Guanhong Chen,Yongmei Liang,Yundang Wu,Thomas Borch,Liping Fang,Fangbai Li
Anaerobic arsenic (As) methylation by fermentative microorganisms, particularly Clostridium-related populations, controls As speciation, mobility, and volatilization in flooded paddy soils, yet the mechanisms promoting this process remain poorly understood. Here, we reveal that phenazine- and phenoxazine-like redox mediators can enhance anaerobic As methylation via reshaping the intracellular electron allocation in a representative As-methylating fermentative bacterium. We integrated As speciation analysis, metabolite profiling, proteomics, and metabolic-flux modeling to determine how resazurin, as a represenative lipophilic redox mediator, reshapes fermentative metabolism and methylated As (MeAs) formation. The membrane-permeable redox mediator resazurin increased the apparent rate constant of MeAs formation by up to fourfold relative to the hydrophilic mediator anthraquinone-2,6-disulfonic acid (AQDS). Unlike AQDS, resazurin enhanced dimethylarsine formation while establishing a more reducing intracellular environment by diverting electrons from hydrogen evolution, indicating altered intracellular electron disposal. At the proteomic level, resazurin induced coordinated increases in As(III) methyltransferase (ArsM) and proteins involved in S-adenosylmethionine (SAM) biosynthesis, representing the primary molecular responses associated with enhanced As methylation. Proteins involved in amino-acid-fueled energy conservation and redox homeostasis were also enriched, potentially creating favorable cellular conditions for SAM-dependent As methylation. In a paddy-soil-derived fermentative consortium, resazurin likewise enhanced MeAs production and increased transcript levels of Clostridium-associated arsM and the SAM synthetase gene (metK). These findings identify lipophilicity-dependent, redox-compound-mediated intracellular electron flow reprogramming as a previously underappreciated control on anaerobic As methylation and provide a mechanistic basis for predicting MeAs formation in flooded soil environments.
{"title":"Lipophilic Redox Mediators Reprogram Intracellular Electron Flow to Promote Arsenic Methylation in Soil Fermentative Bacteria","authors":"Guanhong Chen,Yongmei Liang,Yundang Wu,Thomas Borch,Liping Fang,Fangbai Li","doi":"10.1021/acs.est.6c11234","DOIUrl":"https://doi.org/10.1021/acs.est.6c11234","url":null,"abstract":"Anaerobic arsenic (As) methylation by fermentative microorganisms, particularly Clostridium-related populations, controls As speciation, mobility, and volatilization in flooded paddy soils, yet the mechanisms promoting this process remain poorly understood. Here, we reveal that phenazine- and phenoxazine-like redox mediators can enhance anaerobic As methylation via reshaping the intracellular electron allocation in a representative As-methylating fermentative bacterium. We integrated As speciation analysis, metabolite profiling, proteomics, and metabolic-flux modeling to determine how resazurin, as a represenative lipophilic redox mediator, reshapes fermentative metabolism and methylated As (MeAs) formation. The membrane-permeable redox mediator resazurin increased the apparent rate constant of MeAs formation by up to fourfold relative to the hydrophilic mediator anthraquinone-2,6-disulfonic acid (AQDS). Unlike AQDS, resazurin enhanced dimethylarsine formation while establishing a more reducing intracellular environment by diverting electrons from hydrogen evolution, indicating altered intracellular electron disposal. At the proteomic level, resazurin induced coordinated increases in As(III) methyltransferase (ArsM) and proteins involved in S-adenosylmethionine (SAM) biosynthesis, representing the primary molecular responses associated with enhanced As methylation. Proteins involved in amino-acid-fueled energy conservation and redox homeostasis were also enriched, potentially creating favorable cellular conditions for SAM-dependent As methylation. In a paddy-soil-derived fermentative consortium, resazurin likewise enhanced MeAs production and increased transcript levels of Clostridium-associated arsM and the SAM synthetase gene (metK). These findings identify lipophilicity-dependent, redox-compound-mediated intracellular electron flow reprogramming as a previously underappreciated control on anaerobic As methylation and provide a mechanistic basis for predicting MeAs formation in flooded soil environments.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"7 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281813","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}
