Ultra-efficient peroxymonosulfate utilization and trichloroethylene degradation in heterogeneous catalytic system guided by sheet-like Cu2MnO4 nanoparticles: The role of Cu(III)-O species and free radicals.

Synthesizing cubic spinel Cu2MnO4 with nanosheet structure (SCMO) aimed to construct a "non-radical-mediated radical-oxidative reaction", for increasing PMS utilization efficiency, and solving the defects of SO4•- and •OH through indirect PMS activation by electron transfer process. Compared with box-like Cu2MnO4 (11.1%, 0.0035 min-1) and ordinary Cu2MnO4 nanoparticles (21.3%, 0.0070 min-1), SCMO/PMS showed excellent trichloroethylene removal (98.8%, 0.1577 min-1). The pivotal role of Cu(III) was determined based on EPR analysis, quenching experiments, chemical probe experiments, hydrogen temperature-programmed reduction and Raman spectroscopy analysis, in-situ FTIR and Raman analyses. In brief, the interaction between PMS and SCMO could produce surface-bonded reactive complexes and the subsequent breaking of O-O bond in the sub-stable structure allowed the conversion of Cu(II) to Cu(III), which in turn facilitates the generation of •OH and SO4•-. The density functional theory (DFT) calculations provided supporting evidence for the electron donor role of SCMO and the increase of the electron acceptance capacity of PMS. SCMO/PMS system showed good resistance and degradation efficiency to complex composition and combined pollutants in actually contaminated groundwater, respectively. However, the coexistence of high concentrations of arsenic could significantly affect SCMO performance due to their adsorption on -OH groups, which still need in-depth study.

Higher thermal remediation temperature facilitates the sequential bioaugmented reductive dechlorination.

The coupling of thermal remediation with microbial reductive dechlorination (MRD) has shown promising potential for the cleanup of chlorinated solvent contaminated sites. In this study, thermal treatment and bioaugmentation were applied in series, where prior higher thermal remediation temperature led to improved TCE dechlorination performance with both better organohalide-respiring bacteria (OHRB) colonization and electron donor availability. The 60 °C was found to be a key temperature point where the promotion effect became obvious. Amplicon sequencing and co-occurrence network analysis demonstrated that temperature was a more dominating factor than bioaugmentation that impacted microbial community structure. Higher temperature of prior thermal treatment resulted in the decrease of richness, diversity of indigenous microbial communities, and simplified the network structure, which benefited the build-up of newcoming microorganisms during bioaugmentation. Thus, the abundance of Desulfitobacterium increased from 0.11 % (25 °C) to 3.10 % (90 °C). Meanwhile, released volatile fatty acids (VFAs) during thermal remediation functioned as electron donors and boosted MRD. Our results provided temperature-specific information on synergistic effect of sequential thermal remediation and bioaugmentation, which contributed to better implementation of the coupled technologies in chloroethene-impacted sites.

Innovative strategy for the effective utilization of coal waste slag in the Fenton-like process for the degradation of trichloroethylene.

In response to environmental concerns at the global level, there is considerable momentum in the exploration of materials derived from waste that are both sustainable and eco-friendly. In this study, CS-Fe (carbon, silica, and iron) composite was synthesized from coal gasification slag (CGS) and innovatively applied as a catalyst to activate PS (persulfate) for the degradation of trichloroethylene (TCE) in water. Scanning electron microscope (SEM), fourier transmission infrared spectroscopy (FTIR), energy dispersive x-ray spectroscopy (EDS), brunauer, emmet, and teller (BET) technique, and x-ray diffractometer (XRD) spectra were employed to investigate the surface morphology and physicochemical composition of the CS-Fe composite. CS-Fe catalyst showed a dual nature by adsorption and degradation of TCE simultaneously, displaying 86.1% TCE removal in 3 h. The synthesized CS-Fe had better adsorption (62.1%) than base material CGS (36.4%) due to a larger BET surface area (770.8 m2 g-1), while 24.0% TCE degradation was recorded upon the activation of PS by CS-Fe. FTIR spectra confirmed the adsorption and degradation of TCE by investigating the used and fresh samples of CS-Fe catalyst. Scavengers and Electron paramagnetic resonance (EPR) analysis confirmed the availability of surface radicals and free radicals facilitated the degradation process. The acidic nature of the solution favored the degradation while the presence of bicarbonate ion (HCO3-) hindered this process. In conclusion, these results for real groundwater, surfactant-added solution, and degradation of other TCE-like pollutants propose that the CS-Fe composite offers an economically viable and favorable catalyst in the remediation of organic contaminants within aqueous solutions. Further investigation into the catalytic potential of coal gasification slag-based carbon materials and their application in Fenton reactions is warranted to effectively address a range of environmental challenges.

