Microplastics have become an increasingly concerning pollutant in aquatic environments, and photodegradation is their main degradation pathway in water. Gaining insight into the transformation process of microplastics will enhance our understanding of their behavior and destiny in natural environments. This paper studied the aging process of BER microplastics in aquatic environments under simulated sunlight and investigated the changes in the physical and chemical properties of microplastics and the changes in the leachate. During the photodegradation process, BER-MPs underwent extensive oxidation and reduction in particle size, and the originally smooth surface developed numerous voids, accompanied by yellowing. Introduction of O atoms in the molecular chains increased their hydrophilicity, resulting in the polymer chains breaking away from the plastic particles and dissolving in water. Also, once BER was excited by light, environmentally persistent free radicals are produced on its surface. Moreover, the breaking of C–Br bonds occurred during the photodegradation process of BER-MPs, which suggested that tetrabromobisphenol A would be transformed during the photoaging process of BER even if it was covalently bound to BER.
微塑料已成为水生环境中越来越令人担忧的污染物,光降解是其在水中降解的主要途径。深入了解微塑料的转化过程将加深我们对其在自然环境中的行为和归宿的理解。本文研究了 BER 微塑料在模拟阳光照射下的水生环境老化过程,并考察了微塑料物理和化学性质的变化以及渗滤液的变化。在光降解过程中,BER-MPs 发生了大面积氧化,粒径减小,原本光滑的表面出现了许多空隙,并伴有泛黄现象。在分子链中引入 O 原子增加了其亲水性,导致聚合物链从塑料粒子中断裂并溶解于水。此外,一旦 BER 被光激发,其表面就会产生环境持久性自由基。此外,在 BER-MPs 的光降解过程中,C-Br 键发生断裂,这表明即使四溴双酚 A 与 BER 共价结合,它也会在 BER 的光老化过程中发生转化。
{"title":"Photo-aging of brominated epoxy microplastics in water under simulated solar irradiation†","authors":"Xuefeng Hu, Hao Xie, Yujie Li and Chao Wang","doi":"10.1039/D4EM00208C","DOIUrl":"10.1039/D4EM00208C","url":null,"abstract":"<p >Microplastics have become an increasingly concerning pollutant in aquatic environments, and photodegradation is their main degradation pathway in water. Gaining insight into the transformation process of microplastics will enhance our understanding of their behavior and destiny in natural environments. This paper studied the aging process of BER microplastics in aquatic environments under simulated sunlight and investigated the changes in the physical and chemical properties of microplastics and the changes in the leachate. During the photodegradation process, BER-MPs underwent extensive oxidation and reduction in particle size, and the originally smooth surface developed numerous voids, accompanied by yellowing. Introduction of O atoms in the molecular chains increased their hydrophilicity, resulting in the polymer chains breaking away from the plastic particles and dissolving in water. Also, once BER was excited by light, environmentally persistent free radicals are produced on its surface. Moreover, the breaking of C–Br bonds occurred during the photodegradation process of BER-MPs, which suggested that tetrabromobisphenol A would be transformed during the photoaging process of BER even if it was covalently bound to BER.</p>","PeriodicalId":74,"journal":{"name":"Environmental Science: Processes & Impacts","volume":" 8","pages":" 1380-1390"},"PeriodicalIF":4.3,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141553640","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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}
Gen Pei, Parham Azimi, Donghyun Rim and Joseph G. Allen
The utilization of portable air cleaners (PACs) is a recommended supplemental approach to help remove airborne pathogens and mitigate disease transmission in learning environments. To improve PAC effectiveness, science-based information is needed to optimize their implementation strategies such as the deployment location, height, and number of PACs. In this study, we developed a Computational Fluid Dynamics (CFD) model to assess how PACs perform in occupied classrooms equipped with displacement and mixing ventilation systems. The results show that PACs with a flow rate of 2.6 h−1 reduce the mean aerosol intake of all students by up to 66%. A key benefit of using PACs is to facilitate air mixing and movement in indoor environments with inadequate ventilation, thereby effectively reducing high aerosol concentrations near the infector. Furthermore, our results highlight the impact of PAC location on its performance. PACs achieve the best effectiveness when placed closed to the infector (within a distance <3 m). In the absence of knowing who is infected, deploying a PAC at the center of the room is recommended. Moreover, adjusting PAC flow discharge height to the breathing height of occupants (e.g., 0.9–1.2 m for seated people) can enhance their effectiveness in spaces with poor air mixing.
