Search Results (68)

In conventional low-viscosity solvents, magnetic field effects (MFEs) in photoredox catalysis are often negligible because photogenerated radical ion pairs (RIPs) diffuse apart before significant spin evolution occurs. This study reports using ionic liquids (ILs) as a tunable homogeneous “solvent cage” to observe distinct low-field MFEs in the phenothiazine-mediated photoinduced reductive dechlorination of aryl chlorides. Experimental results demonstrate that MFEs increase significantly with bulk viscosity, reaching saturation at approximately 1000 Gs with a maximum enhancement of about 15%, consistent with the hyperfine coupling mechanism (HFCM). Femtosecond transient absorption spectroscopy (fs-TA) reveals that the ionic liquid environment effectively reduces the radical cage escape rate, matching it with the spin evolution rate. This allows the external magnetic field to intervene in the back electron transfer (BET) process. However, unlike strongly confined micellar systems, the contribution of the triplet charge recombination (TCR) pathway here is moderate, intrinsically limiting the magnetic enhancement amplitude. These findings establish that MFE magnitude is determined by both viscosity-controlled cage dynamics and the efficiency of the TCR channel, providing a mechanistic basis for designing spin-modulated homogeneous photoredox systems. Full article

Amorphous nano zero-valent iron (A-nZVI) was synthesized via liquid-phase reduction and ethylenediamine (EDA) modification to enhance trichloroethylene (TCE) dechlorination. A-nZVI showed a cauliflower-like morphology, where 20–50 nm primary particles formed 500–1000 nm secondary agglomerates with a high surface area. Compared with crystalline nZVI (C-nZVI), A-nZVI exhibited higher electron transfer efficiency and stronger reducing capability (potentiodynamic polarization analysis). TCE removal followed a two-stage model: a rapid adsorption–reduction phase (pseudo-second-order; q_e = 9.48 mg/g, R² = 0.998) and a slower degradation phase (pseudo-first-order; k = 0.0125 h⁻¹, R² = 0.994). No toxic intermediates (e.g., dichloroethylene or vinyl chloride) were detected; products were mainly acetylene, ethylene, and ethane. The electron utilization efficiency increased from 8.47% (C-nZVI) to 15.32% (A-nZVI), while hydrogen evolution decreased by 32%. EDA formed Fe–N coordination bonds that facilitated electron transfer and stabilized the amorphous structure. A-nZVI retained 40% of its activity after four cycles under neutral to alkaline conditions. Full article

Chlorobenzoic acids (CBAs) are a group of chlorinated persistent environmental pollutants with hard biodegradability, high water solubility, and well-documented carcinogenic and endocrine-disrupting properties. Electrocatalytic hydrodechlorination (ECH) is a highly efficient method under mild conditions without harmful by-products, but the ECH process commonly requires adding precious metal catalysts such as palladium (Pd). To address the economic constraints and more effective utilization of Pd, a palladium/manganese dioxide (Pd/MnO₂) composite catalyst was developed in this study by chemical deposition. This method utilized the excellent electrochemical activity of MnO₂ as a carrier as well as the hydrogen storage and activation capacity of Pd. The test showed the optimal Pd loading was 7.5%, and the removal percent of 2,4-dichlorobenzoic acid (2,4-DCBA), a typical CBA, reached 97.3% using 0.5 g/L of Pd/MnO₂ after 120 min of electrochemical reaction. Under these conditions, the dechlorination percent can also be as high as 89.6%. A higher current density enhanced the dechlorination efficiency but showed the lower current utilization efficiency. In practical applications, current density should be minimized on the premise of compliance with the water treatment requirement. Mechanistic studies showed that MnO₂ synergistically promoted hydrolysis dissociation and hydrogen spillover and facilitated Pd-mediated adsorption of atomic hydrogen (H*) for dehydrogenation of 2,4-DCBA. The presence of MnO₂ can effectively disperse the loaded Pd and reduce the amount of Pd via the above process. The catalyst exhibited excellent stability over multiple cycles, and the 2,4-DCBA removal could still reach more than 80% after the five cycles. This work establishes electrocatalytic strategies for effectively reducing Pd usage and maintaining high removal of typical CBAs to support CBA-related water treatment. Full article

