A sequencing electroreduction-electrooxidation system driven by atomic hydrogen for enhancing 2,4-dichloronitrobenzene removal from wastewater.

The sequencing electroreduction-electrooxidation process has emerged as a promising approach for the degradation of the chloronitrobenzenes (CNBs) due to its elimination of electro-withdrawing groups in the reduction process, facilitating further removal in the subsequent oxidation process. Herein, we developed a cathode consisting of atom Pd on a Ti plate, which enabled the electro-generation of atomic hydrogen (H*) and the efficient electrocatalytic activation of H2O2 to hydroxyl radical (•OH). Cyclic voltammetry (CV) curves and electron spin resonance (ESR) spectra verified the existence of H* and •OH. The electroreduction-electrooxidation system achieved 94.7% of 20 mg L-1 2,4-DCNB removal with a relatively low H2O2 addition (5 mM). Moreover, the inhibition rate of Photobacterium phosphoreum in the effluent decreased from 95% to 52% after the sequencing electroreduction-electrooxidation processes. It was further revealed that the H* dominated the electroreduction process and triggered the electrooxidation process. Our work sheds light on the effective removal of electron-withdrawing groups substituted aromatic contaminants from water and wastewater.

Electrochemical oxidation of reverse osmosis concentrate using a pilot-scale reactive electrochemical membrane filtration system: Performance and mechanisms.

Scale-up treatment of real wastewater holds the key to promoting the practical application of electrochemical filtration technology. This work used a pilot-scale Ti/Pd reactive electrochemical membrane (REM) system (12 REM modules with a total REM area of 0.144 m2) to treat high-salinity reverse osmosis concentrate (ROC) from a chemical industry park. The pilot-scale Ti/Pd REM system demonstrated effective electrochemical degradation of ROC wastewater, achieving removal efficiencies of 82.3 ± 1.9% for COD and 46.7 ± 5.6% for TN at a membrane flux of 90 L/(m2·h) and a cell voltage of 5 V, with an energy consumption of 0.045 kWh/g-COD. Singlet oxygen (1O2) and reactive chlorine species were identified as the two primary reactive oxygen species generated in the Ti/Pd REM system. Fluorescence spectroscopy and Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) analysis indicated that the pilot-scale Ti/Pd REM treatment effectively oxidized humic acid-like substance and unsaturated aromatic compounds. Overall, the Ti/Pd REM technology shows a promising application potential for the treatment of high-salinity ROC from the chemical industry.

Anaerobic hydrolysis of recalcitrant tetramethylammonium from semiconductor wastewater: Performance and mechanisms.

The treatment of tetramethylammonium hydroxide (TMAH)-bearing wastewater, generated in the electronic and semiconductor industries, raises significant concerns due to the neurotoxic, recalcitrant, and bio-inhibiting effects of TMAH. In this study, we proposed the use of an anaerobic hydrolysis bioreactor (AHBR) for TMAH removal, achieving a high removal efficiency of approximately 85%, which greatly surpassed the performance of widely-used advanced oxidation processes (AOPs). Density functional theory calculations indicated that the unexpectedly poor efficiency (5.8-8.0%) of selected AOPs can be attributed to the electrostatic repulsion between oxidants and the tightly bound electrons of TMAH. Metagenomic analyses of the AHBR revealed that Proteobacteria and Euryarchaeota played a dominant role in the transformation of TMAH through processes such as methyl transfer, methanogenesis, and acetyl-coenzyme A synthesis, utilizing methyl-tetrahydromethanopterin as a substrate. Moreover, several potential functional genes (e.g., mprF, basS, bcrB, sugE) related to TMAH resistance have been identified. Molecular docking studies between five selected proteins and tetramethylammonium further provided evidence supporting the roles of these potential functional genes. This study demonstrates the superiority of AHBR as a pretreatment technology compared to several widely-researched AOPs, paving the way for the proper design of treatment processes to abate TMAH in semiconductor wastewater.

Efficient removal of bromate from contaminated water using electrochemical membrane filtration with metal heteroatom interface.

Efficient utilization of atomic hydrogen (H*) is of great importance for achieving efficient bromate reduction using electrochemical technologies. Herein, an electrochemical membrane with metal heteroatom interface of Ru and Ni was developed to enhance the utilization efficiency of H* via the membrane filtration process. The RuNi membrane demonstrated 91.3% of bromate removal at 5 mA cm-2 under the flow-through operation (40 L m-2 h-1). Cyclic voltammetry (CV) curves and electron spin resonance (ESR) spectra elucidated that the bromate reduction was mainly attributed to H* -mediated reduction rather than the direct electron transfer between bromate and RuNi active layer. The quenching experiments revealed a significant contribution of adsorbed H* to the bromate removal during the membrane filtration. Based on X-ray photoelectron spectrometry and X-ray diffraction analyses, we found that the resultant Ru0Ni0 structure on the electrochemical membrane could facilitate the generation of H* during the bromate reduction reaction. Besides, the higher pH might suppress the formation of H* and increase the energy barrier for breaking the Br-O bond, resulting in dramatic increase of energy consumption for removing bromate. Our work highlights the potential of utilizing H* in electrochemical membrane for removing bromate in water treatment and remediation.

