Wildfire and stubble burning release substantial amounts of black carbon (BC) into natural environments that experience frequent redox oscillations, such as wetlands and farmlands. Here, we report that redox oscillations can effectively drive ROS production from BC. Following sequential microbial reduction and air exposure, 6.5 ± 0.2 μM/gC hydrogen peroxide (H2O2) and 285.3 ± 9.5 nM/gC hydroxyl radical (•OH) were produced from BC. Moreover, BC derived from various biomass sources, temperatures, and particle sizes exhibits 111.5-fold variations in ROS production. Electrochemical analyses revealed that both the electron transfer capacity and the ROS production selectivity are critical determinants of ROS generation under redox oscillations. The variation in electron transfer capacity (0.3–5.7 mmol e–/gC) is primarily governed by the abundance of electron-storing moieties such as quinones, while the ROS generation selectivity (26.2–72.0%) is influenced by the presence of competitive sites for oxygen reduction reactions, such as carbon defects. These findings provide insights into ROS production from BC under fluctuating redox conditions, with potential implications for elemental cycles and pollutant dynamics in regions prone to wildfire and stubble burning events and substantial BC deposition (e.g., wetlands and rice paddies).
{"title":"Redox Oscillation-Driven Production of Reactive Oxygen Species from Black Carbon","authors":"Xuan Li, Mengxi Tan, Binbin Wu, Jingyi Wang, Junye Ma, Baoliang Chen, Chiheng Chu","doi":"10.1021/acs.est.4c09102","DOIUrl":"https://doi.org/10.1021/acs.est.4c09102","url":null,"abstract":"Wildfire and stubble burning release substantial amounts of black carbon (BC) into natural environments that experience frequent redox oscillations, such as wetlands and farmlands. Here, we report that redox oscillations can effectively drive ROS production from BC. Following sequential microbial reduction and air exposure, 6.5 ± 0.2 μM/g<sub>C</sub> hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and 285.3 ± 9.5 nM/g<sub>C</sub> hydroxyl radical (•OH) were produced from BC. Moreover, BC derived from various biomass sources, temperatures, and particle sizes exhibits 111.5-fold variations in ROS production. Electrochemical analyses revealed that both the electron transfer capacity and the ROS production selectivity are critical determinants of ROS generation under redox oscillations. The variation in electron transfer capacity (0.3–5.7 mmol e<sup>–</sup>/g<sub>C</sub>) is primarily governed by the abundance of electron-storing moieties such as quinones, while the ROS generation selectivity (26.2–72.0%) is influenced by the presence of competitive sites for oxygen reduction reactions, such as carbon defects. These findings provide insights into ROS production from BC under fluctuating redox conditions, with potential implications for elemental cycles and pollutant dynamics in regions prone to wildfire and stubble burning events and substantial BC deposition (e.g., wetlands and rice paddies).","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"65 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678206","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}
Jinyuan Xin, Xinbing Ren, Yongjing Ma, Dandan Zhao, Yonghong Wang, Jianhuai Ye, Zifa Wang, Junji Cao, Jordi Vilà-Guerau de Arellano, Scot T. Martin
Notable anthropogenic heat sources such as coal-fired plants can alter the atmospheric boundary layer structure and the pollutant dispersion, thereby affecting the local environment and microclimate. Herein, in situ measurements inside a coal-fired steel plant were performed by multiple advanced lidars from 21 May to 21 June of 2021 in Yuncheng, Shanxi Province, China. Comparing with an adjacent meteorological site, we found a prominent nighttime dry heat island overhead of the factory, which was 3–10 °C hotter and 30%–60% drier than the surrounding fields. Large-eddy simulations constrained by the measured thermal contrast suggested that the heat-island-induced circulation could upward transport factory-discharged pollutants and horizontally spread them below the residual layer top, forming a mushroom-shaped cloud. The shape, size, and pollutant loading of the cloud were highly determined by thermodynamic variables such as aerodynamic wind and anthropogenic heat flux. Furthermore, these retained residual-layer pollutants can be convected downward to the ground after sunrise through the fumigation effect, causing the peaking phenomena aboveground. These peaks were statistically evidenced to be common in major urban agglomerations in China. The study provides a new insight regarding the origins of residual-layer pollutants and highlights the needs for programming representations of coal-fired heat emissions in mesoscale air-quality models.
