Dechlorination Of Trichloroethylene Research Articles

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.

Sulfidated microscale zero-valent iron/reduced graphene oxide composite (S-mZVI/rGO) for enhanced degradation of trichloroethylene: The role of hydrogen spillover

Atomic hydrogen (H*) has long been thought to play an important role in the dechlorination of trichloroethylene (TCE) by carbon-supported zero-valent iron (ZVI), which offers an alternative pathway for TCE dechlorination. Herein, we demonstrate that the reductive dechlorination of TCE by sulfidated microscale ZVI (S-mZVI) can be further enhanced by promoting the formation of H* through the introduction of reduced graphene oxide (rGO). The completely degradation of 10 mg/L TCE can be achieved by S-mZVI/rGO within 24 h, which was 3.3 times faster than that of S-mZVI. The change in the distribution of TCE degradation products over time suggests that the introduction of rGO leads to a change in the dechlorination pathway. The percentage of ethane in the final products of TCE degradation by S-mZVI/rGO was 34.3 %, while that of S-mZVI was only 21.9 %. The electrochemical tests confirmed the occurrence of hydrogen spillover in the S-mZVI/rGO composite, which promoted the reductive dechlorination of TCE by H*. Although the S-mZVI/rGO composite had stronger hydrogen evolution propensity than S-mZVI, the S-mZVI/rGO composite still exhibited higher electron utilization efficiency than S-mZVI thanks to the increased utilization of hydrogen.

Recent advances and trends of trichloroethylene biodegradation: A critical review.

Trichloroethylene (TCE) is a ubiquitous chlorinated aliphatic hydrocarbon (CAH) in the environment, which is a Group 1 carcinogen with negative impacts on human health and ecosystems. Based on a series of recent advances, the environmental behavior and biodegradation process on TCE biodegradation need to be reviewed systematically. Four main biodegradation processes leading to TCE biodegradation by isolated bacteria and mixed cultures are anaerobic reductive dechlorination, anaerobic cometabolic reductive dichlorination, aerobic co-metabolism, and aerobic direct oxidation. More attention has been paid to the aerobic co-metabolism of TCE. Laboratory and field studies have demonstrated that bacterial isolates or mixed cultures containing Dehalococcoides or Dehalogenimonas can catalyze reductive dechlorination of TCE to ethene. The mechanisms, pathways, and enzymes of TCE biodegradation were reviewed, and the factors affecting the biodegradation process were discussed. Besides, the research progress on material-mediated enhanced biodegradation technologies of TCE through the combination of zero-valent iron (ZVI) or biochar with microorganisms was introduced. Furthermore, we reviewed the current research on TCE biodegradation in field applications, and finally provided the development prospects of TCE biodegradation based on the existing challenges. We hope that this review will provide guidance and specific recommendations for future studies on CAHs biodegradation in laboratory and field applications.

Directional bioelectrochemical dechlorination of trichloroethene to valuable ethylene by introduction poly-3-hydroxybutyrate as a slow release carbon source

Bioelectrochemical dechlorination is one of the prospective and economic strategies for remediation of halogenated organics contaminated site, however, exploring the way of system construction with high detoxification efficiency and low organocarbon risk is still challenging. Herein, the slow-release organic carbon-sources (SOCs) coupled bioelectrochemical dechlorination system with generally accelerated trichloroethene (TCE) dechlorination performance and controllable organocarbon release was reported. It is interestingly found the introduction of Poly-3-hydroxybutyrate (PHB) achieved the greatly improved dechlorination efficiency (2.23 times improved k value) with valuable ethylene as a major metabolite (recovery ratio of 94.00 ± 1.62 %), reflecting the superior TCE detoxification and ethylene recovery potential. Microbial molecular mechanism analysis revealed the enriched electroactive dechlorinators (Geobacter and Desulfovibrio) in cathode representing the positive correlation (r > 0.8, p < 0.05) with TCE removal, were involved in the accelerated TCE dechlorination to 1,2-DCE. The non-electroactive dechlorinator (Dehalococcoides) observed in suspension symbiotically cooperating with some fermenters (Petrimonas, Sedimentibacter, etc.) and positively correlating with 1,2-DCE removal, was responsible for dechlorination of 1,2-DCE to ethylene through utilizing PHB fermentation generated H2 as electron donor. PHB coupled bioelectrochemical dechlorination system realized the quick and directional conversion of TCE to ethylene, while maintaining the organocarbon release at a controllable and stable level, providing a feasible approach for simultaneous pollution removal and resource recovery by applying bioelectrochemical system in chlorinated hydrocarbon contaminated field.