Harnessing Nickel Phthalocyanine-Based Electrochemical CNT Sponges for Ammonia Synthesis from Nitrate in Contaminated Water.

Electrochemical reduction of nitrate to ammonia is of great interest in water treatment with regard to the conversion of contaminants to value-added products, which requires the development of advanced electrodes to achieve high selectivity, stability, and Faradaic efficiency (FE). Herein, nickel phthalocyanine was homogeneously doped into the fiber of a carbon nanotube (CNT) sponge, enabling the production of an electrode with high electrochemical double-layer capacitance (CDL) and a large electrochemically active surface area (ECSA). The as-prepared NiPc-CNT sponge could achieve 97.6% nitrate removal, 88.4% ammonia selectivity, and 86.8% FE at a nitrate concentration of 50 mg-N L-1 under an optimized potential of -1.2 V (vs Ag/AgCl). Meanwhile, the ammonia selectivity could be further improved at the high nitrate concentration. Density functional theory calculations showed that the exposure of Ni-N4 active sites could effectively suppress the hydrogen evolution reaction and dinitrogen generation, enhancing the ammonia selectivity and Faradaic efficiency. Overall, this work sheds light on the conversion of nitrate to ammonia on the metal phthalocyanine-based electrode, offering a novel strategy for managing nitrate in wastewater.

Removal of p-toluenesulfonic acid from wastewater using a filtration-enhanced electro-Fenton reactor.

Rapid global industrialization accompanies the discharge of industrial wastewater. p-Toluenesulfonic acid (PTSA), a kind of aromatic sulfonate that belongs to the refractory organic pollutant, is one of the most widely used chemicals in pharmaceutical, dye, petrochemical and plastic industries. In this study, we developed a filtration-enhanced electro-Fenton (FEEF) reactor to remove PTSA from synthetic wastewater. A filtration-enhanced stainless-steel mesh (FESSM) was used as the cathode. Under the optimal operating conditions of applied voltage 2.5 V, pH = 3.0, addition of 0.2 mM Fe2+ and 1.0 mM H2O2 for 120 min, the removal efficiency of PTSA (initial concentration of 100 mg L-1) could reach 92.6%. Compared with the control anodic oxidation and conventional Fenton system, the FEEF system showed higher ˙OH yield and PTSA removal efficiency, with a lower effluent biological toxicity and operating cost. The enhanced mass transfer rate by the filtration in the FEEF system accelerated the regeneration of catalyst Fe2+ and further promoted the heterogeneous reactions. The Fe species on the surface of FESSM cathode possessed a gradient distribution, the inner layer was dominated by Fe and the outer layer was Fe3+. The degradation pathways of PTSA were proposed, including methyl hydroxylation, sulfonyl hydroxylation, ß-hydrogen hydroxylation, and ring-opening reaction. These results demonstrate that the novel FEEF system is a promising technology for the removal of refractory organic pollutants from industrial wastewater.

Recent advances in electrocatalytic membrane for the removal of micropollutants from water and wastewater.

The increasing occurrence of micropollutants in water and wastewater threatens human health and ecological security. Electrocatalytic membrane (EM), a new hybrid water treatment platform that integrates membrane separation with electrochemical technologies, has attracted extensive attention in the removal of micropollutants from water and wastewater in the past decade. Here, we systematically review the recent advances of EM for micropollutant removal from water and wastewater. The mechanisms of the EM for micropollutant removal are first introduced. Afterwards, the related membrane materials and operating conditions of the EM are summarized and analyzed. Lastly, the challenges and future prospects of the EM in research and applications are also discussed, aiming at a more efficient removal of micropollutants from water and wastewater.

Recent advances in membrane biofilm reactor for micropollutants removal: Fundamentals, performance and microbial communities.

The occurrence of micropollutants (MPs) in water and wastewater imposes potential risks on ecological security and human health. Membrane biofilm reactor (MBfR), as an emerging technology, has attracted much attention for MPs removal from water and wastewater. The review aims to consolidate the recent advances in membrane biofilm reactor for MPs removal from the standpoint of fundamentals, removal performance and microbial communities. First, the configuration and working principles of MBfRs are reviewed prior to the discussion of the current status of the system. Thereafter, a comprehensive review of the MBfR performance for MPs elimination based on literature database is presented. Key information on the microbial communities that are of great significance for the removal performance is then synthesized. Perspectives on the future research needs are also provided in this review to ensure the development of MBfRs for more cost-effective elimination of MPs from water and wastewater.