{"title":"Industrial Dry Heat Island and Dispersion of Air Pollutants Induced by Large Coal-Fired Activities","authors":"Jinyuan Xin, Xinbing Ren, Yongjing Ma, Dandan Zhao, Yonghong Wang, Jianhuai Ye, Zifa Wang, Junji Cao, Jordi Vilà-Guerau de Arellano, Scot T. Martin","doi":"10.1021/acs.est.4c02300","DOIUrl":"https://doi.org/10.1021/acs.est.4c02300","url":null,"abstract":"Notable anthropogenic heat sources such as coal-fired plants can alter the atmospheric boundary layer structure and the pollutant dispersion, thereby affecting the local environment and microclimate. Herein, in situ measurements inside a coal-fired steel plant were performed by multiple advanced lidars from 21 May to 21 June of 2021 in Yuncheng, Shanxi Province, China. Comparing with an adjacent meteorological site, we found a prominent nighttime dry heat island overhead of the factory, which was 3–10 °C hotter and 30%–60% drier than the surrounding fields. Large-eddy simulations constrained by the measured thermal contrast suggested that the heat-island-induced circulation could upward transport factory-discharged pollutants and horizontally spread them below the residual layer top, forming a mushroom-shaped cloud. The shape, size, and pollutant loading of the cloud were highly determined by thermodynamic variables such as aerodynamic wind and anthropogenic heat flux. Furthermore, these retained residual-layer pollutants can be convected downward to the ground after sunrise through the fumigation effect, causing the peaking phenomena aboveground. These peaks were statistically evidenced to be common in major urban agglomerations in China. The study provides a new insight regarding the origins of residual-layer pollutants and highlights the needs for programming representations of coal-fired heat emissions in mesoscale air-quality models.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"20 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142684653","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}
Herein, we pioneered an innovative methodology for the rapid identification and quantitation of methyl parathion (MP) residues, overcoming the drawbacks of existing methods such as poor selectivity, high costs, and intricate operational procedures. A dual-emitting fluoroprobe SiONPs-Eu3+ was engineered based on silica oxide nanoparticles (SiONPs) conjugated with Eu3+, and the synthetic conditions were meticulously optimized to ensure exceptional sensitivity and selectivity to 4-nitrophenol (4-NP), one of the MP hydrolytic products. Upon excitation at 317 nm, the blue fluorescence of SiONPs at 400 nm was quenched, while the red fluorescence of Eu3+ at 616 nm remained nearly unchanged, constituting a ratiometric fluorescent change that significantly enhanced the detection stability. The fluoroprobe rapidly detected 4-NP at concentrations below 80 μM within 10 s and gave a limit of detection (LOD) as low as 0.16 μM, markedly lower than the allowable residue limit of MP in China food safety standards. Also, it exhibited excellent anti-interference properties in complex matrices, remaining unaffected by common amino acids, cations, and pesticides. The underlying mechanism of the fluoroprobe was elucidated through time-dependent density functional theory (TD-DFT) calculations. Under optimized hydrolysis conditions, the detection of MP in real rice samples was successfully achieved. Furthermore, the self-developed and dual-channel portable device was conducive to on-site fluorescence detection of 4-NP, offering enhanced stability in contrast to traditional photography-based methods.
