Pub Date : 2025-03-13DOI: 10.1016/j.watres.2025.123489
Daoyuan Zu, Jianbo Liu, Heting Wei, Kui Yang, Hailin Tian, Jinxing Ma, Zhifeng Yang
Reductant-driven Fenton-like advanced oxidation processes (AOPs) offer the potential to reduce transition metal and oxidant consumption, but the environmental implications of introducing reductants remain unclear. This study employs life cycle assessment (LCA) to evaluate the environmental impacts of reductant-driven Fenton-like systems as an alternative to conventional AOP. Five distinct Fenton-like systems were investigated, and their corresponding life cycle inventories compiled following systematic optimization of operating parameters. Results demonstrate that introducing reductant shifts environmental hotspots from oxidants to the added reductants. Commodity chemical reductants (hydroxylamine and ascorbic acid) significantly reduce energy consumption and environmental damage due to economies of scale. Their per unit Cumulative Energy Demand (CED) and environmental damage value are two orders of magnitude lower than those of specialty chemical reductants (10.31 and 8.93 MJ g−1 MXene and MoS2). Thus, novel catalysts, potentially associated with high energy consumption and toxic byproducts, require careful evaluation of their catalytic efficiency and unit environmental impact to determine overall environmental benefits. Scaling up chemical production, adopting regeneration strategy and transitioning to renewable energy sources represent key strategies for further environmental improvement. This study provides a quantitative framework for assessing the environmental performance of alternative Fenton-like systems, informing the design of more environmentally sustainable water purification technologies.
{"title":"Comparative life cycle assessment of Fenton-like systems: Insights into the environmental benefits of reductant-driven strategies","authors":"Daoyuan Zu, Jianbo Liu, Heting Wei, Kui Yang, Hailin Tian, Jinxing Ma, Zhifeng Yang","doi":"10.1016/j.watres.2025.123489","DOIUrl":"https://doi.org/10.1016/j.watres.2025.123489","url":null,"abstract":"Reductant-driven Fenton-like advanced oxidation processes (AOPs) offer the potential to reduce transition metal and oxidant consumption, but the environmental implications of introducing reductants remain unclear. This study employs life cycle assessment (LCA) to evaluate the environmental impacts of reductant-driven Fenton-like systems as an alternative to conventional AOP. Five distinct Fenton-like systems were investigated, and their corresponding life cycle inventories compiled following systematic optimization of operating parameters. Results demonstrate that introducing reductant shifts environmental hotspots from oxidants to the added reductants. Commodity chemical reductants (hydroxylamine and ascorbic acid) significantly reduce energy consumption and environmental damage due to economies of scale. Their per unit Cumulative Energy Demand (CED) and environmental damage value are two orders of magnitude lower than those of specialty chemical reductants (10.31 and 8.93 MJ g<sup>−1</sup> MXene and MoS<sub>2</sub>). Thus, novel catalysts, potentially associated with high energy consumption and toxic byproducts, require careful evaluation of their catalytic efficiency and unit environmental impact to determine overall environmental benefits. Scaling up chemical production, adopting regeneration strategy and transitioning to renewable energy sources represent key strategies for further environmental improvement. This study provides a quantitative framework for assessing the environmental performance of alternative Fenton-like systems, informing the design of more environmentally sustainable water purification technologies.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"16 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608139","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.watres.2025.123497
Qiya Sun, Dunjie Li, Yunpeng He, Qian Ping, Lin Wang, Yongmei Li
This study developed a novel strategy combining a nanoscale zero-valent iron (nZVI)/peracetic acid (PAA) pretreatment and hydrochar regulation to enhance anaerobic digestion of waste activated sludge (WAS) under ammonia-stressed conditions. The strategy significantly enhanced methane production at ammonia concentrations below 3000 mg/L, with the regulation groups (AN3000/REG) achieving a 50.1% increase in cumulative methane yield. Metagenomic analysis demonstrated a 14.2% enrichment of key functional microorganisms, including syntrophic fatty acid-oxidizing bacteria and hydrogenotrophic methanogens, in the AN3000/REG groups. Some of them promote the conversion of butyrate and valerate to acetate through the upregulation of key genes in the fatty acid β-oxidation pathway, thereby supplying sufficient substrates for acetoclastic methanogenesis. Beyond enhancing acetoclastic methanogenesis, the AN3000/REG groups exhibited significant upregulation of other metabolic pathways, with a 34.2% increase in syntrophic acetate oxidation-hydrogenotrophic methanogenesis genes and a 17.1% increase in methanol/methylotrophic methanogenesis-related genes. These findings were further validated by the metatranscriptomic and metaproteomic combination analyses. Furthermore, the AN3000/REG groups exhibited a significant enhancement in direct interspecies electron transfer (DIET), with functional microbes (e.g., Geobacter, Methanosarcina, and Methanobacterium), pili, and cytochrome c showing significant increases of 1.38-fold, 12.7-fold, and 5.6-fold, respectively. This might be due to the synergistic effects of nZVI and hydrochar in the regulation groups. Additionally, metabolomic analyses revealed that the regulation strategy improved the microbial adaptability to ammonia stress by modulating metabolic products, such as alkaloids. Our study not only provides a promising strategy for alleviating ammonia inhibition during the anaerobic digestion of WAS but also provides a strong basis for understanding the underlying mechanism under ammonia-stressed conditions.
