coupled treatment, an increase in microbial abundance was observed by quantifying DNA concentrations. This demonstrated a synergistic relationship between CMC-S-nZVI and KB-1. Unlike the CMC-S-nZVI only treatment, microcosms containing both CMC-S-nZVI and KB-1 were found to successfully degrade the 1,2-DCA. The coupled treatment degraded TCE and 1,2-DCA at faster rates and generated lesser amounts of vinyl chloride than the KB-1 only treatment, confirming the biostimulatory effect of CMC-S-nZVI. In the KB-1 only treatment with CMC as the sole carbon and energy source, TCE and 1,2-DCA were successfully dechlorinated. Transmission electron microscopy illustrated that CMC-S-nZVI particles were attached to the microbes but did not penetrate the bacterial cells. In summary, synergistic abiotic-biotic dechlorination of TCE and 1,2-DCA was achieved by the combined treatment of CMC-S-nZVI and KB-1, suggesting that multi-contaminant sites can benefit from this approach. Additionally, the four-day aged CMC-S-nZVI performed similar to the freshly-synthesized one, demonstrating that the field-scale remediation can have a more feasible time scale for the preparation and application of these amendments.

A multiple Kirkendall strategy for converting nanosized zero-valent iron to highly active Fenton-like catalyst for organics degradation

Nanosized zero-valent iron (nZVI) is a promising persulfate (PS) activator, however, its structurally dense oxide shell seriously inhibited electrons transfer for O-O bond cleavage of PS. Herein, we introduced sulfidation and phosphorus-doped biochar for breaking the pristine oxide shell with formation of FeS and FePO4-containing mixed shell. In this case, the faster diffusion rate of iron atoms compared to shell components triggered multiple Kirkendall effects, causing inward fluxion of vacancies with further coalescing into radial nanocracks. Exemplified by trichloroethylene (TCE) removal, such a unique "lemon-slice-like" nanocrack structure favored fast outward transfer of electrons and ferrous ions across the mixed shell to PS activation for high-efficient generation and utilization of reactive species, as evidenced by effective dechlorination (90.6%) and mineralization (85.4%) of TCE. [Formula: see text] contributed most to TCE decomposition, moreover, the SnZVI@PBC gradually became electron-deficient and thus extracted electrons from TCE with achieving nonradical-based degradation. Compared to nZVI/PS process, the SnZVI@PBC/PS system could significantly reduce catalyst dosage (87.5%) and PS amount (68.8%) to achieve nearly complete TCE degradation, and was anti-interference, stable, and pH-universal. This study advanced mechanistic understandings of multiple Kirkendall effects-triggered nanocrack formation on nZVI with corresponding rational design of Fenton-like catalysts for organics degradation.

Syntrophic Interactions Ameliorate Arsenic Inhibition of Solvent-Dechlorinating Dehalococcoides mccartyi.

Interactions and nutrient exchanges among members of microbial communities are important for understanding functional relationships in environmental microbiology. We can begin to elucidate the nature of these complex systems by taking a bottom-up approach utilizing simplified, but representative, community members. Here, we assess the effects of a toxic stress event, the addition of arsenite (As(III)), on a syntrophic co-culture containing lactate-fermenting Desulfovibrio vulgaris Hildenborough and solvent-dechlorinating Dehalococcoides mccartyi strain 195. Arsenic and trichloroethene (TCE) are two highly prevalent groundwater contaminants in the United States, and the presence of bioavailable arsenic is of particular concern at remediation sites in which reductive dechlorination has been employed. While we previously showed that low concentrations of arsenite (As(III)) inhibit the keystone TCE-reducing microorganism, D. mccartyi, this study reports the utilization of physiological analysis, transcriptomics, and metabolomics to assess the effects of arsenic on the metabolisms, gene expression, and nutrient exchanges in the described co-culture. It was found that the presence of D. vulgaris ameliorated arsenic stress on D. mccartyi, improving TCE dechlorination under arsenic-contaminated conditions. Nutrient and amino acid export by D. vulgaris may be a stress-ameliorating exchange in this syntrophic co-culture under arsenic stress, based on upregulation of transporters and increased extracellular nutrients like sarcosine and ornithine. These results broaden our knowledge of microbial community interactions and will support the further development and implementation of robust bioremediation strategies at multi-contaminant sites.