{"title":"Rapid Detection of Methyl Parathion Based on SiONPs-Eu3+ Dual-Emitting Fluoroprobe and Its On-Site Application","authors":"Chunyang Chen, Hongke Bie, Jianhang Duan, Zhongjie Li, Yuemao Dou, Huili Wang, Wei Liu, Xuedong Wang","doi":"10.1021/acs.est.4c07422","DOIUrl":"https://doi.org/10.1021/acs.est.4c07422","url":null,"abstract":"Herein, we pioneered an innovative methodology for the rapid identification and quantitation of methyl parathion (MP) residues, overcoming the drawbacks of existing methods such as poor selectivity, high costs, and intricate operational procedures. A dual-emitting fluoroprobe SiONPs-Eu<sup>3+</sup> was engineered based on silica oxide nanoparticles (SiONPs) conjugated with Eu<sup>3+</sup>, and the synthetic conditions were meticulously optimized to ensure exceptional sensitivity and selectivity to 4-nitrophenol (4-NP), one of the MP hydrolytic products. Upon excitation at 317 nm, the blue fluorescence of SiONPs at 400 nm was quenched, while the red fluorescence of Eu<sup>3+</sup> at 616 nm remained nearly unchanged, constituting a ratiometric fluorescent change that significantly enhanced the detection stability. The fluoroprobe rapidly detected 4-NP at concentrations below 80 μM within 10 s and gave a limit of detection (LOD) as low as 0.16 μM, markedly lower than the allowable residue limit of MP in China food safety standards. Also, it exhibited excellent anti-interference properties in complex matrices, remaining unaffected by common amino acids, cations, and pesticides. The underlying mechanism of the fluoroprobe was elucidated through time-dependent density functional theory (TD-DFT) calculations. Under optimized hydrolysis conditions, the detection of MP in real rice samples was successfully achieved. Furthermore, the self-developed and dual-channel portable device was conducive to on-site fluorescence detection of 4-NP, offering enhanced stability in contrast to traditional photography-based methods.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"10 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678202","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}
Fan Wei, Enjing Wei, Yuan Chen, Jinhui Li, Quanyin Tan
Microplastic (MP), an emerging pollutant, has been identified as a critical target in tackling plastic pollution. Although a plethora of studies have explored MP generation from various sources, limited attention has been paid to plastic processing. This study investigated MP (10 μm–5 mm) generation in virgin and waste plastic extrusion processing. MPs at a density of 2.13 × 105–9.79 × 107 (approximately 0.01–10.85 g) were generated when processing 1 t of plastic. Feedstock sources, polymer types, and pelletizing techniques were found to influence the process. With a moderate weight (270.58–527.34 t) but enormous amount (1.34 × 1016–2.63 × 1016) of MPs generated globally in 2022, plastic processing is an underestimated but vital source of MPs, emphasizing the need for MP inspection and appropriate removal technologies in the industry, especially for virgin plastic processing and water ring pelletizing. Further simulation indicated that up to 84.35% of MPs could be removed using commonly available materials in the investigated plastic processing facility, with a higher removal efficiency for larger-sized particles. In this regard, plastic recycling was superior to virgin plastic processing with fewer and larger-sized MPs generated, which could facilitate MP removal and should be fostered.
{"title":"Recycle or Not? An Exploration of Microplastic Generation During Plastic Processing via a Local Case Study","authors":"Fan Wei, Enjing Wei, Yuan Chen, Jinhui Li, Quanyin Tan","doi":"10.1021/acs.est.4c07430","DOIUrl":"https://doi.org/10.1021/acs.est.4c07430","url":null,"abstract":"Microplastic (MP), an emerging pollutant, has been identified as a critical target in tackling plastic pollution. Although a plethora of studies have explored MP generation from various sources, limited attention has been paid to plastic processing. This study investigated MP (10 μm–5 mm) generation in virgin and waste plastic extrusion processing. MPs at a density of 2.13 × 10<sup>5</sup>–9.79 × 10<sup>7</sup> (approximately 0.01–10.85 g) were generated when processing 1 t of plastic. Feedstock sources, polymer types, and pelletizing techniques were found to influence the process. With a moderate weight (270.58–527.34 t) but enormous amount (1.34 × 10<sup>16</sup>–2.63 × 10<sup>16</sup>) of MPs generated globally in 2022, plastic processing is an underestimated but vital source of MPs, emphasizing the need for MP inspection and appropriate removal technologies in the industry, especially for virgin plastic processing and water ring pelletizing. Further simulation indicated that up to 84.35% of MPs could be removed using commonly available materials in the investigated plastic processing facility, with a higher removal efficiency for larger-sized particles. In this regard, plastic recycling was superior to virgin plastic processing with fewer and larger-sized MPs generated, which could facilitate MP removal and should be fostered.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"9 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678204","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 Stone, Darren J. Koppel, Monique T. Binet, Dianne F. Jolley, Stuart L. Simpson