Mengjie Liu,Baofeng Zhu,Nigel J. D. Graham,William A. Mitch,Wenzheng Yu
Unplanned potable reuse introduces effluent-derived organic matter (EfOM) into drinking water sources. While conventional coagulation partially removes EfOM, the residual fraction undergoes chlorination and may form toxic disinfection byproducts (DBPs) that escape current monitoring. However, the molecular mechanisms by which EfOM alters DBP formation pathways remain poorly understood. Here, we combine ultrahigh-resolution mass spectrometry with reaction network analysis to reveal that EfOM significantly redirects chlorine pathways. Compared to EfOM-free surface water, the presence of 20% EfOM decreases direct halogenation pathways (addition and substitution) from 4.2% to 1.8% of total transformation events. This shift occurs because EfOM introduces reduced, high-molecular-weight, heteroatom-rich molecules that cannot be directly halogenated; they require HOCl-driven oxidative fragmentation to generate halogenation-susceptible intermediates. Consequently, chlorinated finished water accumulates sulfur-containing DBPs (CHOS compounds, with relative intensity increasing from 35% to 60%) and complex “orphan” DBPs lacking identifiable precursors (with molecular features linked to elevated toxicity). These findings highlight an urgent need to update DBP monitoring frameworks to include unregulated sulfur-containing and orphan byproducts in de facto reuse scenarios.
{"title":"Unregulated Disinfection Byproducts from de facto Water Reuse: Molecular Evidence for EfOM-Induced Redirection of Chlorination Pathways","authors":"Mengjie Liu,Baofeng Zhu,Nigel J. D. Graham,William A. Mitch,Wenzheng Yu","doi":"10.1021/acs.est.6c07214","DOIUrl":"https://doi.org/10.1021/acs.est.6c07214","url":null,"abstract":"Unplanned potable reuse introduces effluent-derived organic matter (EfOM) into drinking water sources. While conventional coagulation partially removes EfOM, the residual fraction undergoes chlorination and may form toxic disinfection byproducts (DBPs) that escape current monitoring. However, the molecular mechanisms by which EfOM alters DBP formation pathways remain poorly understood. Here, we combine ultrahigh-resolution mass spectrometry with reaction network analysis to reveal that EfOM significantly redirects chlorine pathways. Compared to EfOM-free surface water, the presence of 20% EfOM decreases direct halogenation pathways (addition and substitution) from 4.2% to 1.8% of total transformation events. This shift occurs because EfOM introduces reduced, high-molecular-weight, heteroatom-rich molecules that cannot be directly halogenated; they require HOCl-driven oxidative fragmentation to generate halogenation-susceptible intermediates. Consequently, chlorinated finished water accumulates sulfur-containing DBPs (CHOS compounds, with relative intensity increasing from 35% to 60%) and complex “orphan” DBPs lacking identifiable precursors (with molecular features linked to elevated toxicity). These findings highlight an urgent need to update DBP monitoring frameworks to include unregulated sulfur-containing and orphan byproducts in de facto reuse scenarios.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"23 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149272025","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}
Sectoral decarbonization can substantially reshape the quantity and composition of industrial solid waste and its associated resource recovery potential, yet how these changes evolve along decarbonization pathways remains poorly understood. Here, we develop a sectoral transition framework linking future waste generation, recycling technologies, life cycle environmental impacts, and societal benefits. We focus on the steel and power sectors, which represent major industrial solid waste sources and distinct decarbonization pathways across six major producing regions from 2025 to 2050. By 2050, steel sector wastes remain at 0.61–0.78 Gt, whereas power sector wastes decline from 1.11 Gt in 2025 to 0.17–0.50 Gt. Under four scenarios, cumulative mitigation ranges from 25.68 to 53.39 Gt CO2-eq, with discounted net societal benefits of USD 11.24–23.81 trillion. Steel sector benefits are sensitive to recycling technology shares, whereas power sector benefits are more strongly shaped by transition-driven changes in the waste generation and composition. These findings highlight the importance of integrating evolving waste flows and technology choices into long-term decarbonization and circular economy strategies.