Reductive dechlorination of trichloroethene by sulfided microscale zero-valent iron in fresh and saline groundwater: Reactivity, pathways, and selectivity

S/mZVI is a promising material for groundwater remediation due to its excellent properties. However, the reactivity and electron selectivity toward target contaminant are critical. Thus, this study investigated the effect of complex groundwater chemistries (Milli-Q water, fresh groundwater and saline groundwater) on the reactivity of S/mZVI toward trichloroethylene (TCE), dechlorination pathway, hydrogen evolution kinetic, electron efficiency and aging behaviors. Results showed that sulfidation appreciably increased the reactivity and electron selectivity. The major degradation product of TCE dechlorination by S/mZVI was acetylene, which was consistent with TCE dechlorination by β-elimination. Moreover, reductive β-elimination was still the dominant dechlorination pathway for the application of S/mZVI in three groundwater conditions. However, the rates and the quantities of major products from TCE degradation varied significantly. S/mZVI in saline groundwater can maintain the reactivity towardTCE due to the protection of Fe0 by Fe3O4 deposited on the surface. Thus, the higher TCE removal efficiency and less hydrogen accumulation resulted in the greatest electron efficiency (4.3–79.2%). Overall, S/mZVI was more effective for the application in saline groundwater. This study proved insight into the comprehensive evaluation and implications for the application of S/mZVI based technologies in saline contaminated groundwater.

Soil organic matter and nutrient availability affect the applicability of low-carbon energy source in Dehalococcoides-augmented soil

Dehalococcoides is a functional microorganism that completely dechlorinates trichloroethene (TCE). Augmentation with pure Dehalococcoides is important for reducing environmental disturbances that accompany bioaugmentation. However, the applicability of Dehalococcoides-bioaugmentation to contaminated soils is unclear. In this study, seven low-carbon energy sources (methanol, formate, acetate, ethanol, lactate, citrate, and benzoate) were used as electron donors for Dehalococcides to evaluate its applicability in remediating TCE-contaminated soils. Soil microcosms supplemented with ethanol, formate, or lactate showed relatively high dechlorination activity within 111–180 days. The functional gene profiles predicted by PICRUSt2 from 16 S rRNA gene sequences were similar in the proportions of dehydrogenases, which initiate electron donor oxidation, in all soils and did not seem to reflect Dehalococcoides-bioaugmentation applicability. Soils with higher organic matter content (>3.2%; dry weight base) and protein concentration (>1.6 µg/mL) supported complete dechlorination. These results suggest that organic matter and nutrient availability mainly affect successful TCE dechlorination in Dehalococcoides-augmented soils. The study offers significant experimental support for comprehending the suitability of low-carbon energy sources in successful bioaugmentation, aiming to mitigate environmental disturbances associated with the process.

The effects of arsenic on dechlorination of trichloroethene by consortium DH: Microbial response and resistance

Inorganic arsenic and organochlorines are frequently co-occurring contaminants in anoxic groundwater environments, and the bioremediation of their composite pollution has long been a rigorous predicament. Currently, the dechlorination behaviors and stress responses of microbial dechlorination consortia to arsenic are not yet fully understood. This study assessed the reductive dechlorination performance of a Dehalococcoides-bearing microcosm DH under gradient concentrations of arsenate [As(V)] or arsenite [As(III)] and investigated the response patterns of different functional microorganisms. Our results demonstrated that although the dechlorination rates declined with increasing arsenic concentrations in both As(III/V) scenarios, the inhibitory impact was more pronounced in As(III)-amended groups compared to As(V)-amended groups. Moreover, the vinyl chloride (VC)-to-ethene step was more susceptible to arsenic exposure compared to the trichloroethene (TCE)-to-dichloroethane (DCE) step, while high levels of arsenic exposure [e.g. As(III) > 75 μM] can induce significant accumulation of VC. Functional gene variations and microbial community analyses revealed that As(III/V) affected reductive dechlorination by directly inhibiting organohalide-respiring bacteria (OHRB) and indirectly inhibiting synergistic populations such as acetogens. Metagenomic results indicated that arsenic metabolic and efflux mechanisms were identical among different Dhc strains, and variations in arsenic uptake pathways were possibly responsible for their differential responses to arsenic exposures. By comparison, fermentative bacteria showed high potential for arsenic resistance due to their inherent advantages in arsenic detoxification and efflux mechanisms. Collectively, our findings expanded the understanding of the response patterns of different functional populations to arsenic stress in the dechlorinating consortium and provided insights into modifying bioremediation strategies at co-contaminated sites for furtherance.