Aquatic organisms may frequently be exposed to short-term discharges of contaminants, including those from pesticide use, stormwater runoff, or industrial effluents entering waterways. Here, a new microalgal multispecies flow cytometry-based bioassay is used to assess knowledge gaps in risk assessments posed by the short-term exposure of organisms to contaminants. The toxicities of atrazine, metolachlor, and copper were assessed using four exposure scenarios, a 72 h exposure (continuous), an 18 h pulse exposure, and two 3 h pulse exposures (light and dark conditions), that assessed chronotoxicity. The influence of duration on toxicity explored the utility of two expressions of chemical-exposure dose: pulse-exposure concentration (PeC) and time-weighted average concentrations (TACs). The three coexisting microalgae (Monoraphidium arcuatum, Nannochloropsis-like sp., and Pediastrum duplex) tolerated higher concentrations for shorter 3 and 18 h pulses compared to continuous 72 h exposures. Toxicity estimates calculated on a TAC basis were effective for predicting the toxicity of the pulses of atrazine, metolachlor, and copper. Fluorescence data collected using flow cytometry were linked to physiological diel changes for each species. Chronotoxicity was observed for copper with two species. While continuous contaminant exposures provide a conservative estimate of toxicity compared to pulses, the duration and time of exposure are critical factors to consider when assessing the toxicity of contaminants to microalgae.
{"title":"Application of a Multispecies Pulse-Exposure Microalgal Bioassay to Assess Duration and Time-of-Day Influences on the Toxicity of Chemicals","authors":"Sarah Stone, Darren J. Koppel, Monique T. Binet, Dianne F. Jolley, Stuart L. Simpson","doi":"10.1021/acs.est.4c07875","DOIUrl":"https://doi.org/10.1021/acs.est.4c07875","url":null,"abstract":"Aquatic organisms may frequently be exposed to short-term discharges of contaminants, including those from pesticide use, stormwater runoff, or industrial effluents entering waterways. Here, a new microalgal multispecies flow cytometry-based bioassay is used to assess knowledge gaps in risk assessments posed by the short-term exposure of organisms to contaminants. The toxicities of atrazine, metolachlor, and copper were assessed using four exposure scenarios, a 72 h exposure (continuous), an 18 h pulse exposure, and two 3 h pulse exposures (light and dark conditions), that assessed chronotoxicity. The influence of duration on toxicity explored the utility of two expressions of chemical-exposure dose: pulse-exposure concentration (PeC) and time-weighted average concentrations (TACs). The three coexisting microalgae (<i>Monoraphidium arcuatum</i>, <i>Nannochloropsis</i>-like sp., and <i>Pediastrum duplex</i>) tolerated higher concentrations for shorter 3 and 18 h pulses compared to continuous 72 h exposures. Toxicity estimates calculated on a TAC basis were effective for predicting the toxicity of the pulses of atrazine, metolachlor, and copper. Fluorescence data collected using flow cytometry were linked to physiological diel changes for each species. Chronotoxicity was observed for copper with two species. While continuous contaminant exposures provide a conservative estimate of toxicity compared to pulses, the duration and time of exposure are critical factors to consider when assessing the toxicity of contaminants to microalgae.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"11976 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673054","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}
Jia Xing, Bok H. Baek, Siwei Li, Chi-Tsan Wang, Ge Song, Siqi Ma, Shuxin Zheng, Chang Liu, Daniel Tong, Jung-Hun Woo, Tie-Yan Liu, Joshua S. Fu
Accurate estimation of atmospheric chemical concentrations from multiple observations is crucial for assessing the health effects of air pollution. However, existing methods are limited by imbalanced samples from observations. Here, we introduce a novel deep-learning model-measurement fusion method (DeepMMF) constrained by physical laws inferred from a chemical transport model (CTM) to estimate NO2 concentrations over the Continental United States (CONUS). By pretraining with spatiotemporally complete CTM simulations, fine-tuning with satellite and ground measurements, and employing a novel optimization strategy for selecting proper prior emission, DeepMMF delivers improved NO2 estimates, showing greater consistency and daily variation alignment with observations (with NMB reduced from −0.3 to −0.1 compared to original CTM simulations). More importantly, DeepMMF effectively addressed the sample imbalance issue that causes overestimation (by over 100%) of downwind or rural concentrations in other methods. It achieves a higher R2 of 0.98 and a lower RMSE of 1.45 ppb compared to surface NO2 observations, overperforming other approaches, which show R2 values of 0.4–0.7 and RMSEs of 3–6 ppb. The method also offers a synergistic advantage by adjusting corresponding emissions, in agreement with changes (−10% to −20%) reported in the NEI between 2019 and 2020. Our results demonstrate the great potential of DeepMMF in data fusion to better support air pollution exposure estimation and forecasting.