{"title":"A CFD study on the effect of portable air cleaner placement on airborne infection control in a classroom†","authors":"Gen Pei, Parham Azimi, Donghyun Rim and Joseph G. Allen","doi":"10.1039/D4EM00114A","DOIUrl":"10.1039/D4EM00114A","url":null,"abstract":"<p >The utilization of portable air cleaners (PACs) is a recommended supplemental approach to help remove airborne pathogens and mitigate disease transmission in learning environments. To improve PAC effectiveness, science-based information is needed to optimize their implementation strategies such as the deployment location, height, and number of PACs. In this study, we developed a Computational Fluid Dynamics (CFD) model to assess how PACs perform in occupied classrooms equipped with displacement and mixing ventilation systems. The results show that PACs with a flow rate of 2.6 h<small><sup>−1</sup></small> reduce the mean aerosol intake of all students by up to 66%. A key benefit of using PACs is to facilitate air mixing and movement in indoor environments with inadequate ventilation, thereby effectively reducing high aerosol concentrations near the infector. Furthermore, our results highlight the impact of PAC location on its performance. PACs achieve the best effectiveness when placed closed to the infector (within a distance <3 m). In the absence of knowing who is infected, deploying a PAC at the center of the room is recommended. Moreover, adjusting PAC flow discharge height to the breathing height of occupants (<em>e.g.</em>, 0.9–1.2 m for seated people) can enhance their effectiveness in spaces with poor air mixing.</p>","PeriodicalId":74,"journal":{"name":"Environmental Science: Processes & Impacts","volume":" 9","pages":" 1476-1488"},"PeriodicalIF":4.3,"publicationDate":"2024-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141551511","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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}
This study evaluated the pollution characteristics, spatiotemporal distribution, and ecological risks of eight endocrine-disrupting chemicals (EDCs) in the Minjiang and Tuojiang rivers. Utilizing 3S technology (ArcGIS, remote sensing, GPS) and Fragstats, the research calculated eight landscape pattern indices related to land use types along the Minjiang river and established correlations between landscape factors and EDC distribution through stepwise multiple regression. The results indicated that bisphenol A (BPA) and nonylphenol (NP) were the most concerning EDCs, with detection frequencies of 97–100% and peak concentrations up to 63.35 ng L−1, primarily located in the middle and lower reaches of the Minjiang river and the upper reaches of the Tuojiang river. There was a significant correlation between the spatial distribution of pollutants and landscape patterns, where increased fragmentation, a higher number of patches, and complex patch shapes within a 10-kilometer buffer zone were associated with elevated levels of river pollution. By integrating four classical mathematical models to fit curves for acute and chronic toxicity data of BPA and NP, the findings suggested that BPA posed a higher ecological risk. This interdisciplinary research provided essential theoretical insights for investigating river pollution and its influencing factors, offering a new perspective on simultaneous river pollution control, urban functional zoning, and adjustment of watershed landscape spatial patterns from an urban planning standpoint.
本研究评估了岷江和沱江中八种干扰内分泌的化学物质(EDCs)的污染特征、时空分布和生态风险。研究利用 3S 技术(ArcGIS、遥感、GPS)和 Fragstats,计算了与岷江沿岸土地利用类型相关的 8 个景观格局指数,并通过逐步多元回归建立了景观因子与 EDC 分布之间的相关性。结果表明,双酚 A(BPA)和壬基酚(NP)是关注度最高的 EDCs,检出率为 97%-100%,峰值浓度高达 63.35 ng L-1,主要分布在岷江中下游和沱江上游。污染物的空间分布与景观格局之间存在明显的相关性,在10公里的缓冲区内,破碎化程度增加、斑块数量增多、斑块形状复杂与河流污染水平升高有关。通过整合四个经典数学模型来拟合双酚 A 和 NP 的急性和慢性毒性数据曲线,研究结果表明双酚 A 对生态环境的风险更高。这项跨学科研究为研究河流污染及其影响因素提供了重要的理论依据,从城市规划的角度为同时进行河流污染控制、城市功能分区和流域景观空间格局调整提供了新的视角。
{"title":"New insight into the spatiotemporal distribution and ecological risk assessment of endocrine-disrupting chemicals in the Minjiang and Tuojiang rivers: perspective of watershed landscape patterns†","authors":"Weike Zhao, Peilin Li and Bo Yang","doi":"10.1039/D4EM00052H","DOIUrl":"10.1039/D4EM00052H","url":null,"abstract":"<p >This study evaluated the pollution characteristics, spatiotemporal distribution, and ecological risks of eight endocrine-disrupting chemicals (EDCs) in the Minjiang and Tuojiang rivers. Utilizing 3S technology (ArcGIS, remote sensing, GPS) and Fragstats, the research calculated eight landscape pattern indices related to land use types along the Minjiang river and established correlations between landscape factors and EDC distribution through stepwise multiple regression. The results indicated that bisphenol A (BPA) and nonylphenol (NP) were the most concerning EDCs, with detection frequencies of 97–100% and peak concentrations up to 63.35 ng L<small><sup>−1</sup></small>, primarily located in the middle and lower reaches of the Minjiang river and the upper reaches of the Tuojiang river. There was a significant correlation between the spatial distribution of pollutants and landscape patterns, where increased fragmentation, a higher number of patches, and complex patch shapes within a 10-kilometer buffer zone were associated with elevated levels of river pollution. By integrating four classical mathematical models to fit curves for acute and chronic toxicity data of BPA and NP, the findings suggested that BPA posed a higher ecological risk. This interdisciplinary research provided essential theoretical insights for investigating river pollution and its influencing factors, offering a new perspective on simultaneous river pollution control, urban functional zoning, and adjustment of watershed landscape spatial patterns from an urban planning standpoint.