{"title":"Industrial Solid Wastes Recycling from Steel and Power Sectors Delivers Climate and Net Societal Benefits","authors":"Wenjun Xie,Yuli Shan,Yimeng Ding,Yuying Wu,Miaomiao Liu,Zongwei Ma,Jianxun Yang,Jun Bi,Wen Fang","doi":"10.1021/acs.est.6c09991","DOIUrl":"https://doi.org/10.1021/acs.est.6c09991","url":null,"abstract":"Sectoral decarbonization can substantially reshape the quantity and composition of industrial solid waste and its associated resource recovery potential, yet how these changes evolve along decarbonization pathways remains poorly understood. Here, we develop a sectoral transition framework linking future waste generation, recycling technologies, life cycle environmental impacts, and societal benefits. We focus on the steel and power sectors, which represent major industrial solid waste sources and distinct decarbonization pathways across six major producing regions from 2025 to 2050. By 2050, steel sector wastes remain at 0.61–0.78 Gt, whereas power sector wastes decline from 1.11 Gt in 2025 to 0.17–0.50 Gt. Under four scenarios, cumulative mitigation ranges from 25.68 to 53.39 Gt CO2-eq, with discounted net societal benefits of USD 11.24–23.81 trillion. Steel sector benefits are sensitive to recycling technology shares, whereas power sector benefits are more strongly shaped by transition-driven changes in the waste generation and composition. These findings highlight the importance of integrating evolving waste flows and technology choices into long-term decarbonization and circular economy strategies.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"7 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281885","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}
Persistent and problematic toxic metal and metalloid pollutants (in particular, As, Hg, Pb, Cd, and Cr) have long been challenging and expensive remediation targets in contaminated surface and subsurface environments. Since the advent of environmental regulations and cleanup in the late 20th century, much progress has been made to address sites of legacy metal pollution and limit new contamination. Despite this, metal pollution remains a global problem, particularly in soils and sediments, with many large legacy sites inadequately remediated, metal contamination widespread in developed and developing nations, and new pollution occurring from informal and often illegal extraction and recycling processes. In this perspective, we highlight advances and challenges in science and technology, and key economic and social factors, that have influenced remediation of these “pesky” metals over the last ∼50 years. Through this lens, we consider emerging challenges and opportunities associated with legacy and critical metals, climate resilience, and sustainability.
{"title":"Pesky Metals: Historical Perspective, Advances, and Challenges for Remediation of Problematic Metal Contaminants","authors":"Peggy A. O’Day,Marc Beutel,Dimitri Vlassopoulos","doi":"10.1021/acs.est.6c08900","DOIUrl":"https://doi.org/10.1021/acs.est.6c08900","url":null,"abstract":"Persistent and problematic toxic metal and metalloid pollutants (in particular, As, Hg, Pb, Cd, and Cr) have long been challenging and expensive remediation targets in contaminated surface and subsurface environments. Since the advent of environmental regulations and cleanup in the late 20th century, much progress has been made to address sites of legacy metal pollution and limit new contamination. Despite this, metal pollution remains a global problem, particularly in soils and sediments, with many large legacy sites inadequately remediated, metal contamination widespread in developed and developing nations, and new pollution occurring from informal and often illegal extraction and recycling processes. In this perspective, we highlight advances and challenges in science and technology, and key economic and social factors, that have influenced remediation of these “pesky” metals over the last ∼50 years. Through this lens, we consider emerging challenges and opportunities associated with legacy and critical metals, climate resilience, and sustainability.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"5 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149272023","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}
Timo Diepers,Jan Tautorus,Jan Marcus Hartmann,Niklas von der Assen
Life cycle optimization (LCO) selects optimal processes and supply chains from a set of alternatives given environmental constraints and objectives, supporting the design of sustainable systems and their transitions. However, current approaches rely on static assumptions, overlooking two interacting temporal dimensions: temporal distribution (flows are spread over time) and temporal evolution (processes and supply chains change over time). Because distribution and evolution jointly dictate the magnitude of a flow at a given time, both must be considered simultaneously to accurately optimize against cumulative environmental impacts and time-specific environmental constraints. We present a framework for time-explicit LCO that captures these interdependencies to determine optimal transition pathways. The framework tracks flow timing relative to process installation and dynamically determines flow magnitudes from time-specific process parameters and background supply chains. A case study on integrated methanol and pig iron production demonstrates how time-explicit LCO enables optimization against time-resolved environmental impacts and constraints, revealing mitigation strategies inaccessible to static approaches: prioritizing early high-efficiency technology installation to idle older processes as operational savings outweigh embodied impacts of stranded assets, and avoiding transient resource bottlenecks through diversification. To facilitate widespread application, we provide the open-source Python package optimex, enabling practitioners to design transition pathways that rigorously respect environmental limits.
