Trichloroethylene Degradation Research Articles

Biodegradation of Trichloroethylene by Trametes versicolor and its Physiological Response to Contaminant Stress.

Trichloroethylene (TCE) poses a potentially toxic threat to humans and the environment and widely exists in contaminated sites. White rot fungi effectively degrade refractory pollutants, while a few research studies use white rot fungi to degrade TCE. In this study, we investigated TCE biodegradation by white rot fungi and the potential influencing factors in the environment and attempted to research the effect of TCE on the physiological characteristics of white rot fungi. White rot fungi (Trametes versicolor, Pseudotrametes gibbosa, Pycnoporus sanguines and Pleurotus ostreatus) were added to the liquid medium for shock culture. The results revealed that T. versicolor exhibited the most pronounced efficacy in removing TCE, with a degradation rate of 81.10% within a 7 d period. TCE induces and is degraded by cytochrome P450 enzymes. High pH and Cr(VI) adversely affected the effectiveness of the biodegradation of TCE, but the salinity range of 0-1% had less effect on biodegradation. Overall, the effectiveness of degradation of TCE by T. versicolor has been demonstrated, and it provides a reference for the application prospects of white rot fungi in TCE-contaminated soils.

TCE degradation of modified graphite felt cathode in a flow-through electro-Fenton system and its H2O2 production ability in a real contaminated field

A modified graphite felt (MGF) was prepared with carbon black (CB) and polytetrafluoron (PTFE) for cathodic electrochemical H2O2 production, which was used in a flow-through cathodic electro-Fenton reactor to degrade chlorinated hydrocarbons. Cathode electrode was floating on aqueous surface and 369.1 mg/L H2O2 could be produced after 1 h 150 mA power applied without O2 aeration. The main O2 source for H2O2 production was confirmed from air with this floating position. In a 2.0 L flow-through cathodic electro-Fenton system, 95.97 % degradation efficiency for 5.0 mg/L trichloroethylene (TCE) was achieved in 90 min with 13.4 mL/min influent rate. Reducing the reactor volume to 0.14 L, 5.0 mg/L TCE could be degraded completely in 10 min with continuous 4 L influent. The mixed chlorinated hydrocarbons (TCE, cis-1,1-dichloroethylene, 1,2-dichloroethane, and dichloromethane) were also rapidly degraded in 20 min. The flow-through cathodic electro-Fenton reactor presented excellent degradation ability for chlorinated hydrocarbons with a smaller volume. In the simulated sand tank system, after continuously operated 27 days, H2O2 concentration in electrode well was still remained at 80 mg/L. In the contaminated field in Tianjin, China, H2O2 yield of MGF in groundwater could keep at about 60 mg/L after 220 min operating.

Insight into the role of reactive species on catalyst surface underlying peroxymonosulfate activation by P–Fe2MnO4 loaded on bentonite for trichloroethylene degradation

In this study, bentonite supporting phosphorus-doped Fe2MnO4 (BPF) was synthesized and applied for PMS activation to degrade TCE. Morphology and structure characterization results indicated the successfully synthesized of BPF, and the BPF/PMS system not only featured high TCE removal (97.4%) but also high reaction rate constant (kobs = 0.0554 min−1) and PMS utilization (70.4%, kobs = 0.0228 min−1). According to the results of various experiments, massive oxygen vacancies on P–Fe2MnO4 alter its charge balance and facilitate the electron transfer process named adjacent transfer (direct electron capture by adsorbed PMS from adjacent TCE). Mn(III) is the main adsorption site for PMS, and the hydroxyl groups on the catalyst (Fe sites of P–Fe2MnO4, Si and Al sites of bentonite) can also offer binding sites for PMS. The hydrogen-bonded PMS on Fe(III) and Mn(III) sites will subsequently accept the discharged electrons to generate free radicals and high-valent metal species. Meanwhile, electron loss of HSO5− that chemically bonded to hydroxyl groups on bentonite will generate SO5•−, which will further produce 1O2 through self-bonding. the active species on the catalyst surface contribute 65% of TCE degradation in the heterogeneous catalytic oxidation system.

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.

Acetylene Tunes Microbial Growth During Aerobic Cometabolism of Trichloroethene.

