Zixi Zhang,Chaolong Liu,Zhixing Huang,Kaisong Xiang,Fenghua Shen,Hui Liu
Atmospheric elemental mercury (Hg0) emitted from the nonferrous metallurgy industry poses severe risks to ecosystems. Although metal sulfides are promising in Hg0 adsorption under high-concentration SO2 conditions, they typically suffer from poor performance at elevated temperatures due to weak binding affinity. Herein, a trivalent iron (Fe3+) activation strategy to boost Hg0 adsorption activity of metal sulfides was developed for the first time, which leverages electron-deficient Fe3+ to induce electronic reconstruction. This Fe3+ activation strategy is applicable to various metal sulfides, generating Fe sites with high activity and stability. Among the various candidates, the Fe3+-activated MoS2 delivers a record-theoretical saturated Hg0 adsorption capacity of 69.56 mg·g–1 at 150 °C, which is 4.35 times higher than that of pristine MoS2. The sulfur vacancies on MoS2 serve as the key anchoring sites for Fe3+, generating stable single-atom, dimer, and trimer Fe configurations. These new Fe centers, benefiting from charge modulation, can simultaneously adsorb two Hg atoms via charge transfer and orbital hybridization. The Fe3+-activated MoS2 exhibits strong resistance to SO2 and H2O, maintaining high Hg0 removal efficiency under a smelting gas atmosphere. This work reveals new configurations of Hg adsorption and provides a convenient route to design high-performance sorbents for heavy metal purification.
{"title":"Fe3+ Activation of Metal Sulfides for High-Performance Mercury Removal from Nonferrous Smelting Gas: A Dual Mercury Adsorption Mechanism","authors":"Zixi Zhang,Chaolong Liu,Zhixing Huang,Kaisong Xiang,Fenghua Shen,Hui Liu","doi":"10.1021/acs.est.6c09451","DOIUrl":"https://doi.org/10.1021/acs.est.6c09451","url":null,"abstract":"Atmospheric elemental mercury (Hg0) emitted from the nonferrous metallurgy industry poses severe risks to ecosystems. Although metal sulfides are promising in Hg0 adsorption under high-concentration SO2 conditions, they typically suffer from poor performance at elevated temperatures due to weak binding affinity. Herein, a trivalent iron (Fe3+) activation strategy to boost Hg0 adsorption activity of metal sulfides was developed for the first time, which leverages electron-deficient Fe3+ to induce electronic reconstruction. This Fe3+ activation strategy is applicable to various metal sulfides, generating Fe sites with high activity and stability. Among the various candidates, the Fe3+-activated MoS2 delivers a record-theoretical saturated Hg0 adsorption capacity of 69.56 mg·g–1 at 150 °C, which is 4.35 times higher than that of pristine MoS2. The sulfur vacancies on MoS2 serve as the key anchoring sites for Fe3+, generating stable single-atom, dimer, and trimer Fe configurations. These new Fe centers, benefiting from charge modulation, can simultaneously adsorb two Hg atoms via charge transfer and orbital hybridization. The Fe3+-activated MoS2 exhibits strong resistance to SO2 and H2O, maintaining high Hg0 removal efficiency under a smelting gas atmosphere. This work reveals new configurations of Hg adsorption and provides a convenient route to design high-performance sorbents for heavy metal purification.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"12 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221658","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}
In this study, a long-term atmospheric observation of HFC-23, -32, -125, -134a, -143a, and -152a was conducted at six background stations across China from 2011 to 2023. Using a tracer ratio method with HCFC-22 as the reference, emissions from four main economic regions, Northeast Plain (NEP), North China Plain (NCP), Yangtze River Delta (YRD), and Central South China (CSC), were estimated, and their trends were analyzed over four phases: Phase 1 (2012–2016), Phase 2 (2017–2018), Phase 3 (2019–2020), and Phase 4 (2021–2023). The results show that from 2011 to 2023, the atmospheric mixing ratios of all studied HFCs except HFC-152a exhibited increasing trends. Nationally, emissions of HFC-23 show a decreasing tendency during Phase 4, while emissions of HFC-32, -125, -134a, and -143a continued to rise throughout Phases 3 and 4. These four HFCs were identified as the dominant species, accounting for over 76% of total HFCs’ mass emissions. From Phase 3 to Phase 4, CO2-equivalent HFC emissions per capita increased slightly, whereas emissions per unit GDP decreased, which is mainly attributable to significant HFC reductions in the CSC region. Nevertheless, China’s average HFC emission intensities (whether calculated per unit GDP or per capita) remain approximately 1.5–1.6 times the global average.