{"title":"A Framework for Time-Explicit Life Cycle Optimization","authors":"Timo Diepers,Jan Tautorus,Jan Marcus Hartmann,Niklas von der Assen","doi":"10.1021/acs.est.6c06868","DOIUrl":"https://doi.org/10.1021/acs.est.6c06868","url":null,"abstract":"Life cycle optimization (LCO) selects optimal processes and supply chains from a set of alternatives given environmental constraints and objectives, supporting the design of sustainable systems and their transitions. However, current approaches rely on static assumptions, overlooking two interacting temporal dimensions: temporal distribution (flows are spread over time) and temporal evolution (processes and supply chains change over time). Because distribution and evolution jointly dictate the magnitude of a flow at a given time, both must be considered simultaneously to accurately optimize against cumulative environmental impacts and time-specific environmental constraints. We present a framework for time-explicit LCO that captures these interdependencies to determine optimal transition pathways. The framework tracks flow timing relative to process installation and dynamically determines flow magnitudes from time-specific process parameters and background supply chains. A case study on integrated methanol and pig iron production demonstrates how time-explicit LCO enables optimization against time-resolved environmental impacts and constraints, revealing mitigation strategies inaccessible to static approaches: prioritizing early high-efficiency technology installation to idle older processes as operational savings outweigh embodied impacts of stranded assets, and avoiding transient resource bottlenecks through diversification. To facilitate widespread application, we provide the open-source Python package optimex, enabling practitioners to design transition pathways that rigorously respect environmental limits.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"6 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149272022","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}
Sarah Bancel,Anabelle Espeyte,João Sousa,Maxime Leprêtre,Rémi Recoura-Massaquant,Nicolas Delorme,Laura Garnero,Hervé Quéau,Hélène Budzinski,Sophie Ayciriex,Arnaud Salvador,Arnaud Chaumot,Olivier Geffard,Davide Degli Esposti
Complex mixtures of contaminants can affect aquatic organisms through diverse modes of action, making extrapolations of laboratory findings to field conditions complex. Here, we show that proteomics combined with active biomonitoring may inform about reprotoxic effects in the sentinel species Gammarus fossarum. Proteomic responses provide information on the diversity of underlying mechanisms and may serve as a sensitive early warning signal of reprotoxicity. Females were exposed in situ in 18 French surveillance sites and analyzed for reproductive end points and proteomic levels in the caeca and the ovaries. This study aimed to assess links between reproductive impairment and molecular responses, using the complementary information provided by both tissues. Protein coexpression analysis identified protein clusters associated with organ functions, reproductive impairments, or field exposure. Several modules were significantly associated with field condition or females’ physiological integrity. Interestingly, we identified a large diversity of biological pathways modulated in impacted females exposed to reprotoxic sites, with reproduction-related proteins as potential early biomarkers of reprotoxicity. These results highlight the relevance of considering field conditions and individual physiology within the eco-exposome framework and demonstrate the value of integrating omics and active biomonitoring to uncover diverse molecular signature behind field-induced reprotoxicity in this sentinel species.