{"title":"A Physically Constrained Deep-Learning Fusion Method for Estimating Surface NO2 Concentration from Satellite and Ground Monitors","authors":"Jia Xing, Bok H. Baek, Siwei Li, Chi-Tsan Wang, Ge Song, Siqi Ma, Shuxin Zheng, Chang Liu, Daniel Tong, Jung-Hun Woo, Tie-Yan Liu, Joshua S. Fu","doi":"10.1021/acs.est.4c07341","DOIUrl":"https://doi.org/10.1021/acs.est.4c07341","url":null,"abstract":"Accurate estimation of atmospheric chemical concentrations from multiple observations is crucial for assessing the health effects of air pollution. However, existing methods are limited by imbalanced samples from observations. Here, we introduce a novel deep-learning model-measurement fusion method (DeepMMF) constrained by physical laws inferred from a chemical transport model (CTM) to estimate NO<sub>2</sub> concentrations over the Continental United States (CONUS). By pretraining with spatiotemporally complete CTM simulations, fine-tuning with satellite and ground measurements, and employing a novel optimization strategy for selecting proper prior emission, DeepMMF delivers improved NO<sub>2</sub> estimates, showing greater consistency and daily variation alignment with observations (with NMB reduced from −0.3 to −0.1 compared to original CTM simulations). More importantly, DeepMMF effectively addressed the sample imbalance issue that causes overestimation (by over 100%) of downwind or rural concentrations in other methods. It achieves a higher <i>R</i><sup>2</sup> of 0.98 and a lower RMSE of 1.45 ppb compared to surface NO<sub>2</sub> observations, overperforming other approaches, which show <i>R</i><sup>2</sup> values of 0.4–0.7 and RMSEs of 3–6 ppb. The method also offers a synergistic advantage by adjusting corresponding emissions, in agreement with changes (−10% to −20%) reported in the NEI between 2019 and 2020. Our results demonstrate the great potential of DeepMMF in data fusion to better support air pollution exposure estimation and forecasting.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"2 11 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673062","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}
Binlong Liu, Michael Finkel, Qiyue Qin, Wenxiao Shi, Peter Grathwohl
Redistribution of pollutants between different solid phases occurs frequently in field and laboratory settings. Examples include the input of urban particles carrying pollutants into soils or rivers with suspended particles or passive sampling. Since multiple mass transfer mechanisms are involved and natural particles typically are very heterogeneous, modeling of sorption/desorption kinetics is challenging. Here, we present a semi-analytical model formulated in the Laplace domain to simulate pollutant redistribution kinetics in heterogeneous systems. The model accounts for a coupled process governed by intraparticle and external boundary layer diffusion, and it considers the heterogeneity of various sorbents (e.g., geometric shape, size, sorption capacity coefficient, and solid and porous particles). The model is validated against data of two batch experiments: (i) the redistribution of phenanthrene in spherical polyethylene particles of different sizes and (ii) redistribution of anthracene-d10 and phenanthrene in a heterogeneous sediment suspension with polyethylene passive samplers. It allows to explain the temporary overshooting of concentrations in the aqueous phase due to different kinetic controls of various particles involved (fast desorption vs. slow sorption) as well as initial fast kinetics followed by surprising long tailing in batch experiments. The approach is very flexible and can be used for many different scenarios.