The activation of persulfate (PS) to oxidize and degrade 2,4-dichlorophenol (2,4-DCP) in aqueous solution represents a prevalent advanced oxidation technology. This study established a PS activation system using sulfide-modified nanoscale zero-valent iron supported on biochar (S-nZVI@BC). The optimal conditions included a PS:2,4-DCP mass ratio of 70:1 and S-nZVI@BC:PS of 1.5:1. The activator had excellent stability after being reused five times, which lead to high cost-effectiveness and sustainable usability. This system exhibited broad pH adaptability (3–11), with enhanced efficiency under acidic/neutral conditions. Chloride ion, nitrate, and carbonate had effects during the degradation. During the initial degradation phase, S-nZVI@BC played a primary role, with a greater contribution rate of adsorption than reduction. Fe⁰ played a dominant role in the PS activation process; reactive species—including HO•, SO₄•⁻, and O₂•⁻—were identified as key agents in subsequent degradation stages. The overall degradation processes comprised three distinct stages: dechlorination, ring-opening, and mineralization. Full article

Carbon tetrachloride (CT) is a toxic volatile chlorinated hydrocarbon, posing a serious hazard to ecosystem and human health. This study discussed the bioremediation possibility of groundwater contaminated by CT. Enhanced reductive dechlorination bioremediation (ERD) was used to promote the reductive dechlorination process of CT by adding yeast extract as a supplementary electron donor. The microcosm samples of the Control and Experi group were setup in the experiment, and the CT degradation efficiency and microbial community structure changes over 150 days were monitored. The results showed that the Experi group achieved complete degradation of CT within 40 days, while the control group had no significant change. By analyzing the physical and chemical indexes such as VFAs, sulfate ions, oxidation–reduction potential, pH value and so on, the key changes in the degradation process of CT were revealed. Microbial community analysis showed that specific microorganisms such as Acinetobacter johnsonii, Aeromonas media and Enterobacter mori played a significant role in the degradation of CT. They may produce hydrogen through fermentation to provide electron donors for the reductive dechlorination of CT. In addition, the genes of reductive dehalogenase synthase related to CT degradation were also identified, which provided molecular evidence for understanding the biodegradation mechanism of CT. The results deliver a scientific basis for optimizing the bioremediation strategy of CT-contaminated groundwater. Full article

Microplastics (MPs) and nanoplastics (NPs) can affect microbial abundance and activity, likely by damaging cell membrane components. While their effects on anaerobic digestion are known, less is understood about their impact on microbes involved in contaminant bioremediation. Chlorinated volatile organic contaminants (CVOCs) such as tetrachloroethene (PCE) and explosives like hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) are common in the environment, and their bioremediation is a promising cleanup strategy. This study examined how polystyrene (PS) and polyamide 6 (PA6) MPs and NPs influence CVOC and RDX biodegradation. PS particles did not inhibit the CVOC-degrading community SDC-9, but PA6 MPs impaired the reductive dechlorination of trichloroethene (TCE) to cis-1,2-dichloroethene (cis-DCE), causing a “cis-DCE stall” with no further conversion to vinyl chloride (VC) or ethene. Only 45% of TCE was dechlorinated to cis-DCE, and Dehalococcoides mccartyi abundance dropped 1000-fold in 35 days with PA6 MPs. In contrast, neither PA6 nor PS MPs and NPs affected RDX biotransformation. These results highlight the significant impact of PA6 MPs on CVOC biodegradation and the need to consider plastic pollution in environmental management. Full article