{"title":"Improved anaerobic digestion of waste activated sludge under ammonia stress by nanoscale zero-valent iron/peracetic acid pretreatment and hydrochar regulation: Insights from multi-omics analyses","authors":"Qiya Sun, Dunjie Li, Yunpeng He, Qian Ping, Lin Wang, Yongmei Li","doi":"10.1016/j.watres.2025.123497","DOIUrl":"https://doi.org/10.1016/j.watres.2025.123497","url":null,"abstract":"This study developed a novel strategy combining a nanoscale zero-valent iron (nZVI)/peracetic acid (PAA) pretreatment and hydrochar regulation to enhance anaerobic digestion of waste activated sludge (WAS) under ammonia-stressed conditions. The strategy significantly enhanced methane production at ammonia concentrations below 3000 mg/L, with the regulation groups (AN3000/REG) achieving a 50.1% increase in cumulative methane yield. Metagenomic analysis demonstrated a 14.2% enrichment of key functional microorganisms, including syntrophic fatty acid-oxidizing bacteria and hydrogenotrophic methanogens, in the AN3000/REG groups. Some of them promote the conversion of butyrate and valerate to acetate through the upregulation of key genes in the fatty acid β-oxidation pathway, thereby supplying sufficient substrates for acetoclastic methanogenesis. Beyond enhancing acetoclastic methanogenesis, the AN3000/REG groups exhibited significant upregulation of other metabolic pathways, with a 34.2% increase in syntrophic acetate oxidation-hydrogenotrophic methanogenesis genes and a 17.1% increase in methanol/methylotrophic methanogenesis-related genes. These findings were further validated by the metatranscriptomic and metaproteomic combination analyses. Furthermore, the AN3000/REG groups exhibited a significant enhancement in direct interspecies electron transfer (DIET), with functional microbes (e.g., Geobacter, Methanosarcina, and Methanobacterium), pili, and cytochrome c showing significant increases of 1.38-fold, 12.7-fold, and 5.6-fold, respectively. This might be due to the synergistic effects of nZVI and hydrochar in the regulation groups. Additionally, metabolomic analyses revealed that the regulation strategy improved the microbial adaptability to ammonia stress by modulating metabolic products, such as alkaloids. Our study not only provides a promising strategy for alleviating ammonia inhibition during the anaerobic digestion of WAS but also provides a strong basis for understanding the underlying mechanism under ammonia-stressed conditions.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"69 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.watres.2025.123495
Yongkai Xu, Shuang Hao, Dingxian Jia, Yiwen Qin, Jianxiao Wang, Jie Gao, Jun Xiao, Yunxia Hu
Carboxyl groups in polyamide (PA) reverse osmosis (RO) membrane contribute significantly to fouling and scaling, hindering the sustainable operation of RO in practical applications. Herein, we developed a novel interfacial polymerization (IP) strategy to finely engineer the molecular structure of PA with no carboxyl groups, and to significantly enhance RO membrane fouling/scaling-resistance. During IP, trimesoyl chloride (TMC) at the interface was consumed completely by the diffused m-phenylenediamine (MPD) and glycerol (GLY) under the assistance of benzalkonium chloride (BAC) surfactant. The fabricated RO membrane with no carboxyl groups exhibits sustainable anti-fouling performance with low flux decline ratios and high flux recovery ratios during the five cycles of fouling and cleaning when treating real coke wastewater, surpassing the reported anti-fouling membranes and the renowned commercial fouling-resistant RO membrane (DuPont FilmTec™ CR100). This work provides some insights to precisely tailor the molecular structure of PA RO membrane with sustainable anti-fouling performance.