{"title":"Atmospheric Concentrations and Emissions of Major HFCs at Six Background Stations in China during 2012–2023","authors":"Chen Wang,Wanqi Sun,Bo Yang,Dongqiao Wu,Ningzhang Wang,Qianli Ma,Peng Wang,Liyan Zhou,Haiyang Cai,Zhen Li,Lixin Liu","doi":"10.1021/acs.est.6c08334","DOIUrl":"https://doi.org/10.1021/acs.est.6c08334","url":null,"abstract":"In this study, a long-term atmospheric observation of HFC-23, -32, -125, -134a, -143a, and -152a was conducted at six background stations across China from 2011 to 2023. Using a tracer ratio method with HCFC-22 as the reference, emissions from four main economic regions, Northeast Plain (NEP), North China Plain (NCP), Yangtze River Delta (YRD), and Central South China (CSC), were estimated, and their trends were analyzed over four phases: Phase 1 (2012–2016), Phase 2 (2017–2018), Phase 3 (2019–2020), and Phase 4 (2021–2023). The results show that from 2011 to 2023, the atmospheric mixing ratios of all studied HFCs except HFC-152a exhibited increasing trends. Nationally, emissions of HFC-23 show a decreasing tendency during Phase 4, while emissions of HFC-32, -125, -134a, and -143a continued to rise throughout Phases 3 and 4. These four HFCs were identified as the dominant species, accounting for over 76% of total HFCs’ mass emissions. From Phase 3 to Phase 4, CO2-equivalent HFC emissions per capita increased slightly, whereas emissions per unit GDP decreased, which is mainly attributable to significant HFC reductions in the CSC region. Nevertheless, China’s average HFC emission intensities (whether calculated per unit GDP or per capita) remain approximately 1.5–1.6 times the global average.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"1 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221665","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}
Olivine-based ocean alkalinity enhancement (OAE) is a promising carbon dioxide removal technology; however, the geochemical fate of olivine-derived toxic metals, particularly nickel (Ni) and chromium (Cr) at marine sediment interfaces, remains poorly constrained. We employed dialysis-membrane microcosms to isolate olivine from Mn oxides, allowing only dissolved species to diffuse and react under three olivine loadings (1, 5, and 10 g L–1) in seawater for 60 days. Results revealed that (1) Ni was preferentially sequestered by the Mn oxides, with δ-MnO2 showing higher uptake capacity than birnessite, (2) Cr was co-sequestered with secondary Fe(III) (oxyhydr)oxides rather than adsorbing directly onto Mn oxides, and (3) synergistic Ni2+ isomorphic substitution and Fe(II)-driven Mn(III) reduction rearranged δ-MnO2 into a more stable hexagonal layered framework. Consequently, both δ-MnO2 and birnessite act as long-term Ni sinks, preventing Ni remobilization via desorption or diagenetic phase transitions. These findings support a proposed “spatial decoupling” OAE strategy, where olivine is pre-dissolved in land- or ship-based reactors to remove Cr via Fe co-precipitation. Subsequent discharge of the Ni-bearing alkaline effluent into shallow coastal regions allows benthic Mn oxides to scavenge Ni, reducing toxicity risks associated with direct mineral contact.