Organohalide-respiring bacteria (OHRB) facilitate the reductive dehalogenation of toxic halogenated compounds in the environment, which supports their growth and proliferation. Research conducted on OHRB has achieved notable advancements. However, given the intricacy of the ecosystem and the methodologies employed for microbial isolation, numerous constraints persist. Further exploration is imperative to elucidate the physiological characteristics, ecological functions, and technological applications of OHRB. This study aimed to evaluate the outcomes and insights of prior research via a bibliometric analysis of three obligate OHRB genera—Dehalococcoides, Dehalobacter, and Dehalogenimonas—over a three-decade period from 1994 to 2024, based on the Web of Science (WOS) database. The results show that research on these three bacterial genera has advanced in sequence since the initiation of studies in this field. The research area encompasses the identification and isolation of novel OHRB species, the gene sequencing of related enzymes, and the role of microorganisms in the remediation of environmental pollutants, reflecting a gradual transition from individual investigations of OHRB to the applications of microorganisms in remediating complex environmental pollution. This study systematically reviewed the past research history of this field and conducted an in-depth analysis of research hotspots. The integration of this analysis with technological development trends and practical application requirements provides a theoretical basis and innovative concepts for future research directions in the field of ecological environment restoration. Full article

Chloride ions in zinc refining accelerate equipment corrosion and anode and cathode losses, increase lead content, and reduce zinc quality. Therefore, the removal of chloride ions has become a research priority. The existing copper slag dechlorination process has problems such as the solid film barrier leading to impeded mass transfer, product wrapping triggering active site coverage, and incomplete reactions due to insufficient reaction-driving force, leading to low utilization of copper slag, poor dechlorination efficiency, and long reaction times. To address these issues, a new method of deep dechlorination based on the reduction of Cu²⁺ by liquid-phase mass transfer is proposed in this paper. The process utilizes ascorbic acid as a reducing agent, establishes a homogeneous aqueous phase reaction system, breaks through the solid membrane barrier, and avoids the encapsulation of the product layer, achieving efficient dechlorination. The enol structure of ascorbic acid promotes rapid dechlorination through proton-coupled electron transfer (PCET). Thermodynamic calculations show that compared to the current copper slag dechlorination process, this method increases the reaction-driving force by 18.6%, reduces the Gibbs free energy (ΔG^θ) by 59.3%, and increases the equilibrium constant by 6.7 × 10⁹ times, making the reaction more complete and achieving a higher degree of purification. The experimental results show that under optimized conditions, the chloride ion concentration in the solution decreases from 1 g/L to 0.0917 g/L within 20 min, with a removal rate of 90.8%. The main precipitate is CuCl. This process provides a more efficient solution to the chloride ion contamination problem in the hydrometallurgical zinc refining process. Full article

Polychlorinated biphenyls (PCBs) are classified as persistent organic pollutants (POPs) due to their potential threat to both ecosystems and human health. The Tibetan Plateau (TP), characterized by its low temperatures, pristine ecological conditions, and remoteness from anthropogenic influences, serves as the investigation region. This study analyzed water samples from the temperature glacial watershed and employed the risk assessment method established by the United States Environmental Protection Agency (US EPA) to assess both carcinogenic and non-carcinogenic risks of PCBs in five age groups. The total concentrations of PCBs (∑₃PCBs) varied from 738 to 1914 ng/L, with a mean value of 1058 ng/L, which was comparable to or exceeded levels reported in the surface water around the TP. Notably, the riverine sites located near the villages and towns exhibited the highest pollution levels. Our analyses indicated that glacier melting, long-range atmospheric transport (LRAT), reductive dechlorination processes, and various anthropogenic activities might be potential sources of PCB emission in the Meili Snow Mountains. According to the established national and international water quality standards, as well as toxic equivalency concentrations (TEQs) for dioxin-like PCBs (DL PCBs), the PCB concentrations detected in this study could result in serious biological damage and adverse ecological toxicological effects. However, the PCBs in all samples posed a negligible cancer risk to five age groups, and a non-carcinogenic risk to adults. These findings contribute valuable insights into the risks and sources of PCBs and may serve as a foundational reference for subsequent study of these compounds in the Meili Snow Mountains area of the southeastern TP. Full article