Microbial aerobic cometabolism is a possible treatment approach for large, dilute trichloroethene (TCE) plumes at groundwater contaminated sites. Rapid microbial growth and bioclogging pose a persistent problem in bioremediation schemes. Bioclogging reduces soil porosity and permeability, which negatively affects substrate distribution and contaminant treatment efficacy while also increasing the operation and maintenance costs of bioremediation. In this study, we evaluated the ability of acetylene, an oxygenase enzyme-specific inhibitor, to decrease biomass production while maintaining aerobic TCE cometabolism capacity upon removal of acetylene. We first exposed propane-metabolizing cultures (pure and mixed) to 5% acetylene (v v-1) for 1, 2, 4, and 8 d and we then verified TCE aerobic cometabolic activity. Exposure to acetylene overall decreased biomass production and TCE degradation rates while retaining the TCE degradation capacity. In the mixed culture, exposure to acetylene for 1-8 d showed minimal effects on the composition and relative abundance of TCE cometabolizing bacterial taxa. TCE aerobic cometabolism and incubation conditions exerted more notable effects on microbial ecology than did acetylene. Acetylene appears to be a viable approach to control biomass production that may lessen the likelihood of bioclogging during TCE cometabolism. The findings from this study may lead to advancements in aerobic cometabolism remediation technologies for dilute plumes.

Carboxymethyl cellulose stabilization induced changes in particle characteristics and dechlorination efficiency of sulfidated nanoscale zero-valent iron

Polymer stabilization, exemplified by carboxymethyl cellulose (CMC), has demonstrated effectiveness in enhancing the transport of nanoscale zero-valent iron (nZVI). And, sulfidation is recognized for enhancing the reactivity and selectivity of nZVI in dechlorination processes. The influence of polymer stabilization on sulfidated nZVI (S-nZVI) with various sulfur precursors remains unclear. In this study, CMC-stabilized S-nZVI (CMC-S-nZVI) was synthesized using three distinct sulfur precursors (S2−, S2O42−, and S2O32−) through one-step approach. The antioxidant properties of CMC significantly elevated the concentration of reduced sulfur species (S2−) on CMC-S-nZVIs, marking a 3.1–7.0-fold increase compared to S-nZVIs. The rate of trichloroethylene degradation (km) by CMC-S-nZVIs was observed to be 2.2–9.0 times higher than that achieved by their non-stabilized counterparts. Among the three CMC-S-nZVIs, CMC-S-nZVINa2S exhibited the highest km. Interesting, while the electron efficiency of CMC-S-nZVIs surged by 7.9–12 times relative to nZVI, it experienced a reduction of 7.0–34% when compared with S-nZVIs. This phenomenon is attributed to the increased hydrophilicity of S-nZVI particles due to CMC stabilization, which inadvertently promotes the hydrogen evolution reaction (HER). In conclusion, the findings of this study underscores the impact of CMC stabilization on the properties and dechlorination performance of S-nZVI sulfidated using different sulfur precursors, offering guidance for engineering CMC-S-nZVIs with desirable properties for contaminated groundwater remediation.

Metagenomic sequencing reveals mechanisms of adaptation and biodegradation of dechlorinating bacteria to trichloroethylene

Bioremediation is a sustainable, cost-effective, and eco-friendly way to remediate pollutants. However, the effectiveness of bioremediation is constrained by the underground environmental conditions, resulting in poor natural attenuation of organic pollution and degradation by functional microorganisms. In this study, a dechlorinating bacteria (DB) was enriched from contaminated soil and used to degrade trichloroethylene (TCE) in wastewater. The adaptation and degradation mechanisms of DB to TCE were investigated by degradation product analysis and metagenomic sequencing. The degradation of TCE by DB is pH and additional carbon source dependent. The highest TCE removal amount (1.86 × 10−7 mmol/CFU) was achieved at pH=8, 1% DB inoculum volume, and 400 mg/L sodium acetate concentration. Moreover, DB has a high acid resistance and a removal capacity of 1.18×10−7 mmol/CFU for TCE at pH =2. None of the co-occurring pollutants Cr (VI) and toluene had a significant effect on the ability of DB to degrade TCE in wastewater (maintained at 1.13–1.22×10−7 mmol/CFU). DB dechlorinated TCE mainly through the action of extracellular enzymes (contributed 91% of the total removal ability). DB playing a major role in degradation is Paraclostridium. Significant differences in alpha diversity indices were revealed in the reaction systems after 15 days of exposure to TCE (p < 0.01). The degradation of TCE by DB is mainly accomplished through the defense system, energy synthesis, electron supply and biodegradation. Metagenomic sequencing demonstrated that DB achieved adaptation and degradation of TCE through gene-regulated biological processes such as xenobiotic biodegradation and metabolism, carbohydrate metabolism, biosynthesis of other secondary metabolites, amino acid metabolism, membrane transport, and signal transduction. This study reveals for the first time the biodegradation efficiency and biotransformation process of DB under TCE stress.