{"title":"Carboxyl-free polyamide reverse osmosis membrane with sustainable anti-fouling performance in treating industrial coke wastewater","authors":"Yongkai Xu, Shuang Hao, Dingxian Jia, Yiwen Qin, Jianxiao Wang, Jie Gao, Jun Xiao, Yunxia Hu","doi":"10.1016/j.watres.2025.123495","DOIUrl":"10.1016/j.watres.2025.123495","url":null,"abstract":"<div><div>Carboxyl groups in polyamide (PA) reverse osmosis (RO) membrane contribute significantly to fouling and scaling, hindering the sustainable operation of RO in practical applications. Herein, we developed a novel interfacial polymerization (IP) strategy to finely engineer the molecular structure of PA with no carboxyl groups, and to significantly enhance RO membrane fouling/scaling-resistance. During IP, trimesoyl chloride (TMC) at the interface was consumed completely by the diffused m-phenylenediamine (MPD) and glycerol (GLY) under the assistance of benzalkonium chloride (BAC) surfactant. The fabricated RO membrane with no carboxyl groups exhibits sustainable anti-fouling performance with low flux decline ratios and high flux recovery ratios during the five cycles of fouling and cleaning when treating real coke wastewater, surpassing the reported anti-fouling membranes and the renowned commercial fouling-resistant RO membrane (DuPont FilmTec™ CR100). This work provides some insights to precisely tailor the molecular structure of PA RO membrane with sustainable anti-fouling performance.</div></div>","PeriodicalId":443,"journal":{"name":"Water Research","volume":"280 ","pages":"Article 123495"},"PeriodicalIF":11.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608140","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.watres.2025.123500
Zhipeng Yin , Min Zhang , Runzeng Liu , Yong Cai
The extensive use of per- and polyfluoroalkyl substances (PFAS) in industrial and consumer products poses health risks due to their toxicity. Computational toxicology approaches, particularly quantitative structure-activity relationship (QSAR) models are essential for predicting PFAS bioactivity. However, established QSAR models including machine learning-based ones with traditional molecular descriptors such as constitutional, topological, and geometric descriptors, have limited predictive capability and interpretability. Herein, we proposed a novel machine learning approach that leverages quantitative molecular surface analysis (QMSA) of molecular electrostatic potential. Using QMSA descriptors, five machine learning models (e.g., random forest) achieved outstanding performance, with best accuracy of 0.950 ± 0.017, AUC-ROC of 0.938 ± 0.012, F1-score of 0.734 ± 0.024, and MCC of 0.684 ± 0.111 for five targets (tyrosyl-DNA phosphodiesterase 1 in the absence/presence of camptothecin, ATXN2 protein, transcription factor SMAD3, and transcription factor NRF2), which outperform previously reported models. SHAP analyses revealed that estimated density, molecular volume, positive surface area, and nonpolar surface area were the most important descriptors. These descriptors were deeply involved in PFAS binding to target proteins via non-covalent interactions as evidenced by molecular docking and molecular dynamics simulations. Our results demonstrated that QMSA descriptors-based machine learning models are capable of predicting PFAS toxicity with extraordinary performance and interpretability. This study provides a novel machine learning framework for the high-throughput and cost-effective screening of high-risk emerging PFAS in aquatic environments. By identifying the contaminants that should be prioritized for regulation and treatment among the growing number of PFAS, our work aids in water quality monitoring and risk assessment, and guides decision-making in aquatic environmental management. Furthermore, this work enhances our understanding of the molecular mechanisms involved in PFAS bioactivity.
{"title":"Explainable machine learning models enhance prediction of PFAS bioactivity using quantitative molecular surface analysis-derived representation","authors":"Zhipeng Yin , Min Zhang , Runzeng Liu , Yong Cai","doi":"10.1016/j.watres.2025.123500","DOIUrl":"10.1016/j.watres.2025.123500","url":null,"abstract":"<div><div>The extensive use of per- and polyfluoroalkyl substances (PFAS) in industrial and consumer products poses health risks due to their toxicity. Computational toxicology approaches, particularly quantitative structure-activity relationship (QSAR) models are essential for predicting PFAS bioactivity. However, established QSAR models including machine learning-based ones with traditional molecular descriptors such as constitutional, topological, and geometric descriptors, have limited predictive capability and interpretability. Herein, we proposed a novel machine learning approach that leverages quantitative molecular surface analysis (QMSA) of molecular electrostatic potential. Using QMSA descriptors, five machine learning models (e.g., random forest) achieved outstanding performance, with best accuracy of 0.950 ± 0.017, AUC-ROC of 0.938 ± 0.012, F1-score of 0.734 ± 0.024, and MCC of 0.684 ± 0.111 for five targets (tyrosyl-DNA phosphodiesterase 1 in the absence/presence of camptothecin, ATXN2 protein, transcription factor SMAD3, and transcription factor NRF2), which outperform previously reported models. SHAP analyses revealed that estimated density, molecular volume, positive surface area, and nonpolar surface area were the most important descriptors. These descriptors were deeply involved in PFAS binding to target proteins via non-covalent interactions as evidenced by molecular docking and molecular dynamics simulations. Our results demonstrated that QMSA descriptors-based machine learning models are capable of predicting PFAS toxicity with extraordinary performance and interpretability. This study provides a novel machine learning framework for the high-throughput and cost-effective screening of high-risk emerging PFAS in aquatic environments. By identifying the contaminants that should be prioritized for regulation and treatment among the growing number of PFAS, our work aids in water quality monitoring and risk assessment, and guides decision-making in aquatic environmental management. Furthermore, this work enhances our understanding of the molecular mechanisms involved in PFAS bioactivity.