橄榄石基海洋碱度增强（OAE）是一种很有前途的二氧化碳脱除技术；然而，橄榄石衍生的有毒金属，特别是镍（Ni）和铬（Cr）在海洋沉积物界面的地球化学命运仍然知之甚少。我们采用透析膜显微法从锰氧化物中分离橄榄石，只允许溶解的橄榄石在海水中三种橄榄石负荷（1、5和10 g L-1）下扩散和反应60天。结果表明：(1)Ni优先被Mn氧化物吸附，δ-MnO2比birnite具有更高的吸附能力；(2)Cr与次级Fe(III)（氧）氧化物共同吸附，而不是直接吸附在Mn氧化物上；(3)协同Ni2+同构取代和Fe（II）驱动的Mn（III）还原将δ-MnO2重新排列成更稳定的六边形层状框架。因此，δ-MnO2和硼钼矿都是长期的镍汇，通过解吸或成岩相变阻止了镍的再活化。这些发现支持了“空间解耦”OAE策略，将橄榄石预先溶解在陆上或船上的反应器中，通过铁共沉淀去除Cr。随后将含镍碱性废水排放到浅海沿岸地区，使底底锰氧化物能够清除镍，从而降低与矿物直接接触相关的毒性风险。
{"title":"Divergent Responses of Manganese Oxides to Olivine Dissolution and Their Control on Trace Metal Fates under an Ocean Alkalinity Enhancement Scenario","authors":"Wen Zhuang,Feng Li,Xiaotong Wang,Jihua Liu","doi":"10.1021/acs.est.6c12947","DOIUrl":"https://doi.org/10.1021/acs.est.6c12947","url":null,"abstract":"Olivine-based ocean alkalinity enhancement (OAE) is a promising carbon dioxide removal technology; however, the geochemical fate of olivine-derived toxic metals, particularly nickel (Ni) and chromium (Cr) at marine sediment interfaces, remains poorly constrained. We employed dialysis-membrane microcosms to isolate olivine from Mn oxides, allowing only dissolved species to diffuse and react under three olivine loadings (1, 5, and 10 g L–1) in seawater for 60 days. Results revealed that (1) Ni was preferentially sequestered by the Mn oxides, with δ-MnO2 showing higher uptake capacity than birnessite, (2) Cr was co-sequestered with secondary Fe(III) (oxyhydr)oxides rather than adsorbing directly onto Mn oxides, and (3) synergistic Ni2+ isomorphic substitution and Fe(II)-driven Mn(III) reduction rearranged δ-MnO2 into a more stable hexagonal layered framework. Consequently, both δ-MnO2 and birnessite act as long-term Ni sinks, preventing Ni remobilization via desorption or diagenetic phase transitions. These findings support a proposed “spatial decoupling” OAE strategy, where olivine is pre-dissolved in land- or ship-based reactors to remove Cr via Fe co-precipitation. Subsequent discharge of the Ni-bearing alkaline effluent into shallow coastal regions allows benthic Mn oxides to scavenge Ni, reducing toxicity risks associated with direct mineral contact.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"73 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221657","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}
Organophosphate esters (OPEs) are ubiquitous marine contaminants that raise global concern. While surface inputs are well-studied, the role of subsurface transport remains poorly constrained. Submarine groundwater discharge (SGD) drives seawater-groundwater interactions, yet its impact on OPEs behavior remains overlooked. This study comprehensively investigates the distribution, transport property and sources of OPEs from coastal groundwater to seawater in the Beibu Gulf, China. No statistically significant difference in Σ19OPEs levels was found between groundwater and tidal flat porewater, while both matrices exhibited significantly higher levels than seawater. The high compositional similarity, strong correlations (p < 0.01) and PCA overlap of OPEs in different waters, as well as their shared source profiles indicated the transport potential of OPEs from groundwater to seawater. Multiple statistical modeling integrating OPEs, environmental factors and DOM components reveals the land-to-sea transport pathways and biogeochemical processes of OPEs via SGD. Furthermore, radon isotope analysis verified the presence of SGD, offering evidence for SGD-mediated OPE transport. For the first time, this work integrates pollutant investigation, multiple statistical analysis, and radionuclide tracing, to identify SGD as a previously underestimated vector of coastal OPEs and elucidates its potential transport mechanisms, providing crucial support for integrated land-sea management and risk assessment.