Single-Atom Iron Can Steer Atomic Hydrogen toward Selective Reductive Dechlorination: Implications for Remediation of Chlorinated Solvents-Impacted Groundwater.

Atomic hydrogen (H*) is a powerful and versatile reductant and has tremendous potential in the degradation of oxidized pollutants (e.g., chlorinated solvents). However, its application for groundwater remediation is hindered by the scavenging side reaction of H2 evolution. Herein, we report that a composite material (Fe0@Fe-N4-C), consisting of zerovalent iron (Fe0) nanoparticles and nitrogen-coordinated single-atom Fe (Fe-N4), can effectively steer H* toward reductive dechlorination of trichloroethylene (TCE), a common groundwater contaminant and primary risk driver at many hazardous waste sites. The Fe-N4 structure strengthens the bond between surface Fe atoms and H*, inhibiting H2 evolution. Nonetheless, H* is available for dechlorination, as the adsorption of TCE weakens this bond. Interestingly, H* also enhances electron delocalization and transfer between adsorbed TCE and surface Fe atoms, increasing the reactivity of adsorbed TCE with H*. Consequently, Fe0@Fe-N4-C exhibits high electron selectivity (up to 86%) toward dechlorination, as well as a high TCE degradation kinetic constant. This material is resilient against water matrix interferences, achieving long-lasting performance for effective TCE removal. These findings shed light on the utilization of H* for the in situ remediation of groundwater contaminated with chlorinated solvents, by rational design of earth-abundant metal-based single-atom catalysts.

Laboratory-scale characterization of slow-release permanganate gel (SRP-G) for the in-situ treatment of chlorinated-solvent groundwater plumes.

Significant challenges remain for the remediation of chlorinated-solvent plumes in groundwater, such as trichloroethene (TCE) and tetrachloroethene (PCE). A novel slow-release permanganate gel (SRP-G) technique may show promise for the in-situ treatment (remediation) of chlorinated contaminant plumes in groundwater. A series of laboratory experiments were conducted to characterize the primary physical factors that influence SRP-G gelation processes to optimize SRP-G performance for plume treatment. Specifically, experiments were conducted to quantify gel zeta potential, particle size distribution, and viscosity to determine SRP-G gelation characteristics and processes. These experiments tested various concentrations of two SRP-G amendment solutions (NaMnO4 and KMnO4) prepared with 30-wt.% and 50-wt.% colloidal silica to determine such influences on zeta potential, particle size distribution, and viscosity. The results of this study show that SRP-G solutions with low zeta potential and relatively high pH favor more rapid SRP-G gelation. The concomitant interaction of the predominantly negatively charged colloidal silica particles and the positively charged dissociated cations (Na+ and K+) in the SRP-G solution had the effect of stabilizing charge imbalance via attraction of particles and thereby inducing a greater influence on the gelation process. Gel particle size distribution and changes in viscosity had a significant influence on SRP-G solution gelation. The addition of permanganate (NaMnO4 or KMnO4) increased the average particle size distribution and the viscosity of the SRP-G solution and decreased the overall gelation time. SRP-G amendments (NaMnO4 or KMnO4) prepared with 50-wt.% colloidal silica showed more effective gelation (and reduced gelation time) compared to SRP-G amendments prepared with 30-wt.% colloidal silica. Under the conditions of these experiments, it was determined that both the 7-wt.% NaMnO4 solution and 90 mg/L KMnO4 solution using 50-wt.% colloidal silica would be the optimal injection SRP-G solution concentrations for this in-situ treatment technique.

Microplastic inhibits the sorption of trichloroethylene on modified biochar.

Biochar (BC) was used to remove trichloroethylene (TCE) from soil and water phases, and BC modification changed the sorption behavior of pollutants. Microplastics are emerging pollutants in the soil and water phases. Whether microplastics can affect the sorption of TCE by modified BC is not clear. Thus, batch sorption kinetics and isotherm experiments were conducted to elucidate the sorption of TCE on BC, and BC combined with polyethylene (PE) or polystyrene (PS). The results showed that HCl and NaOH modification increased TCE sorption on BC, while HNO3 modification inhibited TCE sorption on BC. When PE/PS and BC coexisted, the TCE sorption capacity decreased significantly on BC-CK + PE, BC-HCl + PE, BC-HNO3 + PE, BC-NaOH + PE, and BC-NaOH + PS, which was likely due to the preferential sorption of PE/PS on BC samples. We concluded that microplastics can change TCE sorption behavior and inhibit TCE sorption on BC samples. Thus, the interaction of BC and microplastics should be considered when BC is used for TCE removal in soil and water remediation.