</div></div>","PeriodicalId":443,"journal":{"name":"Water Research","volume":"280 ","pages":"Article 123500"},"PeriodicalIF":11.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143618577","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Heteronuclear diatomic engineering has been widely applied to generate selective or nonselective active species in Fenton-like system for wastewater treatment. However, active species adapted to diverse wastewater were different, and flexible control of active species has remained elusive, often necessitating complex and repetitive atom modifications. Here, we proposed a diatomic distance gating strategy that adjusted the spintronic structure of cobalt site for flexible transformation of high-valent cobalt-oxo and sulfate radical for adapted wastewater treatment. Electron paramagnetic resonance spectra, magnetic susceptibility-temperatur curve and partial density of states revealed electron transfer from dx2−y2, dz2 and dyz orbitals of high-spin cobalt to peroxymonosulfate for high-valent cobalt-oxo generation at 3.8 nm, and from dz2 orbital of medium-spin cobalt to peroxymonosulfate for sulfate radical generation at 2.5 nm. The Fenton-like system with 3.8 nm of diatomic distance preferentially degraded contaminants with low n-octanol/water partition constant and high ionization potential, while Fenton-like system with 2.5 nm of diatomic distance readily degraded contaminants with high Hammett substituent constant and low dissociation constant. This study elucidated the effect of diatomic distance on Fenton-like chemistry and provided a blueprint for the design of intelligent Fenton-like system for treating diverse wastewater treatment scenarios.
{"title":"Selective activation of peroxymonosulfate through gating heteronuclear diatomic distance for flexible generation of high-valent cobalt-oxo species or sulfate radicals","authors":"Jingjing Jiang, Yanan Zhang, Yansong Liu, Shengda Liu, Tongze Sun, Bowen Zhao, Ruixin Wang, Chongjun Zhang, Mingxin Huo, Dandan Zhou, Shuangshi Dong","doi":"10.1016/j.watres.2025.123488","DOIUrl":"https://doi.org/10.1016/j.watres.2025.123488","url":null,"abstract":"Heteronuclear diatomic engineering has been widely applied to generate selective or nonselective active species in Fenton-like system for wastewater treatment. However, active species adapted to diverse wastewater were different, and flexible control of active species has remained elusive, often necessitating complex and repetitive atom modifications. Here, we proposed a diatomic distance gating strategy that adjusted the spintronic structure of cobalt site for flexible transformation of high-valent cobalt-oxo and sulfate radical for adapted wastewater treatment. Electron paramagnetic resonance spectra, magnetic susceptibility-temperatur curve and partial density of states revealed electron transfer from <em>dx<sup>2</sup>−y<sup>2</sup>, dz<sup>2</sup></em> and <em>dyz</em> orbitals of high-spin cobalt to peroxymonosulfate for high-valent cobalt-oxo generation at 3.8 nm, and from <em>dz<sup>2</sup></em> orbital of medium-spin cobalt to peroxymonosulfate for sulfate radical generation at 2.5 nm. The Fenton-like system with 3.8 nm of diatomic distance preferentially degraded contaminants with low n-octanol/water partition constant and high ionization potential, while Fenton-like system with 2.5 nm of diatomic distance readily degraded contaminants with high Hammett substituent constant and low dissociation constant. This study elucidated the effect of diatomic distance on Fenton-like chemistry and provided a blueprint for the design of intelligent Fenton-like system for treating diverse wastewater treatment scenarios.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"21 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The response mechanism of microorganisms in partial denitrification (PD) system under antibiotic stress, particularly microbial energy metabolism and electron transfer, remain inadequately understood. This knowledge gap hinders the establishment of ecological links between microbial dynamics and macro-level reactor performance. To address this, moving bed biofilm reactors were employed to investigate the dynamic changes of microbial community and metabolism under sulfadiazine (SDZ) and ciprofloxacin (CIP) stress. Results showed that dosing 2 mg/L SDZ or CIP accelerated nitrite accumulation, achieving this milestone 15 days earlier than in the control group. At the end of the operational phase, nitrate removal efficiencies reached 90.3 ± 18.3 % (Control), 83.5 ± 16.2 % (SDZ-treated) and 93.9 ± 12.4 % (CIP-treated), with nitrate-to nitrite-transformation rates of 61.3 ± 12.7 %, 65.6 ± 13.1 % and 58.0 ± 21.2 %, respectively. The abundances of energy supply related genes, i.e., sucC and PK were higher in the CIP-treated group, while those in the other two groups were similar. The promoted tricarboxylic acid cycle and glycolysis led to NADH and ATP accumulation, accelerating nitrogen metabolism and benefiting early nitrite accumulation in the antibiotic-stressed system. More importantly, increasing antibiotics concentration from 2 mg/L to 4 mg/L induced selective migration of Thauera from floc to biofilm (abundance in floc reduced to < 2.01 %). Metagenomic sequencing indicated that the higher abundance of narGHI in biofilms, compared to flocs, was crucial for maintaining stable PD performance under antibiotic stress. The electron transport related genes, such as IDH1, DLD and DLAT, were more abundant in biofilms than in flocs after SDZ and CIP addition. These findings provide a theoretical basis for understanding the response mechanism of PD consortia to antibiotic.