{"title":"Submarine Groundwater Discharge Acts as a Significant Vector for Coastal Organophosphate Esters: Joint Evidence from Pollution Surveys and Radionuclide Analysis","authors":"Li Zhang,Xiang Li,Xinhui He,Xuemin Feng,Bochao Xu,Shuo Yu,Luqi Zhang,Lu Lu,Qinglong Liang,Kaiyuan Guo,Zhenming Zheng","doi":"10.1021/acs.est.6c11341","DOIUrl":"https://doi.org/10.1021/acs.est.6c11341","url":null,"abstract":"Organophosphate esters (OPEs) are ubiquitous marine contaminants that raise global concern. While surface inputs are well-studied, the role of subsurface transport remains poorly constrained. Submarine groundwater discharge (SGD) drives seawater-groundwater interactions, yet its impact on OPEs behavior remains overlooked. This study comprehensively investigates the distribution, transport property and sources of OPEs from coastal groundwater to seawater in the Beibu Gulf, China. No statistically significant difference in Σ19OPEs levels was found between groundwater and tidal flat porewater, while both matrices exhibited significantly higher levels than seawater. The high compositional similarity, strong correlations (p < 0.01) and PCA overlap of OPEs in different waters, as well as their shared source profiles indicated the transport potential of OPEs from groundwater to seawater. Multiple statistical modeling integrating OPEs, environmental factors and DOM components reveals the land-to-sea transport pathways and biogeochemical processes of OPEs via SGD. Furthermore, radon isotope analysis verified the presence of SGD, offering evidence for SGD-mediated OPE transport. For the first time, this work integrates pollutant investigation, multiple statistical analysis, and radionuclide tracing, to identify SGD as a previously underestimated vector of coastal OPEs and elucidates its potential transport mechanisms, providing crucial support for integrated land-sea management and risk assessment.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"231 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210885","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}
{"title":"Correspondence on “Legacy and Emerging Plasticizers and Stabilizers in PVC Floorings and Implications for Recycling”","authors":"Christopher J. Howick","doi":"10.1021/acs.est.6c04712","DOIUrl":"https://doi.org/10.1021/acs.est.6c04712","url":null,"abstract":"","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"62 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221660","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}
Nitrogen-containing organic compounds (NOCs) are ubiquitous in the troposphere and contribute to the reactive nitrogen cycle and aerosol light absorption, yet their formation mechanisms remain unclear, especially in polluted regions. Here, we characterized NOCs in PM2.5 during winter haze in the North China Plain (NCP), with a comparison to those in the Sichuan Basin (ScB). Reduced-nitrogen NOCs (Re-NOCs) accounted for 40% of organics detected in the ESI+ mode, highlighting their importance within atmospheric NOCs. Compared to dry haze (DH) in NCP, high-molecular-weight (HMW, m/z > 250) Re-NOCs in humid haze (HH) were enhanced, which positively correlated with NH+4 and the mass ratio of aqueous-phase secondary organic aerosols to total water-soluble organic aerosols, along with increases in aliphatic chain length and molecular unsaturation, indicating carbonyl-amino-driven oligomerization and cyclization. Aliphatic Re-NOCs dominated the Re-NOCs during HH, together with strong correlations of a typical NOC oligomer (C8H13N3O2) with water-soluble organic nitrogen and HMW Re-NOCs, further suggesting oligomerization as a key formation pathway for NOCs. We found that stronger aerosol acidity and higher temperature favored oligomerization of Re-NOCs compared to cyclization, resulting in enhanced C8H13N3O2 in ScB relative to that in NCP. Our work revealed oligomerization as a critical mechanism shaping the NOC composition, particularly HMW species.