</p>","PeriodicalId":74,"journal":{"name":"Environmental Science: Processes & Impacts","volume":" 8","pages":" 1360-1372"},"PeriodicalIF":4.3,"publicationDate":"2024-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141490042","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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}
Zerong Guan, Xueqiong Weng, Ligang Zhang and Peiran Feng
Background: polycyclic aromatic hydrocarbons (PAHs) are classified as neurotoxins, but the relationship between exposure to PAHs and cognition in adults is unclear, and their non-linear and mixed exposure association hasn't been explored. Objective: to evaluate the non-linear and joint association between co-exposure to PAHs and multiple cognitive tests in U.S. older people. Methods: restricted cubic spline (RCS) and Bayesian kernel machine regression (BKMR) were conducted to evaluate the non-linear and mixed exposure association, based on the cross-sectional data from NHANES 2011–2014: 772 participants over 60 years old, 4 cognitive test scores, including the Immediate Recall Test (IRT), Delayed Recall Test (DRT), Animal Fluency Test (AFT), and Digit Symbol Substitution test (DSST), and 5 urinary PAH metabolites. Results: a V-shaped nonlinear relationship was found between 3-hydroxyfluorene (3-FLUO), 2-hydroxyfluorene (2-FLUO), and DRT. Negative trends between mixed PAH exposure and IRT, DRT, and DSST scores were observed. 2-FLUO contributed the most to the negative association of multiple PAHs with IRT and DRT scores and 2-hydroxynaphthalene (2-NAP) played the most important role in the decreasing relationship between mixed PAH exposure and DSST scores. Conclusion: our study suggested that PAH exposure in the U.S. elderly might be related to their poor performances in IRT, DRT and DSST. Further prospective studies are needed to validate the association.
{"title":"Association between polycyclic aromatic hydrocarbon exposure and cognitive performance in older adults: a cross-sectional study from NHANES 2011–2014†","authors":"Zerong Guan, Xueqiong Weng, Ligang Zhang and Peiran Feng","doi":"10.1039/D4EM00290C","DOIUrl":"10.1039/D4EM00290C","url":null,"abstract":"<p > <em>Background</em>: polycyclic aromatic hydrocarbons (PAHs) are classified as neurotoxins, but the relationship between exposure to PAHs and cognition in adults is unclear, and their non-linear and mixed exposure association hasn't been explored. <em>Objective</em>: to evaluate the non-linear and joint association between co-exposure to PAHs and multiple cognitive tests in U.S. older people. <em>Methods</em>: restricted cubic spline (RCS) and Bayesian kernel machine regression (BKMR) were conducted to evaluate the non-linear and mixed exposure association, based on the cross-sectional data from NHANES 2011–2014: 772 participants over 60 years old, 4 cognitive test scores, including the Immediate Recall Test (IRT), Delayed Recall Test (DRT), Animal Fluency Test (AFT), and Digit Symbol Substitution test (DSST), and 5 urinary PAH metabolites. <em>Results</em>: a V-shaped nonlinear relationship was found between 3-hydroxyfluorene (3-FLUO), 2-hydroxyfluorene (2-FLUO), and DRT. Negative trends between mixed PAH exposure and IRT, DRT, and DSST scores were observed. 2-FLUO contributed the most to the negative association of multiple PAHs with IRT and DRT scores and 2-hydroxynaphthalene (2-NAP) played the most important role in the decreasing relationship between mixed PAH exposure and DSST scores. <em>Conclusion</em>: our study suggested that PAH exposure in the U.S. elderly might be related to their poor performances in IRT, DRT and DSST. Further prospective studies are needed to validate the association.</p>","PeriodicalId":74,"journal":{"name":"Environmental Science: Processes & Impacts","volume":" 8","pages":" 1348-1359"},"PeriodicalIF":4.3,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141490041","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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}
Delphine K Farmer, Marina E Vance, Dustin Poppendieck, Jon Abbatt, Michael R Alves, Karen C Dannemiller, Cholaphan Deeleepojananan, Jenna Ditto, Brian Dougherty, Olivia R Farinas, Allen H Goldstein, Vicki H Grassian, Han Huynh, Deborah Kim, Jon C King, Jesse Kroll, Jienan Li, Michael F Link, Liora Mael, Kathryn Mayer, Andrew B Martin, Glenn Morrison, Rachel O'Brien, Shubhrangshu Pandit, Barbara J Turpin, Marc Webb, Jie Yu, Stephen M Zimmerman