{"title":"Antibiotics shape the core microbial community distribution between floc and biofilm in an endogenous partial denitrification system: Insight from metabolic pathway","authors":"Kai-Yue Dong, Chao-Xi Yang, Jin-Luo Pang, Rong-Rong Chang, Ke-Yu Chen, Wei Yao, Bao-Cheng Huang, Ren-Cun Jin","doi":"10.1016/j.watres.2025.123491","DOIUrl":"10.1016/j.watres.2025.123491","url":null,"abstract":"<div><div>The response mechanism of microorganisms in partial denitrification (PD) system under antibiotic stress, particularly microbial energy metabolism and electron transfer, remain inadequately understood. This knowledge gap hinders the establishment of ecological links between microbial dynamics and macro-level reactor performance. To address this, moving bed biofilm reactors were employed to investigate the dynamic changes of microbial community and metabolism under sulfadiazine (SDZ) and ciprofloxacin (CIP) stress. Results showed that dosing 2 mg/L SDZ or CIP accelerated nitrite accumulation, achieving this milestone 15 days earlier than in the control group. At the end of the operational phase, nitrate removal efficiencies reached 90.3 ± 18.3 % (Control), 83.5 ± 16.2 % (SDZ-treated) and 93.9 ± 12.4 % (CIP-treated), with nitrate-to nitrite-transformation rates of 61.3 ± 12.7 %, 65.6 ± 13.1 % and 58.0 ± 21.2 %, respectively. The abundances of energy supply related genes, i.e., <em>suc</em>C and <em>PK</em> were higher in the CIP-treated group, while those in the other two groups were similar. The promoted tricarboxylic acid cycle and glycolysis led to NADH and ATP accumulation, accelerating nitrogen metabolism and benefiting early nitrite accumulation in the antibiotic-stressed system. More importantly, increasing antibiotics concentration from 2 mg/L to 4 mg/L induced selective migration of <em>Thauera</em> from floc to biofilm (abundance in floc reduced to < 2.01 %). Metagenomic sequencing indicated that the higher abundance of <em>nar</em>GHI in biofilms, compared to flocs, was crucial for maintaining stable PD performance under antibiotic stress. The electron transport related genes, such as <em>IDH1, DLD</em> and <em>DLAT</em>, were more abundant in biofilms than in flocs after SDZ and CIP addition. These findings provide a theoretical basis for understanding the response mechanism of PD consortia to antibiotic.</div></div>","PeriodicalId":443,"journal":{"name":"Water Research","volume":"280 ","pages":"Article 123491"},"PeriodicalIF":11.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-12DOI: 10.1016/j.watres.2025.123486
Chencheng Dai , Kaixin Li , Yazi Liu , BoChen Teng , Qi Chen , Xin Jin , Dayong Xu , Ran Hong
Hydrated electrons (e−(aq)) are recognized for their potent reducing capabilities, making them significant in environmental engineering, particularly in the degradation of persistent pollutants like perfluoroalkyl compounds (PFCs). This study investigates the influence of attack direction of e−(aq) on the degradation mechanisms of PFCs, addressing a critical gap in understanding due to experimental limitations. Utilizing ab initio molecular dynamics and quantum chemical calculations, we systematically simulated the attack direction of e−(aq) on PFCs, focusing on the formation of anionic radicals and their excited-state reactivity. Our results indicate that the attack direction is pivotal for C-F bond cleavage: e−(aq) targeting the carboxyl end promotes effective bond cleavage, while approaches from the carbon-fluorine chain are hindered by molecular orbital shielding effects. Furthermore, we demonstrate that employing micellar systems to maintain PFCs in an unsolvated anionic state significantly reduces excitation energy, enhances red-shifted absorption, and increases excitation probability. Importantly, the excited-state electronic structure of PFCs closely mirrors that of their anionic radicals. These findings provide a novel strategy for improving the degradation of PFCs, thereby advancing treatment processes for persistent environmental pollutants and contributing to the broader understanding of water quality management.