Dual role of soil in dechlorination of soil-sorbed trichloroethene by CMC stabilized and sulfidated nanoscale zero-valent iron

Carboxymethyl cellulose stabilized and sulfidated nano zero-valent iron (CMC-S-nZVI) can efficiently degrade trichloroethene (TCE) in water. However, little is known about the interaction between CMC-S-nZVI and TCE in soils. Here we studied the effects of two soils, a sandy (LY) and a sandy-loamy soil (DXAL), on TCE dechlorination by two types of CMC-S-nZVI particles. Continuous dechlorination of soil-sorbed TCE was observed for up to 96 h. LY and DXAL soil sorption suppressed 24-h dechlorination by 5–16 % and 25–51 %, respectively, although CMC significantly enhanced TCE release from the soils. Soil clay minerals, including Fe/Mn oxides and organic matter, promoted iron corrosion during the initial stage (< 8 h and < 2 h for the two particle types) through uptake of Fe2+ from the CMC-S-nZVI surface, but inhibited corrosion and TCE dechlorination at the later stage by blocking surface reaction sites, thereby hindering electron transfer. The dual effects of soil were more evident in DXAL, due to its higher content of clays and organic matter. Our findings show that CMC-S-nZVI can effectively dechlorinate soil-sorbed TCE, but reductant demand and the blocking effect from the soil should be considered to optimize engineering designs at TCE-contaminated sites.

Thermally Enhanced Biodegradation of TCE in Groundwater

In situ remediation is usually restricted by temperature, lack of substrate for reductive dechlorination (anaerobic respiration), the presence of dehalogenating microorganisms, and specific bedrock conditions. In this work, trichloroethene (TCE) degradation was studied by a number of methods, from physical–chemical analyses to molecular biological tools. The abundance changes in dechlorinating bacteria were monitored using real-time PCR. The functional genes vcrA and bvcA as well as the 16S rRNA specific for representatives of genera Dehalococcoides, Dehalobacter, and Desulfitobacterium were monitored. Furthermore, the sulfate-reducing bacteria and denitrifying bacteria were observed by amplifying the functional genes apsA and nirK. The elevated temperature and the substrate (whey) addition significantly affected TCE dechlorination. The chlorine index decreased after nine weeks from 2.5 to 0.1 at 22 °C, to 1.1 at 17 °C and 1.7 at 12 °C and complete dechlorination was achieved at 22 °C with whey addition. The achieved results of this work show the feasibility and effectiveness of biological dechlorination of TCE enhanced with elevated temperature and whey addition.

Generation of adsorbed atomic hydrogen by Pd(II) doped Fe(OH)2 enables ultra-fast reductive dechlorination of trichloroethylene

Trichloroethylene (TCE) is a notorious persistent pollutant in groundwater, while most reductive dechlorination processes result in the formation of toxic less-chlorinated by-products. In this work, adsorbed atomic hydrogen (H*) was produced by Pd(II) doped Fe(OH)2, which was used for ultra-fast reductive dechlorination of TCE without the formation of less-chlorinated by-products. When the Fe(OH)2 dosage is 0.5 mM and the Pd(II) dosage is 20 μM, TCE (42 μM) is completely removed in 60 min with the pseudo first-order reaction rate constant of 7.74 h−1. Radical quenching experiment and electrochemical analysis both confirmed that adsorbed H* rather than absorbed H* contribute to the reduction of TCE. Density function theory calculation demonstrated that small Pd clusters were more beneficial to TCE dechlorination than large Pd clusters. The pseudo first-order rate constant for TCE reduction in real groundwater was as high as 0.018 min–1, demonstrating the potential application of Pd/Fe(OH)2 in groundwater remediation.

Fabrication and Characterization of Bimetal Sulfide Hybrid Ag/S-ZVI for Dechlorination of Trichloroethylene

Sulfidated and bimetal modification can improve the reactivity and selectivity of zero-valent iron in contaminant removal. However, previous studies were focused on unilateral material approaches. In this article, a new hybrid composite Ag/S-ZVI was prepared by doping elemental silver on surface of sulfidated nanoscale zerovalent iron (S-nZVI). The results of X-Ray Diffraction (XRD), energy dispersive spectrometer (EDS) and X-ray Photoelectron Spectroscopy (XPS) indicated Ag was dispersed on the surface of S-nZVI. Scanning electron microscope (SEM) images displayed Ag/S-ZVI was irregular clusters with rough surfaces, small agglomeration, and quasi-spherical in shape. The removal of TCE by Ag/S-ZVI was 90.4% within 20 min. The reaction rate constant &lt;i&gt;K&lt;sub&gt;obs&lt;/sub&gt;&lt;/i&gt; of Ag/S-ZVI was 2.59 times or 1.85 times of nZVI or S-nZVI, respectively. Cycling experiments showed that Ag/S-ZVI had good recycling ability, and the removal rate of TCE reached 72.6% at the third cycle. The addition of Ag&lt;sup&gt;+&lt;/sup&gt; makes S-nZVI as an abundant and efficient source of reducing electrons. The Fe&lt;sup&gt;0&lt;/sup&gt; core can break C-Cl bonds by releasing electrons and the surface layer of Ag favors the transfer efficiency of electrons. Such study provides an efficient and robust ternary system for the remediation of TCE in groundwater.