The Chemical Assessment of Surfaces and Air (CASA) study aimed to understand how chemicals transform in the indoor environment using perturbations (e.g., cooking, cleaning) or additions of indoor and outdoor pollutants in a well-controlled test house. Chemical additions ranged from individual compounds (e.g., gaseous ammonia or ozone) to more complex mixtures (e.g., a wildfire smoke proxy and a commercial pesticide). Physical perturbations included varying temperature, ventilation rates, and relative humidity. The objectives for CASA included understanding (i) how outdoor air pollution impacts indoor air chemistry, (ii) how wildfire smoke transports and transforms indoors, (iii) how gases and particles interact with building surfaces, and (iv) how indoor environmental conditions impact indoor chemistry. Further, the combined measurements under unperturbed and experimental conditions enable investigation of mitigation strategies following outdoor and indoor air pollution events. A comprehensive suite of instruments measured different chemical components in the gas, particle, and surface phases throughout the study. We provide an overview of the test house, instrumentation, experimental design, and initial observations - including the role of humidity in controlling the air concentrations of many semi-volatile organic compounds, the potential for ozone to generate indoor nitrogen pentoxide (N2O5), the differences in microbial composition between the test house and other occupied buildings, and the complexity of deposited particles and gases on different indoor surfaces.
{"title":"The chemical assessment of surfaces and air (CASA) study: using chemical and physical perturbations in a test house to investigate indoor processes.","authors":"Delphine K Farmer, Marina E Vance, Dustin Poppendieck, Jon Abbatt, Michael R Alves, Karen C Dannemiller, Cholaphan Deeleepojananan, Jenna Ditto, Brian Dougherty, Olivia R Farinas, Allen H Goldstein, Vicki H Grassian, Han Huynh, Deborah Kim, Jon C King, Jesse Kroll, Jienan Li, Michael F Link, Liora Mael, Kathryn Mayer, Andrew B Martin, Glenn Morrison, Rachel O'Brien, Shubhrangshu Pandit, Barbara J Turpin, Marc Webb, Jie Yu, Stephen M Zimmerman","doi":"10.1039/d4em00209a","DOIUrl":"10.1039/d4em00209a","url":null,"abstract":"<p><p>The Chemical Assessment of Surfaces and Air (CASA) study aimed to understand how chemicals transform in the indoor environment using perturbations (<i>e.g.</i>, cooking, cleaning) or additions of indoor and outdoor pollutants in a well-controlled test house. Chemical additions ranged from individual compounds (<i>e.g.</i>, gaseous ammonia or ozone) to more complex mixtures (<i>e.g.</i>, a wildfire smoke proxy and a commercial pesticide). Physical perturbations included varying temperature, ventilation rates, and relative humidity. The objectives for CASA included understanding (i) how outdoor air pollution impacts indoor air chemistry, (ii) how wildfire smoke transports and transforms indoors, (iii) how gases and particles interact with building surfaces, and (iv) how indoor environmental conditions impact indoor chemistry. Further, the combined measurements under unperturbed and experimental conditions enable investigation of mitigation strategies following outdoor and indoor air pollution events. A comprehensive suite of instruments measured different chemical components in the gas, particle, and surface phases throughout the study. We provide an overview of the test house, instrumentation, experimental design, and initial observations - including the role of humidity in controlling the air concentrations of many semi-volatile organic compounds, the potential for ozone to generate indoor nitrogen pentoxide (N<sub>2</sub>O<sub>5</sub>), the differences in microbial composition between the test house and other occupied buildings, and the complexity of deposited particles and gases on different indoor surfaces.</p>","PeriodicalId":74,"journal":{"name":"Environmental Science: Processes & Impacts","volume":" ","pages":""},"PeriodicalIF":4.3,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141475474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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}
Patrick M. Plehiers, Hans-Georg Pirkl, Lauren Ward and Christian Bögi
Environmental fate and toxicity testing typically requires knowledge of the water solubility of the test substances. Determining the solubility of aromatic diisocyanates in water poses great challenges because of their hydrophobic nature and water-reactivity. The reactive dissolution process is dynamic and the establishment of a steady-state equilibrium cannot readily be observed. In preparation of experimental work, computer simulation was used to derive and evaluate criteria that enable distinguishing homogeneous (i.e., substances would be fully dissolved in water) from heterogeneous (i.e., a separate organic phase would be present) conditions. The simulation utilized available kinetic information and models representing the main physical and chemical processes taking place. It was found that the transition to heterogeneous conditions (i.e., the exceedance of the solubility limit with increasing loading) can be identified by observing either a rapid decline in ultimate yield of the diamine hydrolysis product from near-stoichiometric to much lower values, or a decrease in rate of formation of the diamine hydrolysis product relative to its ultimate yield. The latter criterion is expected to be the more powerful indicator. These criteria can be used in future work to define and interpret an experimental program for determining solubility limits for aromatic diisocyanates or other poorly-soluble, water-reactive substances.