Cations facilitate sulfidation of zero-valent iron by elemental sulfur: Mechanism and dechlorination application

The solid-solid reaction of microscale zero-valent iron (mZVI) with elemental sulfur (S0) in water can form sulfidated mZVI (S-mZVI) with high reactivity and selectivity. However, the inherent passivation layer of mZVI hinders the sulfidation. In this study, we demonstrate that ionic solutions of Me-chloride (Me: Mg2+, Ca2+, K+, Na+ and Fe2+) can accelerate the sulfidation of mZVI by S0. The S0 with S/Fe molar ratio of 0.1 was fully reacted with mZVI in all solutions to form unevenly distributed FeS species on S-mZVIs as confirmed by SEM-EDX and XANES characterization. The cations depassivated the mZVI surface by driving the proton release from the surface site (FeOH) and resulting in localized acidification. The probe reaction test (tetrachloride dechlorination) and open circuit potential (EOCP) measurement demonstrated that Mg2+ was most efficient in depassivating the mZVI and therefore promoting sulfidation. The decrease of surface proton for hydrogenolysis on the S-mZVI synthesized in MgCl2 solution also inhibited the formation of cis-1,2-dichloroethylene by 14–79% compared to other S-mZVIs during trichloroethylene dechlorination. In addition, the synthesized S-mZVIs exhibited the highest reduction capacity reported so far. These findings provide a theoretical basis for the facile on-site sulfidation of mZVI by S0 with cation-rich natural waters for sustainable remediation of contaminated sites.

Degradation of trichloroethylene vapors by micrometric zero-valent Fe[sbnd]Cu and Fe[sbnd]Ni bimetals under partially saturated conditions

The degradation of trichloroethylene (TCE) vapors by zero-valent Iron-Copper (Fe–Cu) and Iron-Nickel (Fe–Ni) bimetals with 1%, 5% and 20% weight content (%wt) of Cu or Ni was tested in anaerobic batch vapor systems carried out at ambient room temperature (20 ± 2 °C) under partially saturated conditions. The concentrations of TCE and byproducts were determined at discrete reaction time intervals (4 h-7 days) by analyzing the headspace vapors. In all the experiments, up to 99.9% degradation of TCE in the gas phase was achieved after 2–4 days with zero-order TCE degradation kinetic constants in the range of 134–332 g mair−3d−1. Fe–Ni showed a higher reactivity towards TCE vapors compared to Fe–Cu, with up to 99.9% TCE dechlorination after 2 days of reaction, i.e., significantly higher than zero-valent iron alone that in previous studies was found to achieve comparable TCE degradation after minimum 2 weeks of reaction. The only detectable byproducts of the reactions were C3–C6 hydrocarbons. Neither vinyl chloride or dichloroethylene peaks were detected in the tested conditions above their method quantification limits that were in the order of 0.01 g mair−3. In view of using the tested bimetals in horizontal permeable reactive barriers (HPRBs) placed in the unsaturated zone to treat chlorinated solvent vapors emitted from contaminated groundwater, the experimental results obtained were integrated into a simple analytical model to simulate the reactive transport of vapors through the barrier. It was found that an HPRB of 20 cm could be potentially effective to ensure TCE vapors reduction.