{"title":"Aqueous Carbonyl-Amino Aggregation Drives Atmospheric Nitrogen-Containing Oligomer Formation in China Haze","authors":"Binyu Xiao,Chenlong Liang,Gehui Wang,Rongjie Li,Luyao Chen,Zheng Li,Haoyang Wang,Can Wu,Jingjing Meng,Yunfei Wu,Renjian Zhang","doi":"10.1021/acs.est.6c09940","DOIUrl":"https://doi.org/10.1021/acs.est.6c09940","url":null,"abstract":"Nitrogen-containing organic compounds (NOCs) are ubiquitous in the troposphere and contribute to the reactive nitrogen cycle and aerosol light absorption, yet their formation mechanisms remain unclear, especially in polluted regions. Here, we characterized NOCs in PM2.5 during winter haze in the North China Plain (NCP), with a comparison to those in the Sichuan Basin (ScB). Reduced-nitrogen NOCs (Re-NOCs) accounted for 40% of organics detected in the ESI+ mode, highlighting their importance within atmospheric NOCs. Compared to dry haze (DH) in NCP, high-molecular-weight (HMW, m/z > 250) Re-NOCs in humid haze (HH) were enhanced, which positively correlated with NH+4 and the mass ratio of aqueous-phase secondary organic aerosols to total water-soluble organic aerosols, along with increases in aliphatic chain length and molecular unsaturation, indicating carbonyl-amino-driven oligomerization and cyclization. Aliphatic Re-NOCs dominated the Re-NOCs during HH, together with strong correlations of a typical NOC oligomer (C8H13N3O2) with water-soluble organic nitrogen and HMW Re-NOCs, further suggesting oligomerization as a key formation pathway for NOCs. We found that stronger aerosol acidity and higher temperature favored oligomerization of Re-NOCs compared to cyclization, resulting in enhanced C8H13N3O2 in ScB relative to that in NCP. Our work revealed oligomerization as a critical mechanism shaping the NOC composition, particularly HMW species.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"55 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210883","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}
Renoxification of nitrate to reactive nitrogen species (RNS) can sustain atmospheric oxidant production. Because nitrate and light-absorbing brown carbon can coexist in biomass burning (BB) plumes, their photochemical interaction may alter RNS cycling. Furthermore, nitration of phenols in biomass burning organic aerosol (BBOA) can form nitrophenols, potentially increasing the warming effect of aged BBOA. Yet the mechanisms of renoxification and nitration in irradiated nitrate-BBOA mixtures remain poorly understood. We experimentally investigate these coupled processes over a wide range of fir-wood BBOA concentrations during aqueous nitrate photolysis (10 mM) under acidic conditions using H2SO4. At low BBOA concentration (TOCBBOA/NO3– ≤ 0.0036 mg L–1/mg L–1), the steady-state production rate of HONO (Pss_HONO) increased as BBOA concentration increased, reaching a maximum enhancement factor of 1.8 driven primarily by triplet-mediated photosensitized reduction of NO2 to HONO. At higher BBOA concentration (TOCBBOA/NO3– > 0.0036 mg L–1/mg L–1), Pss_HONO progressively decreased and was nearly fully suppressed at TOCBBOA/NO3– = 0.7 mg L–1/mg L–1. This inhibition is attributed to reactions of aqueous HNO2/NO2 with phenols, accompanied by formation of nitrophenols. These findings point to a potentially overlooked daytime HONO source and an atmospheric source of nitrophenols, a key class of BrC chromophores, via photochemical interactions between nitrate photolysis and photosensitization of BBOA.