{"title":"Criteria for distinguishing heterogeneous from homogeneous conditions for aromatic diisocyanates in water†","authors":"Patrick M. Plehiers, Hans-Georg Pirkl, Lauren Ward and Christian Bögi","doi":"10.1039/D4EM00200H","DOIUrl":"10.1039/D4EM00200H","url":null,"abstract":"<p >Environmental fate and toxicity testing typically requires knowledge of the water solubility of the test substances. Determining the solubility of aromatic diisocyanates in water poses great challenges because of their hydrophobic nature and water-reactivity. The reactive dissolution process is dynamic and the establishment of a steady-state equilibrium cannot readily be observed. In preparation of experimental work, computer simulation was used to derive and evaluate criteria that enable distinguishing homogeneous (<em>i.e.</em>, substances would be fully dissolved in water) from heterogeneous (<em>i.e.</em>, a separate organic phase would be present) conditions. The simulation utilized available kinetic information and models representing the main physical and chemical processes taking place. It was found that the transition to heterogeneous conditions (<em>i.e.</em>, the exceedance of the solubility limit with increasing loading) can be identified by observing either a rapid decline in ultimate yield of the diamine hydrolysis product from near-stoichiometric to much lower values, or a decrease in rate of formation of the diamine hydrolysis product relative to its ultimate yield. The latter criterion is expected to be the more powerful indicator. These criteria can be used in future work to define and interpret an experimental program for determining solubility limits for aromatic diisocyanates or other poorly-soluble, water-reactive substances.</p>","PeriodicalId":74,"journal":{"name":"Environmental Science: Processes & Impacts","volume":" 8","pages":" 1373-1379"},"PeriodicalIF":4.3,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141496394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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}
Dissolved organic matter (DOM) is ubiquitous in aquatic environments and challenging to characterize due to its heterogeneity. Optical measurements (i.e., absorbance and fluorescence spectroscopy) are popular characterization tools, because they are non-destructive, require small sample volumes, and are relatively inexpensive and more accessible compared to other techniques (e.g., high resolution mass spectrometry). To make inferences about DOM chemistry, optical surrogates have been derived from absorbance and fluorescence spectra to describe differences in spectral shape (e.g., E2:E3 ratio, spectral slope, fluorescence indices) or quantify carbon-normalized optical responses (e.g., specific absorbance (SUVA) or specific fluorescence intensity (SFI)). The most common interpretations relate these optical surrogates to DOM molecular weight or aromaticity. This critical review traces the genesis of each of these interpretations and, to the extent possible, discusses additional lines of evidence that have been developed since their inception using datasets comparing diverse DOM sources or strategic endmembers. This review draws several conclusions. More caution is needed to avoid presenting surrogates as specific to either molecular weight or aromaticity, as these physicochemical characteristics are often correlated or interdependent. Many surrogates are proposed using narrow contexts, such as fractionation of a limited number of samples or dependence on isolates. Further study is needed to determine if interpretations are generalizable to whole-waters. Lastly, there is a broad opportunity to identify why endmembers with low abundance of aromatic carbon (e.g., effluent organic matter, Antarctic lakes) often do not follow systematic trends with molecular weight or aromaticity as observed in endmembers from terrestrial environments with higher plant inputs.