A quantitative study of the effects of particle' properties and environmental conditions on the electron efficiency of Pd and sulfidated nanoscale zero-valent irons

Electron efficiency (or electron selectivity, ɛe) is an important quantitative criterion for zero-valent iron treatment of organohalide contaminated groundwater. The aim of this quantitative study was the systematic exploration and comparison of the effects of the Pd/Fe and S/Fe molar ratios (i.e., [Pd/Fe] and [S/Fe]), trichloroethylene (TCE) concentrations ([TCE]), pH solution, aging time, and water matrices on the ɛe of Pd-nZVI and S-nZVI. To this end, we used TCE as a probe contaminant. The ɛe of Pd-nZVI increased and then decreased with [Pd/Fe], while that of S-nZVI increased with [S/Fe], as more hydrophobic FeS2 was formed on S-nZVI at higher [S/Fe]. The εe of S-nZVI and Pd-nZVI increased with increasing [TCE]. Specifically, the εe of S-nZVI and Pd-nZVI at [TCE] of 200 ppm increased by 24.9 % and 79.3 %, respectively, compared with that at [TCE] of 10 ppm. As the H2 evolution reaction (HER) was more sensitive to surface passivation than TCE dechlorination, the εe of S-nZVI and Pd-nZVI under alkaline conditions was higher than that under basic conditions, and increased by 11.7 % and 37.8 %, respectively, at pH 10 relative to that at pH 6. The εe also increased with the aging time of the S-nZVI and Pd-nZVI particles; the increase was by 27.2 % and 59.6 %, respectively, at aging time of 30 d compared with that of the fresh ones. The ɛe of both particles were higher in artificial groundwater (AGW) than in real groundwater (RGW). For all batch experiments, the εe of S-nZVI increased over the reaction time and tended to outperform that of Pd-nZVI, even though the εe of Pd-nZVI was higher than that of S-nZVI at the initial stage of TCE dechlorination, thereby justifying the longevity of S-nZVI.

Coordinatively Unsaturated Reduced Iron Sites Enable Hemin-Catalyzed Electrochemical Dechlorination of Trichloroethylene

Coordinatively Unsaturated Reduced Iron Sites Enable Hemin-Catalyzed Electrochemical Dechlorination of Trichloroethylene

Unveiling the positive effect of mineral induced natural organic matter (NOM) on catalyst properties and catalytic dechlorination performance: An experiment and DFT study

Herein, we report the significant effects of natural organic matter contained in natural zeolite (Z-NOM) on the physicochemical characteristics of a Ni/Fe@natural zeolite (NF@NZ) catalyst and its decontamination performance toward the dechlorination of trichloroethylene (TCE). Z-NOM predominantly consists of humic-like substances and has demonstrable utility in the synthesis of bimetallic catalysts. Compared to NF@NZ600C (devoid of Z-NOM), NF@NZ had increased dispersibility and mobility and showed significant enhancement in the catalytic dechlorination of TCE owing to the encapsulation of Ni0/Fe0 nanoparticles by Z-NOM. The results of corrosion experiments, spectroscopic analyses, and H2 production experiments confirmed that Ni0 acted as an efficient cocatalyst with Fe0 to enhance the dechlorination of TCE to ethane, and Z-NOM-capped Ni0 showed improved adsorption of TCE and atomic hydrogen on their reactive sites and oxidation resistance. The density functional theory (DFT) studies have substantiated the improved adsorption of TCE due to the presence of NOM (especially by COOH structure) and the enhanced charge density at the Ni site in the Ni/Fe bimetal alloy for the stronger adsorption of hydrogen atoms that ultimately enhanced the TCE reduction reaction. These findings illustrate the efficiency of NOM containing natural minerals toward the synthesis of bimetallic catalysts for practical applications.

Synergistic strengthening of SPC/Fe(II) system by CA coupled with mZVI for trichloroethylene degradation in SDS-containing aqueous solution

This study investigated the effect of synergistic strengthening by citric acid (CA) coupled with micron zero valent iron (mZVI) in Fe(II) catalyzed sodium percarbonate (SPC) system on trichloroethylene (TCE) removal in an aqueous environment with the existence of sodium dodecyl sulfate (SDS). Compared with SPC/Fe(II), SPC/Fe(II)/mZVI, SPC/Fe(II)/CA, and SPC/Fe(II)/CA/mZVI systems, the synergistic strengthening effect by CA and mZVI could maximize TCE removal to 92.0 % and dechlorination of TCE to 88.0 % within 30 min. Furthermore, the synergistic system has the widest pH range of 3–7. The removal of TCE could hardly be improved by only adjusting pH in the system without CA addition, while it could be easily achieved by the synergistic strengthening SPC/Fe(II)/CA/mZVI system. Fe(II) concentration and hydroxyl radical (HO•) amount showed that the presence of CA and mZVI could continuously release Fe(II) and efficiently promote the formation of HO•. Besides HO•, reductive radicals such as superoxide radical (O2−•) and carbon dioxide radical (CO2−•) were also abundant in the SDS environment. Although the reaction kinetic constant was reduced due to the negative effects of weak alkaline pH and inorganic anions in the actual groundwater, the chemical dosages with the original ratio of SPC/Fe(II)/CA/mZVI could still reach 87.8 % TCE degradation, which showed the superiority of this system for remediation of the actual contaminated groundwater.