{"title":"Unveiling the directional dynamics: Hydrated electron driven defluorination in PFOA⁻ and PFOS⁻ through ab Initio molecular dynamics and quantum chemistry","authors":"Chencheng Dai , Kaixin Li , Yazi Liu , BoChen Teng , Qi Chen , Xin Jin , Dayong Xu , Ran Hong","doi":"10.1016/j.watres.2025.123486","DOIUrl":"10.1016/j.watres.2025.123486","url":null,"abstract":"<div><div>Hydrated electrons (<em>e</em><sup>−</sup>(<em>aq</em>)) are recognized for their potent reducing capabilities, making them significant in environmental engineering, particularly in the degradation of persistent pollutants like perfluoroalkyl compounds (PFCs). This study investigates the influence of attack direction of <em>e</em><sup>−</sup>(<em>aq</em>) on the degradation mechanisms of PFCs, addressing a critical gap in understanding due to experimental limitations. Utilizing <em>ab initio</em> molecular dynamics and quantum chemical calculations, we systematically simulated the attack direction of <em>e</em><sup>−</sup>(<em>aq</em>) on PFCs, focusing on the formation of anionic radicals and their excited-state reactivity. Our results indicate that the attack direction is pivotal for C-F bond cleavage: <em>e</em><sup>−</sup>(<em>aq</em>) targeting the carboxyl end promotes effective bond cleavage, while approaches from the carbon-fluorine chain are hindered by molecular orbital shielding effects. Furthermore, we demonstrate that employing micellar systems to maintain PFCs in an unsolvated anionic state significantly reduces excitation energy, enhances red-shifted absorption, and increases excitation probability. Importantly, the excited-state electronic structure of PFCs closely mirrors that of their anionic radicals. These findings provide a novel strategy for improving the degradation of PFCs, thereby advancing treatment processes for persistent environmental pollutants and contributing to the broader understanding of water quality management.</div></div>","PeriodicalId":443,"journal":{"name":"Water Research","volume":"280 ","pages":"Article 123486"},"PeriodicalIF":11.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-12DOI: 10.1016/j.watres.2025.123471
Zhenkun Chu, Kemin Qi, Lusheng Yi, Yaqi Kang, Xiaoyun Xie, Yiru Zhao, Zhaowei Wang
Dissolved organic matter derived from microplastics (MPDOM) and biochar (BDOM), as examples of anthropogenic DOM, have received significant attention. Nonetheless, molecular fractionation particularly the detailed “kinetic architecture” and sequential assembly of MPDOM and BDOM at the mineral-water interface remains elusive, which significantly alters DOM composition and subsequent disinfection byproducts (DBPs) formation. This work systematically investigated these issues using FT-ICR MS, 2D-COS, PARAFAC analysis, and kinetic assays. For MPDOM, polyphenolics-like from plastic additives and breakdown products were rapidly adsorbed onto ferrihydrite, while combustion-derived condensed aromatics-like in BDOM exhibited priority adsorption. These results aligned with the equilibrium adsorption capacity for phenolics and condensed aromatics calculated by the Folin-Ciocalteu and benzenepolycarboxylic acid methods, 13.93 mg g-1 and 0.93 mgC g-1 for MPDOM, 3.66 mg g-1 and 7.16 mgC g-1 for BDOM, respectively. It suggested that mineral affinity of specific compounds relied on both molecular state and origin. The molecular fractionation driven by the co-action of “mineral-OM” and “OM-OM” interactions consequently eroded DBPs formation potential (21.77 % for MPDOM and 23.05 % for BDOM) by preferentially sequestering unsaturated and aromatic substances with higher chlorine reactivity. Our findings highlight molecular fractionation on minerals is a vital geochemical behavior regulating solid-liquid distribution and chlorine reactivity, advancing our understanding of anthropogenic carbon sequestration and cycling.