溶解有机物(DOM)在水生环境中无处不在,由于其异质性,对其进行表征具有挑战性。光学测量(即吸光度和荧光光谱)是常用的表征工具,因为它们不具破坏性,所需样本量小,而且相对便宜,与其他技术(如高分辨率质谱法)相比更容易获得。为了推断 DOM 化学性质,人们从吸收光谱和荧光光谱中推导出光学代用指标,以描述光谱形状的差异(如 E2:E3 比值、光谱斜率、荧光指数)或量化碳归一化光学响应(如特定吸收光谱(SUVA)或特定荧光强度(SFI))。最常见的解释是将这些光学代用指标与 DOM 分子量或芳香度联系起来。本评论追溯了每种解释的起源,并尽可能讨论了自这些解释出现以来,利用比较不同 DOM 来源或战略内含物的数据集开发出的其他证据。本综述得出了几个结论。需要更加谨慎,避免把代用指标说成是分子量或芳香度的特异性指标,因为这些理化特征往往是相互关联或相互依存的。许多代用指标都是在狭窄的范围内提出的。例如,对数量有限的样本进行分馏或依赖于分离物并将解释推广到整个水体的做法值得进一步研究。最后,我们还有很多机会来确定为什么芳香碳含量较低的内含物(如南极湖泊中的排出有机物)通常不会像植物投入量较高的陆地环境中的内含物那样,随着分子量或芳香度的增加而呈现系统化趋势。
{"title":"Critical review of fluorescence and absorbance measurements as surrogates for the molecular weight and aromaticity of dissolved organic matter†","authors":"Julie A. Korak and Garrett McKay","doi":"10.1039/D4EM00183D","DOIUrl":"10.1039/D4EM00183D","url":null,"abstract":"<p >Dissolved organic matter (DOM) is ubiquitous in aquatic environments and challenging to characterize due to its heterogeneity. Optical measurements (<em>i.e.</em>, absorbance and fluorescence spectroscopy) are popular characterization tools, because they are non-destructive, require small sample volumes, and are relatively inexpensive and more accessible compared to other techniques (<em>e.g.</em>, high resolution mass spectrometry). To make inferences about DOM chemistry, optical surrogates have been derived from absorbance and fluorescence spectra to describe differences in spectral shape (<em>e.g.</em>, E2:E3 ratio, spectral slope, fluorescence indices) or quantify carbon-normalized optical responses (<em>e.g.</em>, specific absorbance (SUVA) or specific fluorescence intensity (SFI)). The most common interpretations relate these optical surrogates to DOM molecular weight or aromaticity. This critical review traces the genesis of each of these interpretations and, to the extent possible, discusses additional lines of evidence that have been developed since their inception using datasets comparing diverse DOM sources or strategic endmembers. This review draws several conclusions. More caution is needed to avoid presenting surrogates as specific to either molecular weight or aromaticity, as these physicochemical characteristics are often correlated or interdependent. Many surrogates are proposed using narrow contexts, such as fractionation of a limited number of samples or dependence on isolates. Further study is needed to determine if interpretations are generalizable to whole-waters. Lastly, there is a broad opportunity to identify why endmembers with low abundance of aromatic carbon (<em>e.g.</em>, effluent organic matter, Antarctic lakes) often do not follow systematic trends with molecular weight or aromaticity as observed in endmembers from terrestrial environments with higher plant inputs.</p>","PeriodicalId":74,"journal":{"name":"Environmental Science: Processes & Impacts","volume":" 10","pages":" 1663-1702"},"PeriodicalIF":4.3,"publicationDate":"2024-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/em/d4em00183d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141505200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mohammad Qutob, Mohd Rafatullah, Syahidah Akmal Muhammad, Masoom Raza Siddiqui and Mahboob Alam
The presence of impurities is a significant restriction to the use of natural iron minerals as catalysts in the advanced oxidation process (AOP), especially if applied for soil remediation. This study evaluated the catalytic activity of tropical soil, which has relatively low impurities and naturally contains iron, for the remediation of phenanthrene (PHE) contamination. The system showed good performance, and the best result was 81% PHE removal after 24 h under experimental conditions of pH 7, [PHE]0 = 300 mg/50 g soil, temperature 55 °C, air flow = 260 mL min−1, and [persulfate]0 = 20 mg kg−1, while the mineralization was 61%. Nevertheless, certain limitations were noted in the soil matrix following the remediation procedure, including the appearance of cracks in the soil aggregate, reduction in the crystal size of the soil particles, and decline in the iron and aluminium contents. The results confirmed that the radicals play a major role in the remediation process. SO4˙− was more dominant than O2˙−, while HO˙ played a minor role. Additionally, the by-products were detected by gas chromatography-mass spectroscopy (GC-MS), and the degradation pathway of PHE is proposed. Toxicity assessment tests were performed by using a computational method. In spite of the challenges, this research achieved notable progress in soil remediation, taking a significant step forward in implementing the AOP without catalysts to activate oxidants and remove PHE within the soil. Also, this approach supports sustainability by reducing the need for extra materials and providing an environmentally friendly way of soil remediation.