Surfactant enhanced persulfate system for the synergistic oxidation and reduction of mixed chlorinated hydrocarbons

Surfactant-enhanced in-situ chemical oxidation (S-ISCO) is widely applied in soil and groundwater remediation. However, the role of surfactants in the reactive species (RSs) transformation remains inadequately explored. This work introduced nonionic surfactant Tween-80 (TW-80) into a nano zero-valent iron (nZVI) activated persulfate (PS) system. The findings indicate that PS/nZVI/TW-80 system can realize the concurrent removal of trichloroethylene (TCE), tetrachloroethene (PCE), and carbon tetrachloride (CT), whereas CT cannot be eliminated without TW-80 presence. Further analysis unveiled that hydroxyl (HO•) and sulfate radicals (SO4－•) were the primary species for TCE and PCE degradation, while CT was reductively eliminated by surfactant radicals generated from TW-80. Moreover, the surfactant radicals were found to accelerate Fe(III)/Fe(II) cycle, reduce the production of iron sludge, and increase PS decomposition. The possible degradation routes of mixed chlorinated hydrocarbons (CHCs) and the decomposition pathways of TW-80 were proposed through the density function theory (DFT) calculation and intermediates analysis. Additionally, the effects of other nonionic surfactants on the simultaneous removal of TCE, PCE, and CT, and the practical applications using the actual contaminated groundwater were also evaluated. This study provides theoretical support for the simultaneous removal of CHCs, particularly those containing perchlorinated contaminants, using the S-ISCO techniques.

Efficient activation of peroxymonosulfate for trichloroethylene degradation by cobalt ferrites anchored on CeO2 surfaces: Radical to non-radical pathway shift

This research investigates the unique configuration of cobalt ferrite (Co1.5Fe1.5O4) anchored onto the surface of cerium dioxide (CeO2), which effectively activates peroxymonosulfate (PMS) to degrade trichloroethylene (TCE). Co1.5Fe1.5O4-CeO2/PMS was able to completely degrade 5 mg/L of TCE by comparison between PMS and the components of the prepared composites. In addition, the Co1.5Fe1.5O4-CeO2/PMS system was highly adaptable to pH and aqueous substrates. Quenching experiments combined with ESR spectroscopy results demonstrated that ·OH, SO4·-, O2·-, and 1O2 in the system play an important role in degrading TCE. The Co1.5Fe1.5O4-CeO2/PMS system can maintain 90% degradation efficiency for various pollutants (TCE, carbon tetrachloride (CT), dichloromethane (DCM), 2,4-dichlorophenoxyacetic acid (2,4-D)) as well as the actual wastewater, and the multiple cycling experiments have verified that the Co1.5Fe1.5O4-CeO2/PMS has a good stability. XPS comparisons before and after the reaction revealed that cobalt ferrite exhibited a unique transition from the radical pathway to the non-radical pathway during TCE degradation after the introduction of CeO2. This pathway shift can be attributed to the synergistic interaction between cobalt ferrite and CeO2, which adjusts the electronic structure, facilitates the activation of PMS, and generates more reactive oxygen species to decompose TCE. This research offers valuable insights into the design of efficient advanced oxidation catalysts for the removal of organic pollutants from water and the optimization of degradation pathways.