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.

Real-time monitoring of in situ chemical oxidation (ISCO) of dissolved TCE by integrating electrical resistivity tomography and reactive transport modeling.

Successful in situ chemical oxidation (ISCO) applications require real-time monitoring to assess the oxidant delivery and treatment effectiveness, and to support rapid and cost-effective decision making. Existing monitoring methods often suffer from poor spatial coverage given a limited number of boreholes in most field conditions. The ionic nature of oxidants (e.g., permanganate) makes time-lapse electrical resistivity tomography (ERT) a potential monitoring tool for ISCO. However, time-lapse ERT is usually limited to qualitative analysis because it cannot distinguish between the electrical responses of the ionic oxidant and the ionic products from contaminant oxidation. This study proposed a real-time quantitative monitoring approach for ISCO by integrating time-lapse ERT and physics-based reactive transport models (RTM). Moving past common practice, where an electrical-conductivity anomaly in an ERT survey would be roughly linked to concentrations of anything ionic, we used PHT3D as our RTM to distinguish the contributions from the ionic oxidant and the ionic products and to quantify the spatio-temporal evolution of all chemical components. The proposed approach was evaluated through laboratory column experiments for trichloroethene (TCE) remediation. This ISCO experiment was monitored by both time-lapse ERT and downstream sampling. We found that changes in inverted bulk electrical conductivity, unsurprisingly, did not correlate well with the observed permanganate concentrations due to the ionic products. By integrating time-lapse ERT and RTM, the distribution of all chemical components was satisfactorily characterized and quantified. Measured concentration data from limited locations and the non-intrusive ERT data were found to be complementary for ISCO monitoring. The inverted bulk conductivity data were effective in capturing the spatial distribution of ionic species, while the concentration data provided information regarding dissolved TCE. Through incorporating multi-source data, the error of quantifying ISCO efficiency was kept at most 5 %, compared to errors that can reach up to 68 % when relying solely on concentration data.

Efficient composite chlorinated ethenes removal using gallic acid to enhance Fe/Ni nanoparticles activated persulfate.

As the representative volatile chlorinated hydrocarbons detected in wastewater, the removal of composite chlorinated ethenes is a major challenge in wastewater treatment. In the present study, an efficient removal system for composite chlorinated ethenes was reported, in which gallic acid was used to enhance the activation of persulfate by Fe/Ni nanoparticles. The influences of gallic acid-Fe/Ni and persulfate concentrations, initial pH value, reaction temperature, inorganic anions, and natural organic matters were evaluated in the composite chlorinated ethenes removal. Our results showed that the gallic acid-Fe/Ni-persulfate system with 9.0 mM of gallic acid-Fe/Ni and 30.0 mM of persulfate yielded about 100% trichloroethylene removal and 97.3%-98.6% perchloroethylene removal in the pH range of 3.0-12.0. Electron paramagnetic resonance analysis and radical quenching experiments indicated that SO4•- and •OH were the predominant radical species under acidic and alkaline conditions. Ultraviolet visible spectroscopy and inductively coupled plasma optical emission spectrometer tests revealed the Fe-gallic acid chelation could regulate the concentration of iron ions and improve the reactivity of gallic acid-Fe/Ni. These results demonstrated that the gallic acid-Fe/Ni-persulfate system was a promising strategy for treating composite chlorinated ethenes-containing wastewater.

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.

Particle-Scale Understanding of Arsenic Interactions with Sulfidized Nanoscale Zerovalent Iron and Their Impacts on Dehalogenation Reactivity.