{"title":"A sustainable method for oxidizing phenanthrene in tropical soil using natural iron as a catalyst in a slurry phase reactor with persulfate assistance†","authors":"Mohammad Qutob, Mohd Rafatullah, Syahidah Akmal Muhammad, Masoom Raza Siddiqui and Mahboob Alam","doi":"10.1039/D4EM00328D","DOIUrl":"10.1039/D4EM00328D","url":null,"abstract":"<p >The presence of impurities is a significant restriction to the use of natural iron minerals as catalysts in the advanced oxidation process (AOP), especially if applied for soil remediation. This study evaluated the catalytic activity of tropical soil, which has relatively low impurities and naturally contains iron, for the remediation of phenanthrene (PHE) contamination. The system showed good performance, and the best result was 81% PHE removal after 24 h under experimental conditions of pH 7, [PHE]<small><sub>0</sub></small> = 300 mg/50 g soil, temperature 55 °C, air flow = 260 mL min<small><sup>−1</sup></small>, and [persulfate]<small><sub>0</sub></small> = 20 mg kg<small><sup>−1</sup></small>, while the mineralization was 61%. Nevertheless, certain limitations were noted in the soil matrix following the remediation procedure, including the appearance of cracks in the soil aggregate, reduction in the crystal size of the soil particles, and decline in the iron and aluminium contents. The results confirmed that the radicals play a major role in the remediation process. SO<small><sub>4</sub></small>˙<small><sup>−</sup></small> was more dominant than O<small><sub>2</sub></small>˙<small><sup>−</sup></small>, while HO˙ played a minor role. Additionally, the by-products were detected by gas chromatography-mass spectroscopy (GC-MS), and the degradation pathway of PHE is proposed. Toxicity assessment tests were performed by using a computational method. In spite of the challenges, this research achieved notable progress in soil remediation, taking a significant step forward in implementing the AOP without catalysts to activate oxidants and remove PHE within the soil. Also, this approach supports sustainability by reducing the need for extra materials and providing an environmentally friendly way of soil remediation.</p>","PeriodicalId":74,"journal":{"name":"Environmental Science: Processes & Impacts","volume":" 8","pages":" 1391-1404"},"PeriodicalIF":4.3,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141505201","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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}
Giulia Kommana, Michael Hupfer, Jason Nicholas Woodhouse, Hans-Peter Grossart and Tobias Goldhammer
Iron (Fe) plays an important role in the biogeochemical cycling of carbon and nutrients in aquatic systems. Reactive Fe phases can interact with organic carbon and facilitate the removal of carbon from the biogeochemical cycle; however, this important ecosystem function is often strongly controlled by Fe availability. Due to pollution from lignite mining in the Lusatian province in Northeast Germany, large amounts of iron and sulfate are released into the fluvial-lacustrine system of the Spree River. It was hypothesized that the input of freshly precipitated iron oxyhydroxides from mining areas (e.g., ferrihydrite) alter the biodegradation of particulate organic matter (POM) in downstream lacustrine sediments. To investigate the Fe-dependent degradation of POM, slurries mimicking iron-polluted sediments (85 mg Fe per g, 116 mg Fe per g, and 149 mg Fe per g dry weight) were incubated with plankton or leaf POM under anoxic and oxic headspace conditions, and CO2 and CH4 emissions, water chemistry, and stable isotopes of dissolved inorganic carbon were measured. The experiments revealed that (i) with an increasing Fe content, the CO2 and CH4 emissions were gradually reduced, (ii) CO2 and CH4 production was higher during plankton degradation than during leaf decomposition, and (iii) under oxic conditions, CO2 production was higher and CH4 production was lower when compared to the treatments under anoxic conditions. These findings demonstrate that while benthic mineralization of fresh POM typically releases greenhouse gases into the water column, the availability of iron oxyhydroxides can contribute to reduced greenhouse gas emissions from sediments. This is of considerable relevance for future carbon budgets of similar mining-affected, iron-polluted fluvial-lacustrine river systems.
铁(Fe)在水生系统中碳和营养物质的生物地球化学循环中发挥着重要作用。反应性铁相可与有机碳相互作用,促进生物地球化学循环中碳的去除;然而,这一重要的生态系统功能往往受到铁供应量的强烈控制。由于德国东北部卢萨特省褐煤开采造成的污染,大量铁和硫酸盐被释放到施普雷河的河道-湖泊系统中。据推测,矿区新析出的铁氧氢氧化物(如铁酸盐)会改变下游湖沼沉积物中颗粒有机物(POM)的生物降解。为了研究 POM 的铁依赖性降解,在缺氧和缺氧顶空条件下,模拟铁污染沉积物(每克含铁 85 毫克、每克含铁 116 毫克和每克干重含铁 149 毫克)的泥浆与浮游生物或叶片 POM 一起培养,并测量 CO2 和 CH4 排放、水化学和溶解无机碳的稳定同位素。实验结果表明:(i) 随着铁含量的增加,CO2 和 CH4 的排放量逐渐减少;(ii) 浮游生物降解过程中 CO2 和 CH4 的产生量高于叶片分解过程中;(iii) 与缺氧条件下的处理相比,缺氧条件下 CO2 的产生量更高,CH4 的产生量更低。这些研究结果表明,虽然新鲜 POM 的底栖矿化通常会将温室气体释放到水体中,但铁氧氢氧化物的存在有助于减少沉积物的温室气体排放。这对类似受采矿影响、铁污染的河流-湖泊系统未来的碳预算具有重要意义。