Comparison of trichloroethylene dechlorination in seawater by sulfidated nanoscale zero-valent iron particles prepared by two methods

Sulfidated nanoscale zero-valent iron (S-nZVI) particles have demonstrated great potential in the remediation of trichloroethylene (TCE) due to their high reactivity and electron selectivity. However, very few studies have been carried out to investigate their application in salinity water or seawater. In this work, two kinds of S-nZVI particles were prepared through different methods including the chemical reduction method (CH-S-nZVI) and the bioprecipitation method (BP-S-nZVI), and then their performances in TCE remediation in seawater environment were thoroughly compared. The results suggested that the TCE removal by CH-S-nZVI particles in seawater is reduced compared to that in fresh water. However, the difference is negligible for BP-S-nZVI particles. It indicates that the seawater has a relatively strong inhibitory effect on the TCE degradation by CH-S-nZVI, but the inhibition for BP-S-nZVI is very weak. Furthermore, this work verified that sodium chloride and organic matters have obvious inhibitory effects on the TCE dichlorination, while coexisting ions such as NO3-, SO42- and Mg2+ are helpful to the degradation of TCE. The research proved that the performance of BP-S-nZVI particles in seawater is superior to CH-S-nZVI particles, providing a suitable candidate for the treatment of polluted aquifers in coastal and near-shore areas.

Dual effects of PFOA or PFOS on reductive dechlorination of trichloroethylene (TCE)

PFASs and chlorinated solvents are the common co-contaminants in soil and groundwater at firefighter training areas (FTAs). Although PFASs mixtures could have adverse impacts on bioremediation of trichloroethylene (TCE) by inhibiting Dehalococcoides (Dhc), little is known about the effect and contribution of PFOA or PFOS on dechlorination of TCE by non-Dhc organohalide-respiring bacteria (OHRB). To study this, PFOA and PFOS were amended to the growth medium of a non-Dhc OHRB-containing enrichment culture to determine the impact on dechlorination. This study demonstrated that high levels of PFOA or PFOS (100 mg L–1) inhibited TCE dechlorination in four non-Dhc OHRB-containing community including Geobacter, Desulfuromonas, Desulfitobacterium, and Dehalobacter, but low levels of PFOA or PFOS (≤10 mg L–1) enhanced TCE dechlorination. Four non-Dhc OHRB were less inhibited by PFOA than that by PFOS, and high level of PFOS killed Desulfitobacterium and Dehalobacter and decreased the biodiversity of bacterial community. Although most fermenters were killed by the presence of 100 mg L–1 PFOS, two important co-cultures (Desulfovibrio and Sedimentibacter) of OHRB were enriched, indicating that the syntrophic relationships between OHRB and co-cultures still remained, and PFOA or PFOS inhibited TCE dechlorination by directly repressing non-Dhc OHRB. Our results highlight that the bioattenuation of chloroethene contamination could be confounded by non-Dhc OHRB in high levels of PFOS contaminated subsurface environments at FTAs.

Decoupling Fe0 Application and Bioaugmentation in Space and Time Enables Microbial Reductive Dechlorination of Trichloroethene to Ethene: Evidence from Soil Columns.

Fe0 is a powerful chemical reductant with applications for remediation of chlorinated solvents, including tetrachloroethene and trichloroethene. Its utilization efficiency at contaminated sites is limited because most of the electrons from Fe0 are channeled to the reduction of water to H2 rather than to the reduction of the contaminants. Coupling Fe0 with H2-utilizing organohalide-respiring bacteria (i.e., Dehalococcoides mccartyi) could enhance trichloroethene conversion to ethene while maximizing Fe0 utilization efficiency. Columns packed with aquifer materials have been used to assess the efficacy of a treatment combining in space and time Fe0 and aD. mccartyi-containing culture (bioaugmentation). To date, most column studies documented only partial conversion of the solvents to chlorinated byproducts, calling into question the feasibility of Fe0 to promote complete microbial reductive dechlorination. In this study, we decoupled the application of Fe0 in space and time from the addition of organic substrates andD. mccartyi-containing cultures. We used a column containing soil and Fe0 (at 15 g L-1 in porewater) and fed it with groundwater as a proxy for an upstream Fe0 injection zone dominated by abiotic reactions and biostimulated/bioaugmented soil columns (Bio-columns) as proxies for downstream microbiological zones. Results showed that Bio-columns receiving reduced groundwater from the Fe0-column supported microbial reductive dechlorination, yielding up to 98% trichloroethene conversion to ethene. The microbial community in the Bio-columns established with Fe0-reduced groundwater also sustained trichloroethene reduction to ethene (up to 100%) when challenged with aerobic groundwater. This study supports a conceptual model where decoupling the application of Fe0 and biostimulation/bioaugmentation in space and/or time could augment microbial trichloroethene reductive dechlorination, particularly under oxic conditions.