Co-occurrence of organic contaminants and arsenic oxoanions occurs often at polluted groundwater sites, but the effect of arsenite on the reactivity of sulfidized nanoscale zerovalent iron (SNZVI) used to remediate groundwater has not been evaluated. Here, we study the interaction of arsenite [As(III)] with SNZVI at the individual-particle scale to better understand the impacts on the SNZVI properties and reactivity. Surface and intraparticle accumulation of As was observed on hydrophilic FeS-Fe0 and hydrophobic FeS2-Fe0 particles, respectively. X-ray absorption spectroscopy indicated the presence of realgar-like As-S and elemental As0 species at low and high As/Fe concentration ratios, respectively. Single-particle inductively coupled plasma time-of-flight mass spectrometry analysis identified As-containing particles both with and without Fe. The probability of finding As-containing particles without Fe increased with the S-induced hydrophobicity of SNZVI. The interactions of SNZVI materials with coexisting arsenite inhibited their reactivity with water (∼5.8-230.7-fold), trichloroethylene (∼3.6-67.5-fold), and florfenicol (∼1.1-5.9-fold). However, the overall selectivity toward trichloroethylene and florfenicol relative to water was improved (up to 9.0-fold) because the surface-associated As increased the SNZVI hydrophobicity. These results indicate that reactions of SNZVI with arsenite can remove As from groundwater and improve the properties of SNZVI for dehalogenation selectivity.

Quantitative analysis of TCE biodegradation pathway in landfill cover utilizing continuous monitoring, droplet digital PCR and multi-omics sequencing technology.

The remediation of volatile chlorinated hydrocarbons in the quasi-vadose zone has become a significant challenge. We applied an integrated approach to assess the biodegradability of trichloroethylene to identify the biotransformation mechanism. The formation of the functional zone biochemical layer was assessed by analyzing the distribution of landfill gas, physical and chemical properties of cover soil, spatial-temporal variations of micro-ecology, biodegradability of landfill cover soil and distributional difference metabolic pathway. Real-time online monitoring showed that trichloroethylene continuously undergoes anaerobic dichlorination and simultaneous aerobic/anaerobic conversion-aerobic co-metabolic degradation on the vertical gradient of the landfill cover system and reduction in trans-1,2-dichloroethylene in the anoxic zone but not 1,1-dichloroethylene. PCR and diversity sequencing revealed the abundance and spatial distribution of known dichlorination-related genes within the landfill cover, with 6.61 ± 0.25 × 104-6.78 ± 0.09 × 106 and 1.17 ± 0.78 × 103-7.82 ± 0.07 × 105 copies per g/soil of pmoA and tceA, respectively. In addition, dominant bacteria and diversity were significantly linked with physicochemical factors, and Mesorhizobium, Pseudoxanthomonas and Gemmatimonas were responsible for biodegradation in the aerobic, anoxic and anaerobic zones. Metagenome sequencing identified 6 degradation pathways of trichloroethylene that may occur in the landfill cover; the main pathway was incomplete dechlorination accompanied by cometabolic degradation. These results indicate that the anoxic zone is important for trichloroethylene degradation.

Bioelectrochemical system accelerates reductive dechlorination through extracellular electron transfer networks.

Bioelectrochemical system is considered as a promising approach for enhanced bio-dechlorination. However, the mechanism of extracellular electron transfer in the dechlorinating consortium is still a controversial issue. In this study, bioelectrochemical systems were established with cathode potential settings at -0.30 V (vs. SHE) for trichloroethylene reduction. The average dechlorination rate (102.0 µM Cl·d-1) of biocathode was 1.36 times higher than that of open circuit (74.7 µM Cl·d-1). Electrochemical characterization via cyclic voltammetry illustrated that electrostimulation promoted electrochemical activity for redox reactions. Moreover, bacterial community structure analyses indicated electrical stimulation facilitated the enrichment of electroactive and dechlorinating populations on cathode. Metagenomic and quantitative polymerase chain reaction (qPCR) analyses revealed that direct electron transfer (via electrically conductive pili, multi-heme c-type cytochromes) between Axonexus and Desulfovibrio/cathode and indirect electron transfer (via riboflavin) for Dehalococcoides enhanced dechlorination process in BES. Overall, this study verifies the effectiveness of electrostimulated bio-dechlorination and provides novel insights into the mechanisms of dechlorination process enhancement in bioelectrochemical systems through electron transfer networks.

Remediation of groundwater contaminated with trichloroethylene (TCE) using a long-lasting persulfate/biochar barrier.