{"title":"Photochemical Interactions of Nitrate Photolysis and Photosensitization of BBOA: Enhanced HONO Production and the Formation of Nitrophenols","authors":"Ruifeng Zhang,Yong Jie Li,Chak K. Chan","doi":"10.1021/acs.est.6c13970","DOIUrl":"https://doi.org/10.1021/acs.est.6c13970","url":null,"abstract":"Renoxification of nitrate to reactive nitrogen species (RNS) can sustain atmospheric oxidant production. Because nitrate and light-absorbing brown carbon can coexist in biomass burning (BB) plumes, their photochemical interaction may alter RNS cycling. Furthermore, nitration of phenols in biomass burning organic aerosol (BBOA) can form nitrophenols, potentially increasing the warming effect of aged BBOA. Yet the mechanisms of renoxification and nitration in irradiated nitrate-BBOA mixtures remain poorly understood. We experimentally investigate these coupled processes over a wide range of fir-wood BBOA concentrations during aqueous nitrate photolysis (10 mM) under acidic conditions using H2SO4. At low BBOA concentration (TOCBBOA/NO3– ≤ 0.0036 mg L–1/mg L–1), the steady-state production rate of HONO (Pss_HONO) increased as BBOA concentration increased, reaching a maximum enhancement factor of 1.8 driven primarily by triplet-mediated photosensitized reduction of NO2 to HONO. At higher BBOA concentration (TOCBBOA/NO3– > 0.0036 mg L–1/mg L–1), Pss_HONO progressively decreased and was nearly fully suppressed at TOCBBOA/NO3– = 0.7 mg L–1/mg L–1. This inhibition is attributed to reactions of aqueous HNO2/NO2 with phenols, accompanied by formation of nitrophenols. These findings point to a potentially overlooked daytime HONO source and an atmospheric source of nitrophenols, a key class of BrC chromophores, via photochemical interactions between nitrate photolysis and photosensitization of BBOA.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"1 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210889","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}
Xinkai Wang,Yiyi Li,Qifan Liu,Yongcheng Li,Li Li,Ling Ruan,Wei Liu,Yufeng Gong,Yuhe He
Novel organophosphate esters (OPEs), formed through chemical transformation of commercial antioxidants, are emerging contaminants with widespread environmental occurrence and potential health effects. Despite their widespread detection, the atmospheric reactivity, persistence, and transformation of novel OPEs remain unknown. Here, the heterogeneous OH oxidation of two surface-bound novel OPEs [tris(2,4-ditert-butylphenyl) phosphate (TDtBPP) and triisodecyl phosphate (TiDeP)] was explored by investigating the reaction kinetics and chemical mechanisms. The measured heterogeneous rate constants for TDtBPP and TiDeP were (2.81 ± 0.12) × 10–12 and (1.99 ± 0.16) × 10–12 cm3 molecules–1 s–1, respectively, equivalent to atmospheric lifetimes of up to 6.3 and 9.0 days. These lifetimes are significantly longer than previously predicted values (<1 day), suggesting that they are much more persistent in air than predicted. Based on UPLC-HRMS measurements, 22 transformation products from the heterogeneous reactions were identified for the first time. Analysis of atmospheric particle samples from two megacities in China identified four TDtBPP transformation products, demonstrating that the oxidation chemistry can occur under genuine environmental conditions. In-silico hazard screening further indicated that many transformation products may be more bioaccumulative and more toxic than the parent novel OPEs. The results not only provide new insights into the atmospheric persistence of novel OPEs but also underscore the significance of considering atmospheric transformation in the risk assessment of these emerging contaminants.