Electrochemical Dechlorination of Trichloroethylene by Manganese Phthalocyanine: Performance and Mechanisms

Trichloroethylene (TCE) is one of the most abundant persistent organic pollutant in subsurface environment. TCE can be reduced electrochemically, but the extremely negative applied potential limits the application of this technology. Manganese phthalocyanine (MnPc) catalyst was used for the electrochemical reductive dechlorination of TCE. The results show that MnPc can be reduced by electrons attachment at −-0.21 V, −-1.22 V and −-1.77 V, respectively. With the decrease of applied potential from −-0.3 V to −-1.8 V, the transformation from TCE to dichloroethylene (DCE) efficiency increased from 19.9% to 41.8% after 5 hours of reaction. Although the electron transfer ability was enhanced with applied potential decreasing, the intensive HER caused the electron selectivity decreased when MnPc attached more electrons. MnPc catalyze the electrochemical reduction of TCE, which has potential application on the remediation of TCE-contaminated groundwater.

[4Fe–4S]-Mediated Proton-Coupled Electron Transfer Enables the Efficient Degradation of Chloroalkenes by Reductive Dehalogenases

Reductive dehalogenases (RDases) are key enzymes involved in the degradation of organohalide compounds. Despite extensive experimental and computational studies, the catalytic mechanism of RDases remains unclear. We show here that the proximal [4Fe–4S]1+ cluster of the reductive dehalogenase PceA can mediate a proton-coupled electron transfer (PCET) process to quench the substrate radical. Such a [4Fe–4S]1+-mediated PCET process is enhanced by both exchange and super-exchange interactions. The participation of [4Fe–4S]1+ in mediating a PCET process in RDases is unexpected, although well known in reducing Co(II). In addition, in RDases, the Arg305 residue acts as an efficient proton donor for the PCET reactions. The deprotonated Tyr246 serves to maintain the favorable conformation of Arg305 during catalysis and sustains its proton donation ability, which is requested during the PCET reaction. Such a novel mechanism enables the efficient detoxification of chloroalkene pollutants by the reductive dehalogenase PceA, which also rationalizes the selective dechlorination of trichloroethene to form cis-1,2-dichloroethylene. These results highlight the critical role of the proximal [4Fe–4S].

Phosphidation of microscale zero-valent iron (P-mZVI) for enhanced dechlorination of trichloroethylene

Microscale zero-valent iron (mZVI) has a great application potential in the remediation of chlorinated organic compounds contaminated groundwater. However, the dechlorination of trichloroethylene (TCE) with mZVI often leads to the formation of toxic incomplete dechlorination products. Herein, ferrophosphorus, a byproduct of phosphorus production, has been used to modify mZVI through ball milling to get P-doped mZVI (P-mZVI). The XRD, SEM and XPS results indicated the uniform distribution of FePx species in mZVI. The phosphidation significantly promoted the dechlorination of TCE by mZVI with the degradation rate increased from 0.0073 h−1 to 0.0146 h−1. Tafel tests revealed the P-mZVI was more susceptible to water corrosion than mZVI due to primary cell effect. The cyclic voltammetry results indicated the formation of atomic hydrogen (H*) in the P-mZVI system, and H* could diffuse into the lattice of Fe0 to form H*abs. Owing to the strong reducing capability of H*, the dechlorination pathway of TCE was mainly hydrogenolysis, favoring the formation of C2H4 while almost no C2H2. The XPS results indicated that phosphorus existed as phosphate after dechlorination. Considering that phosphate is an essential nutrient for microorganism growth, the dechlorination products of P-mZVI may boost the metabolism of ingenious microbiota.