{"title":"Mechanistic Modeling of Pollutant Mass Redistribution (Sorption/Desorption) in Heterogeneous Systems Explaining Unexpected Slow Kinetics","authors":"Binlong Liu, Michael Finkel, Qiyue Qin, Wenxiao Shi, Peter Grathwohl","doi":"10.1021/acs.est.4c03176","DOIUrl":"https://doi.org/10.1021/acs.est.4c03176","url":null,"abstract":"Redistribution of pollutants between different solid phases occurs frequently in field and laboratory settings. Examples include the input of urban particles carrying pollutants into soils or rivers with suspended particles or passive sampling. Since multiple mass transfer mechanisms are involved and natural particles typically are very heterogeneous, modeling of sorption/desorption kinetics is challenging. Here, we present a semi-analytical model formulated in the Laplace domain to simulate pollutant redistribution kinetics in heterogeneous systems. The model accounts for a coupled process governed by intraparticle and external boundary layer diffusion, and it considers the heterogeneity of various sorbents (e.g., geometric shape, size, sorption capacity coefficient, and solid and porous particles). The model is validated against data of two batch experiments: (i) the redistribution of phenanthrene in spherical polyethylene particles of different sizes and (ii) redistribution of anthracene-d10 and phenanthrene in a heterogeneous sediment suspension with polyethylene passive samplers. It allows to explain the temporary overshooting of concentrations in the aqueous phase due to different kinetic controls of various particles involved (fast desorption vs. slow sorption) as well as initial fast kinetics followed by surprising long tailing in batch experiments. The approach is very flexible and can be used for many different scenarios.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"69 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673053","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 sustainable and affordable environmental application of Pd catalysis needs further improvement of Pd mass activity. Besides the well-recognized importance of physical utilization efficiency─the ratio of surface atoms forming reactant-accessible reactive sites─a lesser-known fact is that the congestion of these reactive sites, which we term as the chemical utilization efficiency, also influences the mass activity. Herein, by leveraging the 100% physical utilization efficiency of a fully exposed Pd cluster (Pdn) and the hydrogenation activity of TiNiN, we developed Pdn/TiNiN as a high physical and chemical utilization efficiency catalyst. During the catalytic hydrodechlorination of 4-chlorophenol and the subsequent hydrogenation of phenol, Pdn focuses on H2 dissociation and C–Cl cleavage, while TiNiN facilitates the subsequent hydrogenation of phenol into less toxic cyclohexanone via H-spillover. This synergy results in a 20–40-fold increase in the hydrodechlorination rate. The enhanced chemical utilization efficiency of Pd informs the design of Pdn/TiNiN microspheres for the conversion of halogenated organics from pharmaceutical wastewater and the design of a fixed-bed reactor to transfer trace amounts of 4-CP from river water. Ultimately, this approach decentralizes the use of Pd in environmental catalysis and reduction processes.
{"title":"Improving the Chemical Utilization Efficiency of Pd Hydrodechlorination Catalysts through Hydrogen-Spillover Empowered Synergy between Pd and TiNiN Support","authors":"Wenxuan Wang, Xiaoling Zhang, Wei Ran, Chunyan Ma, Jiefang Sun, Muyao Zhao, Wenxiao Pan, Jingfu Liu, Rui Liu, Guibin Jiang","doi":"10.1021/acs.est.4c05860","DOIUrl":"https://doi.org/10.1021/acs.est.4c05860","url":null,"abstract":"The sustainable and affordable environmental application of Pd catalysis needs further improvement of Pd mass activity. Besides the well-recognized importance of physical utilization efficiency─the ratio of surface atoms forming reactant-accessible reactive sites─a lesser-known fact is that the congestion of these reactive sites, which we term as the chemical utilization efficiency, also influences the mass activity. Herein, by leveraging the 100% physical utilization efficiency of a fully exposed Pd cluster (Pd<sub><i>n</i></sub>) and the hydrogenation activity of TiNiN, we developed Pd<sub><i>n</i></sub>/TiNiN as a high physical and chemical utilization efficiency catalyst. During the catalytic hydrodechlorination of 4-chlorophenol and the subsequent hydrogenation of phenol, Pd<sub><i>n</i></sub> focuses on H<sub>2</sub> dissociation and C–Cl cleavage, while TiNiN facilitates the subsequent hydrogenation of phenol into less toxic cyclohexanone via H-spillover. This synergy results in a 20–40-fold increase in the hydrodechlorination rate. The enhanced chemical utilization efficiency of Pd informs the design of Pd<sub><i>n</i></sub>/TiNiN microspheres for the conversion of halogenated organics from pharmaceutical wastewater and the design of a fixed-bed reactor to transfer trace amounts of 4-CP from river water. Ultimately, this approach decentralizes the use of Pd in environmental catalysis and reduction processes.