{"title":"OH-Initiated Heterogeneous Reactions of Novel Organophosphate Esters: Insights into Oxidation Chemistry and Atmospheric Persistence","authors":"Xinkai Wang,Yiyi Li,Qifan Liu,Yongcheng Li,Li Li,Ling Ruan,Wei Liu,Yufeng Gong,Yuhe He","doi":"10.1021/acs.est.6c12069","DOIUrl":"https://doi.org/10.1021/acs.est.6c12069","url":null,"abstract":"Novel organophosphate esters (OPEs), formed through chemical transformation of commercial antioxidants, are emerging contaminants with widespread environmental occurrence and potential health effects. Despite their widespread detection, the atmospheric reactivity, persistence, and transformation of novel OPEs remain unknown. Here, the heterogeneous OH oxidation of two surface-bound novel OPEs [tris(2,4-ditert-butylphenyl) phosphate (TDtBPP) and triisodecyl phosphate (TiDeP)] was explored by investigating the reaction kinetics and chemical mechanisms. The measured heterogeneous rate constants for TDtBPP and TiDeP were (2.81 ± 0.12) × 10–12 and (1.99 ± 0.16) × 10–12 cm3 molecules–1 s–1, respectively, equivalent to atmospheric lifetimes of up to 6.3 and 9.0 days. These lifetimes are significantly longer than previously predicted values (<1 day), suggesting that they are much more persistent in air than predicted. Based on UPLC-HRMS measurements, 22 transformation products from the heterogeneous reactions were identified for the first time. Analysis of atmospheric particle samples from two megacities in China identified four TDtBPP transformation products, demonstrating that the oxidation chemistry can occur under genuine environmental conditions. In-silico hazard screening further indicated that many transformation products may be more bioaccumulative and more toxic than the parent novel OPEs. The results not only provide new insights into the atmospheric persistence of novel OPEs but also underscore the significance of considering atmospheric transformation in the risk assessment of these emerging contaminants.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"12 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149221661","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}
David Haaf,Michael McGlade,Athena A. Nghiem,Duyen Thi Vu,Tobias Steinert,Viet Hung Pham,Linh Khanh Bui,Thanh Ngoc Tong,Duong Du Bui,Andrea Stenke,Michael Berg,Lenny H. E. Winkel
Abstract Elevated arsenic concentrations in groundwater pose health risks. Geogenic arsenic contamination is driven by biogeochemical mobilization and groundwater dynamics. Intensive pumping can initially exacerbate contamination by drawing arsenic or mobilizing organic matter into aquifers, but over longer time scales may also promote dilution and flushing in some settings. To better understand the mechanisms controlling arsenic concentrations, we examined changes over two decades in Hanoi (Vietnam), a hotspot of geogenic arsenic contamination and groundwater pumping. Arsenic concentrations from 470 wells sampled in the year 2000 were compared with 434 wells sampled in the same area in 2013 and 2023. Median concentrations declined from 14 to 8 μg/L between 2000 and 2023, while mean concentrations and the proportion of high-arsenic wells (>100 μg/L) remained similar. Using hydrochemical and groundwater-level data, CatBoost models combined with SHAP analysis assessed changes in predictor importance. In 2000, arsenic was more strongly associated with redox predictors, whereas groundwater-level predictors became more important in 2023. Within wells used to evaluate groundwater-level change (n = 251), larger decadal declines were associated with lower arsenic concentrations (median = 31 μg/L) than wells without declines (median = 120 μg/L). We hypothesize a decadal mechanism shift, from redox to hydrological controls, particularly driving arsenic declines.
{"title":"Modeled\u0000Groundwater Decline is Associated with Lower\u0000Arsenic Concentrations in Hanoi","authors":"David Haaf,Michael McGlade,Athena A. Nghiem,Duyen Thi Vu,Tobias Steinert,Viet Hung Pham,Linh Khanh Bui,Thanh Ngoc Tong,Duong Du Bui,Andrea Stenke,Michael Berg,Lenny H. E. Winkel","doi":"10.1021/acs.est.6c07700","DOIUrl":"https://doi.org/10.1021/acs.est.6c07700","url":null,"abstract":"Abstract Elevated arsenic concentrations in groundwater pose health risks. Geogenic arsenic contamination is driven by biogeochemical mobilization and groundwater dynamics. Intensive pumping can initially exacerbate contamination by drawing arsenic or mobilizing organic matter into aquifers, but over longer time scales may also promote dilution and flushing in some settings. To better understand the mechanisms controlling