{"title":"Molecular Fractionation on Ferrihydrite Eroded the Disinfection Byproduct Formation Potential of Dissolved Organic Matter Derived from Microplastics and Biochar","authors":"Zhenkun Chu, Kemin Qi, Lusheng Yi, Yaqi Kang, Xiaoyun Xie, Yiru Zhao, Zhaowei Wang","doi":"10.1016/j.watres.2025.123471","DOIUrl":"https://doi.org/10.1016/j.watres.2025.123471","url":null,"abstract":"Dissolved organic matter derived from microplastics (MPDOM) and biochar (BDOM), as examples of anthropogenic DOM, have received significant attention. Nonetheless, molecular fractionation particularly the detailed “kinetic architecture” and sequential assembly of MPDOM and BDOM at the mineral-water interface remains elusive, which significantly alters DOM composition and subsequent disinfection byproducts (DBPs) formation. This work systematically investigated these issues using FT-ICR MS, 2D-COS, PARAFAC analysis, and kinetic assays. For MPDOM, polyphenolics-like from plastic additives and breakdown products were rapidly adsorbed onto ferrihydrite, while combustion-derived condensed aromatics-like in BDOM exhibited priority adsorption. These results aligned with the equilibrium adsorption capacity for phenolics and condensed aromatics calculated by the Folin-Ciocalteu and benzenepolycarboxylic acid methods, 13.93 mg g<sup>-1</sup> and 0.93 mgC g<sup>-1</sup> for MPDOM, 3.66 mg g<sup>-1</sup> and 7.16 mgC g<sup>-1</sup> for BDOM, respectively. It suggested that mineral affinity of specific compounds relied on both molecular state and origin. The molecular fractionation driven by the co-action of “mineral-OM” and “OM-OM” interactions consequently eroded DBPs formation potential (21.77 % for MPDOM and 23.05 % for BDOM) by preferentially sequestering unsaturated and aromatic substances with higher chlorine reactivity. Our findings highlight molecular fractionation on minerals is a vital geochemical behavior regulating solid-liquid distribution and chlorine reactivity, advancing our understanding of anthropogenic carbon sequestration and cycling.","PeriodicalId":443,"journal":{"name":"Water Research","volume":"32 1","pages":""},"PeriodicalIF":12.8,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-12DOI: 10.1016/j.watres.2025.123490
Yuanyuan Xu , Shiqi Tian , Susu Jiang , Jun Ma , Gang Wen
Various methods have been explored to activate potassium permanganate (Mn(VII)) for the elimination of organic compounds, typically by generating highly-reactive manganese species (RMnS) or mediated by electron transfer process (ETP). However, the oxidation selectivity, transformation pathways, toxicity byproduct potential, and efficacy in complicated water matrices associated with RMnS and ETP have not been comprehensively evaluated and compared, which is important for selecting a fit-of-purpose mechanism for water remediation. This study selected Mn(VII)/graphite process and ultraviolet (UV)/Mn(VII) process as the model ETP-dominated system and RMnS-dominated system, respectively. RMnS demonstrated significantly higher degradation efficiency for bromophenols, with oxidation rate constants 2.69–6.28 times higher than ETP. The oxidation efficiency of RMnS could be enhance under alkaline condition, whereas the degradation efficiency of ETP is dependent on the combined effects of solution pH and pKa of compounds. Furthermore, RMnS exhibited a stronger dehalogenation capacity, enabling the almost complete release of bromide ions from bromophenols with the formation of non-brominated organic product. Correspondingly, the RMnS process obviously reduced the brominated disinfection byproducts formation potential (DBPFPs). Mass spectrometry results revealed that the ETP process tended to form more polymeric brominated dimer products during the oxidation of bromophenol, leading to more DBPFPs production. ETP process showed superior degradation efficiency in real water backgrounds due to robustness against complicated water matrices, and displayed lower energy and oxidant consumption. Findings of this study elucidated the efficiency and mechanistic differences between RMnS and ETP, providing guidance for selecting activation methods to enhance KMnO4-based water treatment process.