Efficacy of a novel electrochemical membrane-aerated biofilm reactor for removal of antibiotics from micro-polluted surface water and suppression of antibiotic resistance genes.

An electrochemical membrane-aerated biofilm reactor (EMABR) was developed for removing sulfamethoxazole (SMX) and trimethoprim (TMP) from contaminated water. The exertion of electric field greatly enhanced the degradation of SMX and TMP in the EMABR (~60%) compared to membrane-aerated biofilm reactor (MABR, < 10%), due to the synergistic effects of the electro-oxidation (the generation of reactive oxygen species) and biological degradation. Microbial community analyses demonstrated that the EMABR enriched the genus of Xanthobacter, which was potentially capable of degrading aromatic intermediates. Moreover, the EMABR had a lower relative abundance of antibiotic resistance genes (ARGs) (0.23) compared to the MABR (0.56), suggesting the suppression of ARGs in the EMABR. Further, the SMX and TMP degradation pathways were proposed based on the detection of key intermediate products. This study demonstrated the potential of EMABR as an effective technology for removing antibiotics from micro-polluted surface water and suppressing the development of ARGs.

Efficacy of electrochemical membrane bioreactor for virus removal from wastewater: Performance and mechanisms.

Wastewater treatment facilities play pivotal roles in preventing the transmission of water-borne viruses and protecting human health. In this study, a new electrochemical membrane bioreactor (EMBR) was proposed to achieve a long-lasting and efficient removal of virus from wastewater. Results showed that applying a low electric field (2.0 V) in EMBR system could achieve ~100% removal efficiency at both batch tests and continuous flow experiments. In contrast, the control MBR, without the exertion of electric field, exhibited a very low removal efficiency (19.8% on average). Moreover, the fouling in EMBR was significantly mitigated, which enabled its operation duration almost 3 times longer than that of the control. Further explorations suggested that the reactive oxidants generated on electrodes in the EMBR system were mainly responsible for MS2 removal. This study demonstrated the potential of utilizing the EMBR process to achieve an enhanced virus disinfection efficiency during the wastewater treatment process.

Membrane Biofouling Control by Surface Modification of Quaternary Ammonium Compound Using Atom-Transfer Radical-Polymerization Method with Silica Nanoparticle as Interlayer.

A facile approach to fabricate antibiofouling membrane was developed by grafting quaternary ammonium compounds (QACs) onto polyvinylidene fluoride (PVDF) membrane via surface-initiated activators regenerated by electron transfer atom-transfer radical-polymerization (ARGET ATRP) method. During the modification process, a hydrophilic silica nanoparticle layer was also immobilized onto the membrane surface as an interlayer through silicification reaction for QAC grafting, which imparted the membrane with favorable surface properties (e.g., hydrophilic and negatively charged surface). The QAC-modified membrane (MQ) showed significantly improved hydrophilicity and permeability mainly due to the introduction of silica nanoparticles and exposure of hydrophilic quaternary ammonium groups instead of long alkyl chains. Furthermore, the coverage of QAC onto membrane surface enabled MQ membrane to have clear antibacterial effect, with an inhibition rate ~99.9% of Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive), respectively. According to the batch filtration test, MQ had better antibiofouling performance compared to the control membrane, which was ascribed to enhanced hydrophilicity and antibacterial activity. Furthermore, the MQ membrane also exhibited impressive stability of QAC upon suffering repeated fouling-cleaning tests. The modification protocols provide a new robust way to fabricate high-performance antibiofouling QAC-based membranes for wastewater treatment.

Enhanced removal of pharmaceuticals and personal care products from real municipal wastewater using an electrochemical membrane bioreactor.

A novel electrochemical membrane bioreactor (EMBR) was developed for enhancing PPCPs removal from real municipal wastewater. Compared to the control MBR (CMBR) without applying electric field, EMBR exhibited higher removal efficiencies for 14 PPCPs among all investigated PPCPs, including 3 fluoroquinolones, 2 macrolides, 6 sulfonamides and 3 anti-inflammatory drugs, while no significant difference was observed for the rest 8 PPCPs. The enhanced removal of 14 PPCPs was mainly attributed to electrooxidation by the direct anodic oxidation and reactive oxygen species-mediated indirect oxidation. Moreover, membrane fouling rates of EMBR (0.55 ± 0.10 kPa/d) were significantly reduced compared with CMBR (0.99 ± 0.09 kPa/d). Microbial activities and community analyses demonstrated that the applied electric field had no noticeable adverse impact on microbial viabilities, richness and diversity. These findings demonstrated that this EMBR enhanced pollutant removal and mitigated membrane fouling simultaneously, highlighting the potential of the novel technology to be used for removing PPCPs from wastewater.