{"title":"Proteomic Profiling for In Situ Exposure in a Sentinel Freshwater Species to Describe the Crustacean Reproductive Effects of Aquatic Contamination","authors":"Sarah Bancel,Anabelle Espeyte,João Sousa,Maxime Leprêtre,Rémi Recoura-Massaquant,Nicolas Delorme,Laura Garnero,Hervé Quéau,Hélène Budzinski,Sophie Ayciriex,Arnaud Salvador,Arnaud Chaumot,Olivier Geffard,Davide Degli Esposti","doi":"10.1021/acs.est.6c10136","DOIUrl":"https://doi.org/10.1021/acs.est.6c10136","url":null,"abstract":"Complex mixtures of contaminants can affect aquatic organisms through diverse modes of action, making extrapolations of laboratory findings to field conditions complex. Here, we show that proteomics combined with active biomonitoring may inform about reprotoxic effects in the sentinel species Gammarus fossarum. Proteomic responses provide information on the diversity of underlying mechanisms and may serve as a sensitive early warning signal of reprotoxicity. Females were exposed in situ in 18 French surveillance sites and analyzed for reproductive end points and proteomic levels in the caeca and the ovaries. This study aimed to assess links between reproductive impairment and molecular responses, using the complementary information provided by both tissues. Protein coexpression analysis identified protein clusters associated with organ functions, reproductive impairments, or field exposure. Several modules were significantly associated with field condition or females’ physiological integrity. Interestingly, we identified a large diversity of biological pathways modulated in impacted females exposed to reprotoxic sites, with reproduction-related proteins as potential early biomarkers of reprotoxicity. These results highlight the relevance of considering field conditions and individual physiology within the eco-exposome framework and demonstrate the value of integrating omics and active biomonitoring to uncover diverse molecular signature behind field-induced reprotoxicity in this sentinel species.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"8 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149281893","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}
Jianmin Zou,Yihui Zhang,Mengzhe Zhao,Yixin Huang,Shuwen Yan,Weihua Song
Solar-driven activation of peroxymonosulfate (PMS) is a promising advanced oxidation process for water and wastewater treatment; however, the kinetics of emerging contaminant removal in real water matrices remain poorly understood. In this study, we investigated PMS photosensitization in three environmentally relevant water matrices and evaluated its role in the abatement of 42 pharmaceuticals and personal care products (PPCPs). Under simulated solar irradiation, CDOM promoted PMS transformation and generated multiple photochemically produced reactive intermediates (PPRIs). A multiple-probe chemical method was employed to quantify the cumulative exposure doses of HO•, SO4•–, Cl2•–, CO3•–, and 1O2. Across the tested matrices, PPRI exposure doses followed the order CO3•– > 1O2 > Cl2•– ∼ SO4•– > HO•. The measured PPRI exposure doses, together with second-order rate constants, reasonably predicted PPCP removal in the solar/PMS/CDOM system. For several phenolic and aniline-containing PPCPs, DOM-mediated inhibition was observed and was attributed to reductive back-reaction of one-electron oxidation intermediates; incorporating inhibition factors improved the agreement between calculated and experimental removal efficiencies. Furthermore, four commonly detected PPCPs, sucralose, metformin, caffeine, and carbamazepine, were first identified as practical indicator compounds for estimating PPRI exposure without adding external probe chemicals. These findings provide a mechanistic framework for predicting PPCP attenuation during solar/PMS treatment in CDOM-rich waters and highlight the importance of secondary radicals in real aquatic matrices.