{"title":"A comparative study of reactive manganese species and electron transfer pathway in oxidation efficiency and environmental impact: Which activation route for potassium permanganate is optimal?","authors":"Yuanyuan Xu , Shiqi Tian , Susu Jiang , Jun Ma , Gang Wen","doi":"10.1016/j.watres.2025.123490","DOIUrl":"10.1016/j.watres.2025.123490","url":null,"abstract":"<div><div>Various methods have been explored to activate potassium permanganate (Mn(VII)) for the elimination of organic compounds, typically by generating highly-reactive manganese species (RMnS) or mediated by electron transfer process (ETP). However, the oxidation selectivity, transformation pathways, toxicity byproduct potential, and efficacy in complicated water matrices associated with RMnS and ETP have not been comprehensively evaluated and compared, which is important for selecting a fit-of-purpose mechanism for water remediation. This study selected Mn(VII)/graphite process and ultraviolet (UV)/Mn(VII) process as the model ETP-dominated system and RMnS-dominated system, respectively. RMnS demonstrated significantly higher degradation efficiency for bromophenols, with oxidation rate constants 2.69–6.28 times higher than ETP. The oxidation efficiency of RMnS could be enhance under alkaline condition, whereas the degradation efficiency of ETP is dependent on the combined effects of solution pH and p<em>K</em>a of compounds. Furthermore, RMnS exhibited a stronger dehalogenation capacity, enabling the almost complete release of bromide ions from bromophenols with the formation of non-brominated organic product. Correspondingly, the RMnS process obviously reduced the brominated disinfection byproducts formation potential (DBPFPs). Mass spectrometry results revealed that the ETP process tended to form more polymeric brominated dimer products during the oxidation of bromophenol, leading to more DBPFPs production. ETP process showed superior degradation efficiency in real water backgrounds due to robustness against complicated water matrices, and displayed lower energy and oxidant consumption. Findings of this study elucidated the efficiency and mechanistic differences between RMnS and ETP, providing guidance for selecting activation methods to enhance KMnO<sub>4</sub>-based water treatment process.</div></div>","PeriodicalId":443,"journal":{"name":"Water Research","volume":"280 ","pages":"Article 123490"},"PeriodicalIF":11.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599412","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-12DOI: 10.1016/j.watres.2025.123492
Ran Yin , Xuan Hou , Senhao Lu , Chii Shang , Jinfeng Wang , Hongqiang Ren
While photo-based advanced oxidation processes (AOPs) are promising for the abatement of micropollutants in water and wastewater, they are inevitably influenced by the components of the background water matrix. As one of the major water matrix components, natural organic matter (NOM) generates photochemically produced reactive intermediates (PPRIs, e.g., 3NOM* and NOM•−) upon photolysis. PPRIs have recently been found to activate oxidants (e.g., H2O2) and generate reactive species (e.g., HO•), offering a novel and sustainable approach to degrade micropollutants in water. To facilitate the application of this NOM-mediated process, we summarize the fundamentals from the relevant literature, including PPRI generation, the mechanism of photosensitized activation of oxidants, performance of the processes for micropollutant degradation, and the factors influencing photosensitized activation. NOM•− is the PPRI activating H2O2 whereas the rest of the oxidants are primarily activated by 3NOM*. Resulting from the photosensitized activation, NOM and oxidant can exhibit synergism for micropollutant degradation under solar irradiation. Various factors, such as NOM properties, irradiation wavelength, pH, and other water matrix components (e.g., inorganic carbon and metal ions), affect the efficiency of photosensitized activation. Accordingly, we identify several future research directions: (1) investigating the wavelength dependency of photosensitized activation, (2) manipulating NOM structures in pre-treated processes, and (3) evaluating the formation of undesired byproducts.
{"title":"Making waves: Sustainable control of micropollutants via NOM-mediated photosensitized activation of oxidants","authors":"Ran Yin , Xuan Hou , Senhao Lu , Chii Shang , Jinfeng Wang , Hongqiang Ren","doi":"10.1016/j.watres.2025.123492","DOIUrl":"10.1016/j.watres.2025.123492","url":null,"abstract":"<div><div>While photo-based advanced oxidation processes (AOPs) are promising for the abatement of micropollutants in water and wastewater, they are inevitably influenced by the components of the background water matrix. As one of the major water matrix components, natural organic matter (NOM) generates photochemically produced reactive intermediates (PPRIs, e.g., <sup>3</sup>NOM* and NOM<sup>•−</sup>) upon photolysis. PPRIs have recently been found to activate oxidants (e.g., H<sub>2</sub>O<sub>2</sub>) and generate reactive species (e.g., HO<sup>•</sup>), offering a novel and sustainable approach to degrade micropollutants in water. To facilitate the application of this NOM-mediated process, we summarize the fundamentals from the relevant literature, including PPRI generation, the mechanism of photosensitized activation of oxidants, performance of the processes for micropollutant degradation, and the factors influencing photosensitized activation. NOM<sup>•−</sup> is the PPRI activating H<sub>2</sub>O<sub>2</sub> whereas the rest of the oxidants are primarily activated by <sup>3</sup>NOM*. Resulting from the photosensitized activation, NOM and oxidant can exhibit synergism for micropollutant degradation under solar irradiation. Various factors, such as NOM properties, irradiation wavelength, pH, and other water matrix components (e.g., inorganic carbon and metal ions), affect the efficiency of photosensitized activation. Accordingly, we identify several future research directions: (1) investigating the wavelength dependency of photosensitized activation, (2) manipulating NOM structures in pre-treated processes, and (3) evaluating the formation of undesired byproducts.</div></div>","PeriodicalId":443,"journal":{"name":"Water Research","volume":"280 ","pages":"Article 123492"},"PeriodicalIF":11.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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