Electrochemical reduction is a promising strategy for the dechlorination of halogenated organic compounds, offering advantages such as enhanced electron transfer efficiency and increased hydrogen atom concentration. It has garnered significant attention for application in mitigating halogenated disinfection by-products (DBPs) in drinking water, owing to its high efficiency and simple operation. In this study, trichloroacetic acid (TCAA), a representative DBP, was selected as the target contaminant. A novel composite cathode comprising a metal–organic framework MIL-53(Fe)@C supported on an Nd magnet (MIL-53(Fe)@C-MAG) and its dechlorination performance for TCAA were systematically investigated. The innovative aspect of this study is the magnetic attachment of the MOF catalyst to the carbonized cathode surface treated through carbonization, which fundamentally differs from conventional solvent-based adhesion methods. Compared to the bare electrode, the MIL-53(Fe)@C-MAG achieved a TCAA removal efficiency exceeding 96.03% within 8 h of contact time. The structural characterization revealed that the α-Fe⁰ crystalline phase serves as the primary active center within the MIL-53(Fe)@C catalyst, facilitating efficient electron transfer and TCAA degradation. The scavenger experiments revealed that TCAA reduction involves a dual pathway: direct electron transfer and atomic hydrogen generation. The modified MIL-53(Fe)@C-MAG electrode exhibited robust electrolytic performance over a broad pH range of 3–7, with TCAA removal efficiency showing a positive correlation with current density within the range of 10–50 mA/cm². Furthermore, the electrode maintained exceptional stability, retaining more than 90% removal efficiency after five consecutive operational cycles. The versatility of the system was further validated by the rapid and efficient dechlorination of various chlorinated DBPs, demonstrating the broad applicability of the electrode. The innovative magnetic composite electrode demonstrates a significant advancement in electrochemical dechlorination technology, offering a reliable and efficient solution for the purification of drinking water contaminated with diverse halogenated DBPs. These results provide valuable insights into the development of electrolysis for dechlorination in water treatment applications. Full article

The excessive levels of neonicotinoid insecticides, particularly thiacloprid (THI), in the environment have become a significant threat to ecosystems. This study investigates the catalytic degradation of THI using pinewood biochar (PBC), zero-valent iron (ZVI), and ZVI/PBC composite, with a particular focus on the reaction activity modulation mediated by organic acids (humic acid: HA and oxalic acid: OA). Reductive dechlorination dominated THI degradation as observed by Cl⁻ release kinetics. Compared to HA (39.73%), the OA (73.44%) addition markedly increased the THI removal efficiency by ZVI/PBC, which alone has a lower removal efficacy, i.e., 37.29%. The increase in the THI removal rate was attributed to its enhanced electron transfer capacity. As confirmed by electrochemical characterization, the addition of organic acids promotes electron transfer between THI and catalysts (ZVI, PBC, or ZVI/PBC), thereby improving the removal efficiency of THI. XRD/XPS analyses elucidated that OA preferentially converted passivating Fe₂O₃/Fe₃O₄ on ZVI/PBC to reactive FeOOH and formed electron-conductive Fe–COO bonds, thereby suppressing oxide layer formation. PBC amplified these effects through ZVI dispersion and electron shuttling, reducing aggregation-induced activity loss. These findings provide a mechanistic framework for optimizing ligand-engineered iron composites, offering practical strategies to enhance pesticide remediation efficiency in organic acid-rich environmental systems. Full article

The removal of chlorinated organic pollutants from wastewater is a critical environmental challenge, as traditional methods for treating toxic pollutants like phenol and chlorophenols often suffer from high energy consumption and long treatment times, limiting their practical use. Electrocatalytic filtration has emerged as a promising alternative, but efficient, energy-saving electrocatalytic membranes for pollutants like 4-chlorophenol (4-CP) are still underexplored. A new type of electrocatalytic coupling membrane catalyst, ASP/CM (PANI-encapsulated aluminum silicate/ceramic membrane), was prepared using inexpensive silicate and polyaniline as the base materials, with in situ polymerization combined with co-focus magnetron sputtering. Under optimal conditions (25 mA/cm², 10 mM Na₂SO₄, 1.0 mL·min⁻¹ flow rate, and 50 μM 4-CP concentration), the membrane achieved about 95.1% removal of 4-CP and the degradation rate after five cycles was higher than 85%. In addition, O₂^•− and •OH are important active species in the electrocatalytic degradation of 4-CP. The 4-CP electrocatalytic membrane filtration process is a dual process of cathode reduction dechlorination and anodic oxidation. This work offers new insights into developing next-generation electrocatalytic membranes and expands the practical applications of electrocatalytic filtration systems. Full article