Evaluation of Passive Vapor Diffusion Samplers to Quantify Acetylene, Ethene, and Ethane in Groundwater

AbstractAcetylene, ethene, and ethane are products from the degradation of trichloroethene (TCE) in contaminated aquifers. However, the volatility of these gases makes it challenging to avoid excessive losses during sampling. The objective of this study was to compare the quantification of acetylene, ethene, and ethane using passive vapor diffusion (PVD) samplers vs. conventional low‐flow groundwater collection. Samples were obtained from 8 to 13 monitoring wells at three sites that show potential for biotic and abiotic degradation of TCE in fractured rock aquifers. Method reporting limits (MRLs) for the PVD samplers were 0.25 μg/L for acetylene (0.0094 μM) and 0.28 μg/L for ethene and ethane (0.0099 and 0.0092 μM, respectively); the MRLs for conventional low‐flow groundwater samples were ~40% higher. For two of the sites, the maximum concentrations of acetylene, ethene, and ethane obtained with the PVD samplers were comparable to the conventional low‐flow samples. The frequency of detection for these gases with the PVD samplers was also comparable to conventional low‐flow groundwater sampling. For one of the sites with higher levels of acetylene (maximum of 13 μg/L), the concentrations from the PVD samplers were approximately twofold higher than those with conventional low‐flow groundwater sampling. Based on robust detection of acetylene, ethene, and/or ethane, it appears likely that degradation of TCE is occurring at the three sites that were sampled. The use of PVD samplers can reduce the possibility of false negative results to provide another line of evidence in support of natural attenuation.

Persulfate activation via iron sulfide nanoparticles for enhanced trichloroethylene degradation and its applications in groundwater remediation

Trichloroethylene (TCE) is known for its carcinogenic properties and limited environmental degradation. Therefore, TCE degradation was carried out using a catalyzed system, i.e., an advanced oxidation process (AOP) for an aqueous solution. This study focuses on activating sodium persulfate (PS) by laboratory-synthesized iron sulfide nanoparticles (FeS-NPs) with a particle size of 115.17 nm for enhanced TCE degradation. Field emission scanning electron microscope (FESEM), transmission electron microscopy (TEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET) analyses were employed to investigate physio-chemical properties and surface morphologies of synthesized FeS-NPs catalyst. PS/FeS-NPs exhibited outstanding performance, achieving a remarkable degradation (99.07 %) of TCE in 60 min of reaction time, surpassing the degradation demonstrated by commercially available PS/FeS (25 %). The dominant involvement of Fe transformation and SO4•ˉ, OH•, and 1O2 radicals in TCE degradation was validated through scavenging and electron paramagnetic resonance (EPR) investigation. Moreover, the PS/FeS-NPs system was found efficient (97⁓99 %) in both acidic and basic solutions, although it is noteworthy that highly basic (pH 11) mediums may impact the degradation efficiency (13.8 %). Recycling and stability experiments revealed significant efficiency of the PS/FeS-NPs system during the second run (90.02 %) and third run (68.25 %). These core revelations validate the efficiency of FeS-NPs in TCE degradation in an aqueous solution. Conclusively, the PS/FeS-NPs system encouraged TCE degradation outcomes, depicting strong potential for prolonged benefits in the remediation of TCE-polluted water.

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.

Aerobic co-metabolic cis-Dichloroethene degradation with Trichloroethene as primary substrate and effects of concentration ratios

Pollution with chloroethenes threaten groundwater resources worldwide. Cis-Dichloroethene (cDCE) and Trichloroethene (TCE) are widespread pollutants that often occur together at contaminated sites, either as primary discharges or as degradation products of anaerobic dechlorination. In this study, comprehensive microcosm experiments were conducted with groundwater samples of seven sites contaminated with chloroethenes. In total, twelve wells with different pollutant concentrations and chloroethene compositions were sampled, and aerobic microcosms including sterile controls were set up. The results revealed interactions as well as interferences between cDCE and TCE. First, co-metabolic cDCE degradation with TCE as growth substrate was detected for the first time in this work. Transformation yields Ty' (molar ratio of co-substrate degraded to primary substrate degraded) of the degradation process were determined and showed a linear relationship with the cDCE/TCE concentration ratio. At low cDCE/TCE ratio, aerobic metabolic TCE degradation can result in complete cDCE removal due to co-metabolic degradation. Secondly, interfering effects were detected at notable cDCE levels resulting in deceleration of TCE degradation and residual concentrations which were also correlating linearly with the cDCE/TCE concentration ratio. These findings are significant for investigating chloroethene contaminated sites and planning remediation strategies. In particular, the efficiency biological remediation methods in the presence of both pollutants can be evaluated more precisely through the knowledge of interactions and interferences. Our study emphasizes that co-contaminants and possible effects of contaminant mixtures on the degradation rates of individual substances should be considered in general.