arsenic concentrations, we examined changes over two decades in Hanoi (Vietnam), a hotspot of geogenic arsenic contamination and groundwater pumping. Arsenic concentrations from 470 wells sampled in the year 2000 were compared with 434 wells sampled in the same area in 2013 and 2023. Median concentrations declined from 14 to 8 μg/L between 2000 and 2023, while mean concentrations and the proportion of high-arsenic wells (&gt;100 μg/L) remained similar. Using hydrochemical and groundwater-level data, CatBoost models combined with SHAP analysis assessed changes in predictor importance. In 2000, arsenic was more strongly associated with redox predictors, whereas groundwater-level predictors became more important in 2023. Within wells used to evaluate groundwater-level change (n = 251), larger decadal declines were associated with lower arsenic concentrations (median = 31 μg/L) than wells without declines (median = 120 μg/L). We hypothesize a decadal mechanism shift, from redox to hydrological controls, particularly driving arsenic declines.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"37 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149209895","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}
He Cai,Thomas Neill,Katherine Morris,Anthony Stockdale,Samuel Shaw
Technetium-99 is a long-lived, high-yield fission product whose solubility is controlled by redox conditions. Here, to explore targeted effluent treatment approaches, pertechnetate (Tc(VII)O4–) reductive retention as Tc(IV) during coprecipitation of Fe(II)-doped Ni–Al–CO3 layered double hydroxide (LDH) was investigated. During LDH formation via base addition to an acidic Ni2+, Al3+, Fe2+, and Tc(VII)O4– bearing solution, there was essentially complete TcO4– removal at low (9.6 Bq/mL) and high (2.9 kBq/mL) concentrations. Characterization of experiments using X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and X-ray absorption spectroscopy (XAS) confirmed that, during base titration, a two-stage process occurred, with Al3+ forming amorphous Al (hydr)oxide between pH 4 and 6 in the first stage, followed by hydrolysis of Fe2+/Ni2+ and formation of LDH particles between pH 6 and 9 in stage two. During the first stage, TcO4– was removed from solution, and XAS confirmed it was reduced to Tc(IV) by Fe(II) associated with the amorphous Al (hydr)oxide, forming hydrous Tc(IV)O2-like chains on the Al (hydr)oxide surface. During the second stage, XAS showed that Tc(IV) was incorporated within the newly formed LDH structure. Overall, these data provide novel insights into the application of LDH formation in Tc sequestration and suggest novel effluent treatment pathways to produce an inorganic solid.
{"title":"Reductive Incorporation of Technetium-99 in Fe(II)-Doped Layered Double Hydroxide","authors":"He Cai,Thomas Neill,Katherine Morris,Anthony Stockdale,Samuel Shaw","doi":"10.1021/acs.est.6c09361","DOIUrl":"https://doi.org/10.1021/acs.est.6c09361","url":null,"abstract":"Technetium-99 is a long-lived, high-yield fission product whose solubility is controlled by redox conditions. Here, to explore targeted effluent treatment approaches, pertechnetate (Tc(VII)O4–) reductive retention as Tc(IV) during coprecipitation of Fe(II)-doped Ni–Al–CO3 layered double hydroxide (LDH) was investigated. During LDH formation via base addition to an acidic Ni2+, Al3+, Fe2+, and Tc(VII)O4– bearing solution, there was essentially complete TcO4– removal at low (9.6 Bq/mL) and high (2.9 kBq/mL) concentrations. Characterization of experiments using X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and X-ray absorption spectroscopy (XAS) confirmed that, during base titration, a two-stage process occurred, with Al3+ forming amorphous Al (hydr)oxide between pH 4 and 6 in the first stage, followed by hydrolysis of Fe2+/Ni2+ and formation of LDH particles between pH 6 and 9 in stage two. During the first stage, TcO4– was removed from solution, and XAS confirmed it was reduced to Tc(IV) by Fe(II) associated with the amorphous Al (hydr)oxide, forming hydrous Tc(IV)O2-like chains on the Al (hydr)oxide surface. During the second stage, XAS showed that Tc(IV) was incorporated within the newly formed LDH structure. Overall, these data provide novel insights into the application of LDH formation in Tc sequestration and suggest novel effluent treatment pathways to produce an inorganic solid.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"13 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149210884","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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