{"title":"Solar Activation of Peroxymonosulfate by Chromophoric Dissolved Organic Matter Enables Predictable Micropollutant Attenuation in Real Waters","authors":"Jianmin Zou,Yihui Zhang,Mengzhe Zhao,Yixin Huang,Shuwen Yan,Weihua Song","doi":"10.1021/acs.est.6c09034","DOIUrl":"https://doi.org/10.1021/acs.est.6c09034","url":null,"abstract":"Solar-driven activation of peroxymonosulfate (PMS) is a promising advanced oxidation process for water and wastewater treatment; however, the kinetics of emerging contaminant removal in real water matrices remain poorly understood. In this study, we investigated PMS photosensitization in three environmentally relevant water matrices and evaluated its role in the abatement of 42 pharmaceuticals and personal care products (PPCPs). Under simulated solar irradiation, CDOM promoted PMS transformation and generated multiple photochemically produced reactive intermediates (PPRIs). A multiple-probe chemical method was employed to quantify the cumulative exposure doses of HO•, SO4•–, Cl2•–, CO3•–, and 1O2. Across the tested matrices, PPRI exposure doses followed the order CO3•– > 1O2 > Cl2•– ∼ SO4•– > HO•. The measured PPRI exposure doses, together with second-order rate constants, reasonably predicted PPCP removal in the solar/PMS/CDOM system. For several phenolic and aniline-containing PPCPs, DOM-mediated inhibition was observed and was attributed to reductive back-reaction of one-electron oxidation intermediates; incorporating inhibition factors improved the agreement between calculated and experimental removal efficiencies. Furthermore, four commonly detected PPCPs, sucralose, metformin, caffeine, and carbamazepine, were first identified as practical indicator compounds for estimating PPRI exposure without adding external probe chemicals. These findings provide a mechanistic framework for predicting PPCP attenuation during solar/PMS treatment in CDOM-rich waters and highlight the importance of secondary radicals in real aquatic matrices.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"5 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149272008","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}
Guanju Zhuang,Shiyun Xu,Wenwen Xu,Yanyang Zhang,Zhichao Yang,Xiaolin Zhang,Bingcai Pan
Calcium phosphate (Ca–P) scaling, which is ubiquitous in nature and in water systems, has been shown to interfere with the capture of phosphate by ferric oxide-based sorbents, thereby deteriorating their decontamination performance in repeated cycles. Here, we show that a specifically designed gel-type nanocomposite, namely HFO@N201, enables Ca-enhanced phosphate sequestration while restricting Ca–P scaling via nanoconfinement. Increasing the initial Ca2+ concentration from 0 to 160 mg/L improved phosphate uptake from ∼4.5 to ∼6.2 mg/g in the first cycle. After 20 adsorption-regeneration cycles, phosphate uptake remained at ∼6.4 mg/g in the Ca-containing system, twice that of ∼3.2 mg/g in the Ca-free system. In fixed-bed tests, the presence of Ca2+ enhanced the working capacity from ∼1350 to ∼1800 bed volumes, which could be observed again in the subsequent cycle. Asynchronous release of Fe, P, and Ca during acidic elution of P-loaded HFO@N201 indicates heterogeneous and nonstoichiometric Ca-associated phosphate retention rather than formation of a mature bulk Ca–P phase. XRD, TEM, EXAFS, and Mössbauer spectroscopy further show that the retained Ca–P species remained weakly ordered and that the nanosized ferrihydrite-like Fe phase persisted during cyclic operation. Thermodynamic analysis, classical nucleation theory, and molecular dynamics simulations further support that the nanoconfinement structure of HFO@N201 (∼2 nm) creates a low-mobility hydration environment that restricts solvent exchange, ion rearrangement, and long-range ordering, thereby stabilizing Ca–P species in a weakly ordered interfacial state. Our work demonstrates nanoconfinement as a strategy to exploit Ca-enhanced phosphate capture while reducing Ca–P scaling in regenerable sorbents.