Comparative investigation of organic contaminant removal in the synthesized greigite (Fe3S4)- and other iron sulfide-enhanced PDS/Fe(II) systems: Efficiencies, kinetics, and mechanism insights

In this research, greigite (Fe3S4) was innovatively applied for the enhancement of PDS/Fe(II) system. From XRD and SEM analyses, Fe3S4 was successfully synthesized and appeared uniform sphere-like particles with a petal-like structure. Trichloroethylene (TCE), as the target, was significantly degraded from 28.5 % to 92.8 % in PDS/Fe(II)/Fe3S4 system. The enhanced mechanisms, differences, and superiority of Fe3S4 against the other three iron sulfides were elucidated as follows: (1) on account of the abundant reduction sites on its surface, Fe3S4 could not only directly release Fe(II) and accelerate Fe(II) regeneration by sulfur substances, but also participate in the process of O2−• generation, and (2) the reaction mainly took place on Fe3S4 surface, in which the surface-bound reactive species (RSs) were of great importance for TCE degradation. Through EPR, quantification, and scavenging tests of RSs, HO•, SO4−•, and O2−• were all the dominant RSs responsible for TCE removal. Besides, these enhanced systems had high tolerance on complex water conditions and could remediate various contaminants in actual groundwater. Three TCE degradation pathways were deduced in four iron sulfide-enhanced systems and the toxicities of intermediates were evaluated, recommending that Fe3S4-enhanced system was of the least toxicity and most favorable for application in practice.

Pd@Bi2Ru2O7/BiVO4 Z-Scheme Heterojunction Nanocomposite Photocatalyst for the Degradation of Trichloroethylene.

Photocatalytic degradation of chlorinated persistent organic pollutants is a very challenging process due to the high redox potential of the C-Cl bond that requires wide band gap catalysts that are activated under UV light. Designing a Z-scheme heterojunction between visible light-activated metal oxides with compatible band gaps enables these redox potentials. Herein, we report the design of a pyrochlore/Aurivillius Z-scheme heterojunction to enhance the photocatalytic activity of BiVO4 for the degradation of trichloroethylene. We prepared Bi2Ru2O7/BiVO4 heterostructured photocatalysts by a controlled hydrothermal approach. Upon optimizing the Bi2Ru2O7 ratio to 1.0 wt %, the heterostructured photocatalyst demonstrated enhanced activity in the degradation of trichloroethylene (TCE) under simulated sunlight irradiation compared to bare BiVO4 and Bi2Ru2O7, respectively. Decorating the surface of the catalyst with palladium nanodomains to create the Pd@Bi2Ru2O7/BiVO4 nanocomposite showed a substantial increase in the photocatalytic degradation of TCE. The material characterization indicated that the architecture of the material provides a synergy of enhancing the redox potential of the photocatalyst and improving the charge carrier dynamics. Furthermore, the photoelectrochemical characterization confirmed that the dual heterojunctions in the Pd@Bi2Ru2O7/BiVO4 nanocomposite resulted in improved interfacial charge carrier transfer and enhanced the electron/hole separation efficiency compared to the nonpalladized catalysts. This work provides a promising approach for band gap engineering of visible light photocatalysts for the degradation of halogenated persistent organic pollutants.

Oxalate-modified microscale zero-valent iron for trichloroethylene elimination by adsorption enhancement and accelerating electron transfer

Trichloroethylene (TCE) with trace concentrations is often detected in soils and groundwater, posing potential damages to public health. The elimination of TCE can be achieved through reductive dechlorination using zero-valent iron (ZVI). However, ZVI usually suffers from the presence of passive iron (hydro)oxides layer and low electron transfer rate, thus leading to the unsatisfactory reactivity. Herein, we fabricated oxalated ZVI (Ox-ZVIbm) by mechanical ball-milling of micro-scale ZVI and H2C2O4·2H2O to modify the ZVI surface composition. To be specific, the modification of the iron oxide shell by oxalic acid facilitated the generation of unsaturated coordination Fe(II), enhancing TCE adsorption. Furthermore, the formed FeC2O4 on the iron oxide shell improved electron transfer efficiency, contributing to the enhanced TCE reductive dechlorination. Impressively, the rate of TCE degradation by Ox-ZVIbm was 10-fold higher than that of ZVIbm without oxalate modification. Moreover, Ox-ZVIbm samples were filled in a laboratory Permeable Reactive Barriers (PRB) column to treat actual underground wastewater containing TCE pollutants. The effluent concentration of TCE maintained steadily below 0.21 mg/L for over 10 days, complying with the National Groundwater Class IV standard (GBT 14848–2017). This marks a significant step toward practical groundwater treatment.