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"23 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678211","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}
Shiyi Hong, Zekang Su, Yali Zhang, Guiping Hu, Qiaojian Zhang, Zhiqiang Ji, Li Wang, Shanfa Yu, Xiaojun Zhu, Fang Yuan, Guang Jia
Genotoxic and immunosuppressive characteristics are central to the carcinogenic profile of hexavalent chromium [Cr(VI)], with dysregulation of circulating exosomal miRNA potentially acting as oncogenes or tumor suppressors or participating in the carcinogenic landscape of heavy metals through immunomodulation. In this two-stage epidemiological investigation, we unveiled for the first time the perturbations of exosomal miRNAs among individuals exposed to Cr(VI), alongside their significant correlations with biomarkers of genetic injury (γ-H2AX positivity in circulating lymphocytes and the urinary 8-OHdG levels) and immunological indicators (immunosuppressive PD-1 expression), which was supported by validation in an external cohort. Employing a support vector machine model, we discerned that exosomal miRNAs, particularly miR-4467, miR-345-5p, miR-144-3p, and miR-206, exhibited a remarkable capacity to delineate the genetic damage stratum within the population with high precision, and the target genes predicted of these miRNAs further elucidated their intricate regulatory interplay with the effector biomarkers. Additionally, employing a Bayesian mediation framework, we observed the intermediary function of miR-4467 in the nexus between chromium exposure and the escalation of urinary 8-OHdG levels (mediation effect: 0.47, P < 0.05). Although our findings suggested a link between extracellular miRNAs and immunosuppressive biomarkers, this association did not achieve validation in the external cohort, possibly due to population heterogeneity. Collectively, this study advanced our understanding of the epigenetic orchestration of health hazards of Cr(VI) by exosomal miRNAs, shedding light on their expression signatures and their intricate interplay with Cr(VI)-induced genetic and immunological perturbations, thus providing novel perspectives on the toxic pathways of heavy metals.
{"title":"Exosomal miRNAs as Participators of Hexavalent Chromium-Induced Genotoxicity and Immunotoxicity: A Two-Stage Population Study","authors":"Shiyi Hong, Zekang Su, Yali Zhang, Guiping Hu, Qiaojian Zhang, Zhiqiang Ji, Li Wang, Shanfa Yu, Xiaojun Zhu, Fang Yuan, Guang Jia","doi":"10.1021/acs.est.4c06411","DOIUrl":"https://doi.org/10.1021/acs.est.4c06411","url":null,"abstract":"Genotoxic and immunosuppressive characteristics are central to the carcinogenic profile of hexavalent chromium [Cr(VI)], with dysregulation of circulating exosomal miRNA potentially acting as oncogenes or tumor suppressors or participating in the carcinogenic landscape of heavy metals through immunomodulation. In this two-stage epidemiological investigation, we unveiled for the first time the perturbations of exosomal miRNAs among individuals exposed to Cr(VI), alongside their significant correlations with biomarkers of genetic injury (γ-H2AX positivity in circulating lymphocytes and the urinary 8-OHdG levels) and immunological indicators (immunosuppressive PD-1 expression), which was supported by validation in an external cohort. Employing a support vector machine model, we discerned that exosomal miRNAs, particularly miR-4467, miR-345-5p, miR-144-3p, and miR-206, exhibited a remarkable capacity to delineate the genetic damage stratum within the population with high precision, and the target genes predicted of these miRNAs further elucidated their intricate regulatory interplay with the effector biomarkers. Additionally, employing a Bayesian mediation framework, we observed the intermediary function of miR-4467 in the nexus between chromium exposure and the escalation of urinary 8-OHdG levels (mediation effect: 0.47, <i>P</i> < 0.05). Although our findings suggested a link between extracellular miRNAs and immunosuppressive biomarkers, this association did not achieve validation in the external cohort, possibly due to population heterogeneity. Collectively, this study advanced our understanding of the epigenetic orchestration of health hazards of Cr(VI) by exosomal miRNAs, shedding light on their expression signatures and their intricate interplay with Cr(VI)-induced genetic and immunological perturbations, thus providing novel perspectives on the toxic pathways of heavy metals.