Groundwater contamination by chlorinated solvents causes potential threats to water resources and human health. Therefore, it is important to develop effective technologies to remediate contaminated groundwater. This study uses biodegradable hydrophilic polymers, hydroxypropyl methylcellulose (HPMC), hydroxyethyl cellulose (HEC) and polyvinyl pyrrolidone (PVP) as binders to manufacture persulfate (PS) tablets for the sustained release of persulfate to treat trichloroethylene (TCE) in groundwater. The release time for different tablets decreases in the order: HPMC (8-15 days) > HEC (7-8 days) > PVP (2-5 days). The efficiency with which persulfate is released is: HPMC (73-79%) > HEC (60-72%) > PVP (12-31%). HPMC is the optimal binder for the manufacture of persulfate tablets and persulfate is released from a tablet of HPMC/PS ratio (wt/wt) of 4/3 for 15 days at a release rate of 1127 mg/day. HPMC/PS/biochar (BC) ratios (wt/wt/wt) between 1/1/0.02 and 1/1/0.0333 are suitable for PS/BC tablets. PS/BC tablets release persulfate for 9-11 days at release rates of 1243 to 1073 mg/day. The addition of too much biochar weakens the structure of the tablets, which results in a rapid release of persulfate. TCE is oxidized by a PS tablet with an efficiency of 85% and a PS/BC tablet eliminates more TCE, with a removal efficiency of 100%, due to oxidation and adsorption during the 15 days of reaction. Oxidation is the predominant mechanism for TCE elimination by a PS/BC tablet. The adsorption of TCE by BC fits well with the pseudo-second-order kinetics and the pseudo-first-order kinetics, which describes the removal of TCE by PS and PS/BC tablets. The results of this study show that a PS/BC tablet can be used in a permeable reactive barrier for long-term passive remediation of groundwater.

Kinetic models for hydroxyl radical production and contaminant removal during soil/sediment oxygenation.

Hydroxyl radical (•OH) oxidation has been identified as a significant pathway for element cycling and contaminant removal in redox fluctuating environments. Fe(II) has been found to be the main electron contributor for •OH production. Despite the recognition of the mechanisms of •OH production from the oxidation of Fe(II) in soils/sediments by O2, the kinetic model about Fe(II) oxidation, •OH production and contaminant removal is not yet clear. To address this knowledge gap, we conducted a series of experiments to explore the variation of different Fe(II) species, •OH and trichloroethylene (TCE, a representative contaminant) during sediment oxygenation, followed by the development of a kinetic model. In this model, Fe(II) species in sediments was divided into three categories based on the sequential chemical extraction method: ion exchangeable Fe(II), surface-adsorbed Fe(II) and mineral structural Fe(II),. Results showed that the kinetic model accurately fitted the concentration time trajectories of different Fe(II) species, •OH and TCE in this study as well as in previous studies. Model analysis indicated that the relative contribution of surface-adsorbed Fe(II) and reactive mineral structural Fe(II) in •OH production was 16.4%-33.9% and 66.1%-83.6%, respectively. However, ion-exchangeable Fe(II) not only fails to contribute to •OH production but also reduces the •OH yield relative to H2O2 decomposition. Poorly reactive mineral structural Fe(II) can serve as an electron pool to regenerate these reactive Fe(II) and facilitate •OH production. Regarding TCE degradation, Fe(II) species plays a dual role in contributing to •OH production while competing with TCE for •OH consumption, with the quenching efficiency being related to their content and reactivity toward •OH. This kinetic model offers a practical approach to describing and predicting •OH production and associated environmental impacts at the oxic-anoxic interface.

Degradation of trichloroethylene by double dielectric barrier discharge (DDBD) plasma technology: Performance, product analysis and acute biotoxicity assessment.

Trichloroethylene is carcinogenic and poorly degraded by microorganisms in the environment. Advanced Oxidation Technology is considered to be an effective treatment technology for TCE degradation. In this study, a double dielectric barrier discharge (DDBD) reactor was established to decompose TCE. The influence of different condition parameters on DDBD treatment of TCE was investigated to determine the appropriate working conditions. The chemical composition and biotoxicity of TCE degradation products were also investigated. Results showed that when SIE was 300 J L-1, the removal efficiency could reach more than 90%. The energy yield could reach 72.99 g kWh-1 at low SIE and gradually decreased with the increase of SIE. The k of the Non-thermal plasma (NTP) treatment of TCE was about 0.01 L J-1. DDBD degradation products were mainly polychlorinated organic compounds and produced more than 373 mg m-3 ozone. Moreover, a plausible TCE degradation mechanism in the DDBD reactors was proposed. Lastly, the ecological safety and biotoxicity were evaluated, indicating that the generation of chlorinated organic products was the main cause of elevated acute biotoxicity.

Enhanced trichloroethylene biodegradation: The mechanism and influencing factors of combining microorganism and carbon­iron materials.