Enhanced Biogenic Sulfidation of Zero-Valent Iron in Columns: Implications for Promoting Dechlorination in Permeable Reactive Barriers.

Biogenic sulfidation of zero-valent iron (ZVI) using sulfate reducing bacteria (SRB) has shown enhanced dechlorination rates comparable to those produced by chemical sulfidation. However, controlling and sustaining biogenic sulfidation to enhance in situ dechlorination are poorly understood. Detailed interactions between SRB and ZVI were examined for 4 months in column experiments under enhanced biogenic sulfidation conditions. SRB proliferation and changes in ZVI surface properties were characterized along the flow paths. The results show that ZVI can stimulate SRB activity by removing excessive free sulfide (S2-), in addition to lowering reduction potential. ZVI also hinders downgradient movement of SRB via electrostatic repulsion, restricting SRB presence near the upgradient interface. Dissolved organic carbon (e.g., >2.2 mM) was essential for intense biogenic sulfidation in ZVI columns. The presence of SRB in the upgradient zone appeared to promote the formation of iron polysulfides. Biogenic FeSx deposition increased the S content on ZVI surfaces ∼3-fold, corresponding to 3-fold and 2-fold improvements in the trichloroethylene degradation rate and electron efficiency in batch tests. Elucidation of SRB and ZVI interactions enhances sustained sulfidation in ZVI permeable reactive barrier.

Degradation of trichloroethylene by biochar supported nano zero-valent iron (BC-nZVI): The role of specific surface area and electrochemical properties

Direct electron transfer and the involvement of atomic hydrogen (H⁎) are considered the main mechanisms for reductive dechlorination promoted by nano zero-valent iron (nZVI) supported on highly conductive carbon. It is still unclear how precisely H⁎, the specific surface area, and the electrochemical characteristics contribute to biochar supported nano zero-valent iron (BC-nZVI) activity in chlorinated hydrocarbon contaminant removal. In this study, a range of BC-nZVIs were prepared by a liquid-phase reduction process, and the contributions of specific surface area and electrochemical performance to H⁎ generation and electron transfer have been assessed. The mechanism of trichloroethylene (TCE) dechlorination by BC-nZVIs has been evaluated in terms of removal efficiency and the ultimate degradation products. The results have demonstrated that BC-nZVIs exhibit a higher specific surface area and TCE degradation efficiency compared with the bare nZVI. Ethane, ethylene, and acetylene were the principal TCE degradation products. The elimination of TCE was not significantly affected by differences in BC-nZVI specific surface area, but electron transfer and sustained generation of H⁎ were dependent on the catalyst electrochemical characteristics. The electrochemical properties of biochar serve to lower the corrosion potential of nZVI, improving electronic transfer capability and reactivity and promoting direct electron transfer for the degradation of TCE. In addition, the enhanced electrochemical properties also facilitate the reaction of nZVI with water and can promote the sustained generation of H⁎. Generation of H⁎ played a key role in reductive dechlorination over BC-nZVIs, which was related to the properties of the biochar support. This study focuses on the role of H⁎ and electrochemical performance in TCE reductive dechlorination, and provides a theoretical foundation and experimental support for the practical application of BC-nZVIs.

Controlled-Release Materials for Remediation of Trichloroethylene Contamination in Groundwater

Groundwater contamination by trichloroethylene (TCE) presents a pressing environmental challenge with far-reaching consequences. Traditional remediation methods have shown limitations in effectively addressing TCE contamination. This study reviews the limitations of conventional remediation techniques and investigates the application of oxidant-based controlled-release materials, including encapsulated, loaded, and gel-based potassium permanganate since the year 2000. Additionally, it examines reductant controlled-release materials and electron donor-release materials such as tetrabutyl orthosilicate (TBOS) and polyhydroxybutyrate (PHB). The findings suggest that controlled-release materials offer a promising avenue for enhancing TCE degradation and promoting groundwater restoration. This study concludes by highlighting the future research directions and the potential of controlled-release materials in addressing TCE contamination challenges.

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.