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"38 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673035","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}
Gabriel Stefanelli-Silva, Pâmela Friedemann, Beatriz Rocha de Moraes, Romulo Augusto Ando, Lúcia de Siqueira Campos, Mônica Angélica Varella Petti, Craig R. Smith, Paulo Yukio Gomes Sumida
Anthropogenic debris has been documented in Antarctica for the past 40 years. Upon breakdown, large pieces become microdebris, which reaches the seafloor through a variety of physical and biological processes. The Antarctic benthos, deeply reliant on sinking organic particles, is thus vulnerable to ingesting microdebris. By using benthic specimens sampled between 1986 and 2016 and deposited in biological collections, we provide the first record of microdebris in Southern Ocean deep-sea invertebrates. Specimens from 15 species (n = 169 organisms) had their gut content examined, with 13 species yielding microdebris in the shape of fibers (n = 85 fibers). The highest ingestion percentages were recorded in the sea cucumbers Heterocucumis steineni (100%), Molpadia violacea (83%) and Scotoplanes globosa (75%), and in the brittle star Amphioplus peregrinator (53%). Deposit- and suspension-feeding were the strategies which yielded the most fibers, accounting for 83.53% of particles. Seven fibers were identified as microplastics, composed of polyamide, polycarbonate, polyester, polyethylene terephthalate, polyisoprene and polysulfone. We also provide the earliest record of a microplastic in Antarctica, a polysulfone fiber ingested by a Boreomysis sp. mysid caught in 1986. The occurrence of fibers in the world’s most remote continental margin renews concerns of pollution in seemingly isolated regions.
{"title":"Bottom-Feeders Eat Their Fiber: Ingestion of Anthropogenic Microdebris by Antarctic Deep-Sea Invertebrates Depends on Feeding Ecology","authors":"Gabriel Stefanelli-Silva, Pâmela Friedemann, Beatriz Rocha de Moraes, Romulo Augusto Ando, Lúcia de Siqueira Campos, Mônica Angélica Varella Petti, Craig R. Smith, Paulo Yukio Gomes Sumida","doi":"10.1021/acs.est.4c09487","DOIUrl":"https://doi.org/10.1021/acs.est.4c09487","url":null,"abstract":"Anthropogenic debris has been documented in Antarctica for the past 40 years. Upon breakdown, large pieces become microdebris, which reaches the seafloor through a variety of physical and biological processes. The Antarctic benthos, deeply reliant on sinking organic particles, is thus vulnerable to ingesting microdebris. By using benthic specimens sampled between 1986 and 2016 and deposited in biological collections, we provide the first record of microdebris in Southern Ocean deep-sea invertebrates. Specimens from 15 species (n = 169 organisms) had their gut content examined, with 13 species yielding microdebris in the shape of fibers (n = 85 fibers). The highest ingestion percentages were recorded in the sea cucumbers <i>Heterocucumis steineni</i> (100%), <i>Molpadia violacea</i> (83%) and <i>Scotoplanes globosa</i> (75%), and in the brittle star <i>Amphioplus peregrinator</i> (53%). Deposit- and suspension-feeding were the strategies which yielded the most fibers, accounting for 83.53% of particles. Seven fibers were identified as microplastics, composed of polyamide, polycarbonate, polyester, polyethylene terephthalate, polyisoprene and polysulfone. We also provide the earliest record of a microplastic in Antarctica, a polysulfone fiber ingested by a <i>Boreomysis</i> sp. mysid caught in 1986. The occurrence of fibers in the world’s most remote continental margin renews concerns of pollution in seemingly isolated regions.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"1 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678207","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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