Trichloroethylene (TCE) is one of the most prevalent contaminants with long-term persistence and a strong carcinogenic risk. Biological dechlorination has gradually become the mainstream method due to its advantages of low treatment cost and high environmental friendliness. However, microorganisms are easily restricted by environmental factors, such as an insufficient energy supply and a slow biological dechlorination process. This study focused on the coupled degradation of TCE with the combination of microorganisms and assistant materials (biochar, nZVI, nZVI modified biochar, HPO3 modified biochar), and set up microorganisms (alone) and materials (alone) as separate controls. Biochar provided nutrients, increased contact with pollutants, and promoted electron transfer to improve TCE degradation, although it did not change the pathway of degradation. The coupled treatment with anaerobic microorganisms (Micro) and 1 g/L unmodified biochar (BC) had the strongest degradation capacity. Compared with microorganisms alone, the addition of biochar resulted in the complete removal of TCE within 4 days. The influence of ambient temperature was mainly related to microbial activity, and 35 °C showed better degradation than 20 °C. Under 20 °C, 1 g/L of nZVI significantly promoted microbial dechlorination. As the dosage increased to 2 g/L and 4 g/L, nZVI showed a strong toxic effect. After 16 days, TCE was completely converted to ethylene by Micro-BC with C3H5O3Na, while 4.40 µmol dichloroethane (DCE) and 1.48 µmol vinyl chloride (VC) remained in the treatment with Micro-BC alone. As an electron acceptor, NaNO3 directly competed with TCE in the reduction process, which decreased the reduction efficiency of TCE. These findings provide a better understanding of the mechanism of the chemical materials coupling microbial dechlorination process and an optimal treatment method for trichloroethylene degradation.

Performance Enhancement of Biogenetic Sulfidated Zero-Valent Iron for Trichloroethylene Degradation: Role of Extracellular Polymeric Substances.

Chemical sulfidation has been considered as an effective strategy to improve the reactivity of zero-valent iron (S-ZVI). However, sulfidation is a widespread biogeochemical process in nature, which inspired us to explore the biogenetic sulfidation of ZVI (BS-ZVI) with sulfate-reducing bacteria (SRB). BS-ZVI could degrade 96.3% of trichloroethylene (TCE) to acetylene, ethene, ethane, and dichloroethene, comparable to S-ZVI (97.0%) with the same S/Fe ratio (i.e., 0.1). However, S-ZVI (0.21 d-1) exhibited a faster degradation rate than BS-ZVI (0.17 d-1) based on pseudo-first-order kinetic fitting due to extracellular polymeric substances (EPSs) excreted from SRB. Organic components of EPSs, including polysaccharides, humic acid-like substances, and proteins in BS-ZVI, were detected with 3D-EEM spectroscopy and FT-IR analysis. The hemiacetal groups and redox-activated protein in EPS did not affect TCE degradation, while the acetylation degree of EPS increased with the concentration of ZVI and S/Fe, thus inhibiting the TCE degradation. A low concentration of HA-like substances attached to BS-ZVI materials promoted electron transport. However, EPS formed a protective layer on the surface of BS-ZVI materials, reducing its TCE reaction rate. Overall, this study showed a comparable performance enhancement of ZVI toward TCE degradation through biogenetic sulfidation and provided a new alternative method for the sulfidation of ZVI.

Adsorption and reduction of trichloroethylene by sulfidated nanoscale zerovalent iron (S-nZVI) supported by Mg(OH)2.

Sulfidated nanoscale zerovalent iron (S-nZVI) supported on a flower spherical Mg(OH)2 with different Mg/Fe ration were successfully synthesized. The synthesized materials were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), Brunauer-Emmett-Teller (BET), and X-ray photoelectron spectroscopy (XPS). The results showed that S-nZVI particles were well dispersed on the petals of the flower spherical Mg(OH)2. The influence of factors, including the initial solution pH, Mg/Fe, S/Fe were studied. The trichloroethylene (TCE) adsorption data on Mg(OH)2 and S-nZVI @Mg(OH)2 fit well to a Langmuir isotherm model, and the maximum adsorption of S-nZVI @Mg(OH)2 was 253.55 mg/g, which was 2.6-fold of S-nZVI. Meanwhile, the S-nZVI @Mg(OH)2 composite expanded the pH selection range of S-nZVI from 2 to 11. Cycling experiments showed that removal rate was 58.3% for the 5th cycle. TCE removal was due to synergistic action of reduction coupled with adsorption. During this process, 65.43% of total remove TCE from ion chromatography data was reduced and 34.57% of total remove TCE was adsorbed finally. At the same time, adsorption favors reduction. These observations indicated that the S-nZVI @Mg(OH)2 can be considered as potential adsorbents to remove TCE for environment remediation.

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.