Actions for improving water quality are critical and include the remediation of polluted groundwater. The effectiveness of the remediation strategy to remove contamination by chlorinated solvents may be increased by combining physicochemical treatments (i.e., adsorption) and biological degradation (i.e., biological reductive dechlorination (BRD)). Recent studies have shown the potentialities of bio-based materials for bioremediation purposes, including polyhydroxybutyrate (PHB), a biodegradable microbial polyester tested as a fermentable source of slow-release electron donors. Further, a low-cost biochar derived from the pyrolysis of pinewood waste (PWB), used as sorbent material, has recently been proposed to accelerate reductive microbial dehalogenation. Here, we propose a coupled adsorption and biodegradation (CAB) process for trichloroethylene (TCE) removal in a mini pilot-scale reactor composed of two reactive zones, the first one filled with PHB and the second one with PWB. This work aimed to evaluate the performance of the CAB process with particular regard to the effectiveness of the PWB in sustaining the biofilm, mostly enriched by Dehalococcoides mccartyi. The main results showed the CAB system treated around 1300 L of contaminated water, removing 102 mg TCE per day. Combining PHB and PWB had a positive effect on the growth of the dechlorinating community with a high abundance of Dhc cells. Full article

The present study focuses on a site contaminated with halogenated hydrocarbons, utilizing a detailed inventory of contamination data to achieve the precise characterization of groundwater pollution. Employing MOFLOW-2000 software, a groundwater flow model was established for the study area. In conjunction with MT3DMS, a predictive model was constructed to simulate and forecast the spatiotemporal distribution of contaminant migration and attenuation following site remediation. The simulation area was delineated based on geographical features, with the vertical simulation range of strata also determined. To establish a hydrogeological conceptual model for the target remediation site, comprehensive hydrogeological data were collected, encompassing geological structures, hydrological parameters, and rainfall information. Model calibration was based on the six layers of low-permeability aquifer intervals revealed by geological exploration wells MW1–5, as well as the distribution of groundwater-level contours and rainfall data. Based on data from September 2010, an initial three-dimensional model of tetrachloroethylene (PCE) distribution was generated. Subsequently, a solute transport model for PCE was established, incorporating various enhanced reductive dechlorination (ERD) remediation strategies applied at different times and locations. Calibration against actual monitoring data revealed the presence of unmonitored dense non-aqueous phase liquids (DNAPLs) at the site, contributing to the continuous release and elevation of PCE concentrations. By accounting for DNAPL release, the calibrated transport and attenuation model closely matched observed concentration decay patterns, effectively capturing the actual dynamics of contaminant transport and attenuation within the groundwater system. The modeling approach proposed in this study provides important support for contamination remediation and attenuation at the current site, and it is also applicable to simulating and predicting pollution scenarios at similar sites. Full article

A new membrane-less bioelectrochemical reactor configuration was developed for contaminated groundwater remediation. The new bioelectrochemical reactor configuration was inspired by the utilisation of a permeable reactive barrier (PBR) configuration with no separation membrane. The corresponding reactive zones were created by using graphite granules and mixed metal oxide (MMO) electrodes to stimulate the reductive and oxidative biological degradation of chlorinated aliphatic hydrocarbons. In the present study, the PBR-like bioelectrochemical reactor has been preliminarily operated with synthetic contaminated groundwater, testing the reductive dechlorination activity on cis-dichloroethylene (cisDCE). Moreover, to assess the effects of competing anions presence for the electron donor (i.e., the cathode), the synthetic wastewater contained sulphate and nitrate anions. In the PBR-like reactor operation, nearly all cisDCE was removed in the initial sampling port, with only VC detected as the observable RD product. During the same biotic test of the PRB reactor, the presence of both the reductive dechlorination and anions reduction was confirmed by the complete nitrate reduction in the cathodic chamber of the PRB reactor. On the contrary, sulphate reduction showed a lower activity; indeed, only 25% of the influent sulphate was removed by the PRB reactor. Full article