{"title":"Nanoconfinement Decouples Calcium-Enhanced Phosphate Capture from Calcium Phosphate Crystal Maturation","authors":"Guanju Zhuang,Shiyun Xu,Wenwen Xu,Yanyang Zhang,Zhichao Yang,Xiaolin Zhang,Bingcai Pan","doi":"10.1021/acs.est.6c11456","DOIUrl":"https://doi.org/10.1021/acs.est.6c11456","url":null,"abstract":"Calcium phosphate (Ca–P) scaling, which is ubiquitous in nature and in water systems, has been shown to interfere with the capture of phosphate by ferric oxide-based sorbents, thereby deteriorating their decontamination performance in repeated cycles. Here, we show that a specifically designed gel-type nanocomposite, namely HFO@N201, enables Ca-enhanced phosphate sequestration while restricting Ca–P scaling via nanoconfinement. Increasing the initial Ca2+ concentration from 0 to 160 mg/L improved phosphate uptake from ∼4.5 to ∼6.2 mg/g in the first cycle. After 20 adsorption-regeneration cycles, phosphate uptake remained at ∼6.4 mg/g in the Ca-containing system, twice that of ∼3.2 mg/g in the Ca-free system. In fixed-bed tests, the presence of Ca2+ enhanced the working capacity from ∼1350 to ∼1800 bed volumes, which could be observed again in the subsequent cycle. Asynchronous release of Fe, P, and Ca during acidic elution of P-loaded HFO@N201 indicates heterogeneous and nonstoichiometric Ca-associated phosphate retention rather than formation of a mature bulk Ca–P phase. XRD, TEM, EXAFS, and Mössbauer spectroscopy further show that the retained Ca–P species remained weakly ordered and that the nanosized ferrihydrite-like Fe phase persisted during cyclic operation. Thermodynamic analysis, classical nucleation theory, and molecular dynamics simulations further support that the nanoconfinement structure of HFO@N201 (∼2 nm) creates a low-mobility hydration environment that restricts solvent exchange, ion rearrangement, and long-range ordering, thereby stabilizing Ca–P species in a weakly ordered interfacial state. Our work demonstrates nanoconfinement as a strategy to exploit Ca-enhanced phosphate capture while reducing Ca–P scaling in regenerable sorbents.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"254 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149272019","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}
Noor Hamdan,John Qian,Sarah Prasek,Ian Pepper,Carsten Prasse
The widespread use of biosolids as an agricultural soil amendment has raised concerns about the release of organic contaminants into the environment. This study identifies biosolids-associated organic contaminants (BOCs) in soils from municipal biosolid-amended plots across the United States. Soil samples were collected from 18 sites in 15 states, representing biosolids applications from the 1980s to the present. Samples were taken at three depths (30, 90, and 180 cm) from plots with no, low, and high application histories. Samples were extracted using QuEChERS and analyzed by liquid chromatography–high-resolution mass spectrometry (LC-HRMS) using a nontargeted analysis (NTA) approach. A total of 111 BOCs were detected across biosolid-amended plots. BOCs were detected most frequently in surface soils (30 cm), with significantly fewer detections at subsurface depths (p < 0.001). Cumulative loading rate and application frequency were significant predictors of the number of BOCs detected (p = 0.003 and p = 0.017, respectively). Quality-adjusted hazard scores for human health, ecological impact, and environmental fate identified 4-nitrophenol (44%), PFBS (41%), and miconazole (38%), among others as the highest-priority BOCs. This NTA-hazard prioritization workflow provides a strategy for identifying compounds warranting further evaluation for potential environmental and human health risks.
{"title":"Nontargeted Identification and Prioritization of Organic Contaminants in Biosolid-Amended Soils across the United States","authors":"Noor Hamdan,John Qian,Sarah Prasek,Ian Pepper,Carsten Prasse","doi":"10.1021/acs.est.6c13101","DOIUrl":"https://doi.org/10.1021/acs.est.6c13101","url":null,"abstract":"The widespread use of biosolids as an agricultural soil amendment has raised concerns about the release of organic contaminants into the environment. This study identifies biosolids-associated organic contaminants (BOCs) in soils from municipal biosolid-amended plots across the United States. Soil samples were collected from 18 sites in 15 states, representing biosolids applications from the 1980s to the present. Samples were taken at three depths (30, 90, and 180 cm) from plots with no, low, and high application histories. Samples were extracted using QuEChERS and analyzed by liquid chromatography–high-resolution mass spectrometry (LC-HRMS) using a nontargeted analysis (NTA) approach. A total of 111 BOCs were detected across biosolid-amended plots. BOCs were detected most frequently in surface soils (30 cm), with significantly fewer detections at subsurface depths (p < 0.001). Cumulative loading rate and application frequency were significant predictors of the number of BOCs detected (p = 0.003 and p = 0.017, respectively). Quality-adjusted hazard scores for human health, ecological impact, and environmental fate identified 4-nitrophenol (44%), PFBS (41%), and miconazole (38%), among others as the highest-priority BOCs. This NTA-hazard prioritization workflow provides a strategy for identifying compounds warranting further evaluation for potential environmental and human health risks.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"4 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149272016","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 effect of oxidation degree on sludge dewaterability during oxone-induced preoxidation was investigated. The optimal oxone concentration increased free cells and membrane permeabilization while limiting cell lysis, releasing bound water, and producing a drier sludge cake without reducing the filtrate volume. Dewaterability enhancement was mainly driven by the shift of low-molecular-weight proteins and polysaccharides (<20 kDa) from intracellular polymeric substances (IPS) to extracellular polymeric substances (EPS), along with selective degradation of hydrophilic glucose and peptidoglycan in EPS. Organic matter transferred to the outer EPS layer was mainly derived from the cellular constituents of Gram-negative bacteria in sludge. Importantly, IPS was found to exert a distinct and non-negligible influence on sludge dewatering with its oxidative response fundamentally differing from that of EPS. As the oxidation intensity increased, the ratio of protein to polysaccharide rose in loosely bound EPS but declined in IPS, whereas carboxyl and lactone groups decreased in both soluble and loosely bound EPS fractions, while carboxyl groups concurrently increased within IPS. IPS contained more hydrophobic components than did EPS at all oxone concentrations. Excessive oxidation induced cell disruption and hydrophilic debris, impairing sludge dewaterability. Cell membrane permeabilization, rather than cell lysis, was the key factor affecting sludge dewaterability.
{"title":"Unraveling the Bound-Water Removal Mystery: Preoxidation Enhances Sludge Dewatering via Cell Permeabilization and Transformation of Intracellular Polymeric Substances to Extracellular Polymeric Substances","authors":"Yizhang Jiang,Eran Friedler,Yikun Geng,Yan Zhou,Ling Tan,Keke Xiao","doi":"10.1021/acs.est.6c14464","DOIUrl":"https://doi.org/10.1021/acs.est.6c14464","url":null,"abstract":"The effect of oxidation degree on sludge dewaterability during oxone-induced preoxidation was investigated. The optimal oxone concentration increased free cells and membrane permeabilization while limiting cell lysis, releasing bound water, and producing a drier sludge cake without reducing the filtrate volume. Dewaterability enhancement was mainly driven by the shift of low-molecular-weight proteins and polysaccharides (<20 kDa) from intracellular polymeric substances (IPS) to extracellular polymeric substances (EPS), along with selective degradation of hydrophilic glucose and peptidoglycan in EPS. Organic matter transferred to the outer EPS layer was mainly derived from the cellular constituents of Gram-negative bacteria in sludge. Importantly, IPS was found to exert a distinct and non-negligible influence on sludge dewatering with its oxidative response fundamentally differing from that of EPS. As the oxidation intensity increased, the ratio of protein to polysaccharide rose in loosely bound EPS but declined in IPS, whereas carboxyl and lactone groups decreased in both soluble and loosely bound EPS fractions, while carboxyl groups concurrently increased within IPS. IPS contained more hydrophobic components than did EPS at all oxone concentrations. Excessive oxidation induced cell disruption and hydrophilic debris, impairing sludge dewaterability. Cell membrane permeabilization, rather than cell lysis, was the key factor affecting sludge dewaterability.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"253 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149272010","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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