{"title":"Reduced greenhouse gas emissions from particulate organic matter degradation in iron-enriched sediments†","authors":"Giulia Kommana, Michael Hupfer, Jason Nicholas Woodhouse, Hans-Peter Grossart and Tobias Goldhammer","doi":"10.1039/D4EM00185K","DOIUrl":"10.1039/D4EM00185K","url":null,"abstract":"<p >Iron (Fe) plays an important role in the biogeochemical cycling of carbon and nutrients in aquatic systems. Reactive Fe phases can interact with organic carbon and facilitate the removal of carbon from the biogeochemical cycle; however, this important ecosystem function is often strongly controlled by Fe availability. Due to pollution from lignite mining in the Lusatian province in Northeast Germany, large amounts of iron and sulfate are released into the fluvial-lacustrine system of the Spree River. It was hypothesized that the input of freshly precipitated iron oxyhydroxides from mining areas (<em>e.g.</em>, ferrihydrite) alter the biodegradation of particulate organic matter (POM) in downstream lacustrine sediments. To investigate the Fe-dependent degradation of POM, slurries mimicking iron-polluted sediments (85 mg Fe per g, 116 mg Fe per g, and 149 mg Fe per g dry weight) were incubated with plankton or leaf POM under anoxic and oxic headspace conditions, and CO<small><sub>2</sub></small> and CH<small><sub>4</sub></small> emissions, water chemistry, and stable isotopes of dissolved inorganic carbon were measured. The experiments revealed that (i) with an increasing Fe content, the CO<small><sub>2</sub></small> and CH<small><sub>4</sub></small> emissions were gradually reduced, (ii) CO<small><sub>2</sub></small> and CH<small><sub>4</sub></small> production was higher during plankton degradation than during leaf decomposition, and (iii) under oxic conditions, CO<small><sub>2</sub></small> production was higher and CH<small><sub>4</sub></small> production was lower when compared to the treatments under anoxic conditions. These findings demonstrate that while benthic mineralization of fresh POM typically releases greenhouse gases into the water column, the availability of iron oxyhydroxides can contribute to reduced greenhouse gas emissions from sediments. This is of considerable relevance for future carbon budgets of similar mining-affected, iron-polluted fluvial-lacustrine river systems.</p>","PeriodicalId":74,"journal":{"name":"Environmental Science: Processes & Impacts","volume":" 7","pages":" 1227-1244"},"PeriodicalIF":4.3,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141441818","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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}
Holly Barrett, Jianxian Sun, Yuhao Chen, Diwen Yang, Jonathan Verreault, Magali Houde, Frank Wania and Hui Peng
The elevated concentrations of organohalogen contaminants in the endangered St. Lawrence Estuary (SLE) belugas have prompted the hypothesis that aryl hydrocarbon receptor (AhR) activity may be a contributor towards their potential adverse effects. While indirect associations between AhR and contaminant levels have been reported in SLE beluga tissues, AhR activity was never directly measured. Using bioassays and nontargeted analysis, this study contrasted AhR activity and agonist profiles between pooled tissue extracts of endangered SLE and non-threatened Arctic belugas. Tissue extracts of SLE belugas exhibited significantly higher overall AhR activity than that of Arctic belugas, with a 2000s SLE beluga liver extract exerting significantly higher activity than blubber extracts of SLE and Arctic belugas from the same time period. Contrary to our expectations, well-known AhR agonists detected by nontargeted analysis, including polychlorinated biphenyls (PCBs), were only minor contributors to the observed AhR activity. Instead, Tox21 suspect screening identified more polar chemicals, such as dyes and natural indoles, as potential contributors. Notably, the natural product bromoindole was selectively detected in SLE beluga liver at high abundance and was further confirmed as an AhR agonist. These findings highlighted the significance of the AhR-mediated toxicity pathway in belugas and underscored the importance of novel AhR agonists, particularly polar compounds, in its induction.
{"title":"Emerging investigator series: nontargeted screening of aryl hydrocarbon receptor agonists in endangered beluga whales from the St. Lawrence Estuary: beyond legacy contaminants†","authors":"Holly Barrett, Jianxian Sun, Yuhao Chen, Diwen Yang, Jonathan Verreault, Magali Houde, Frank Wania and Hui Peng","doi":"10.1039/D4EM00243A","DOIUrl":"10.1039/D4EM00243A","url":null,"abstract":"<p >The elevated concentrations of organohalogen contaminants in the endangered St. Lawrence Estuary (SLE) belugas have prompted the hypothesis that aryl hydrocarbon receptor (AhR) activity may be a contributor towards their potential adverse effects. While indirect associations between AhR and contaminant levels have been reported in SLE beluga tissues, AhR activity was never directly measured. Using bioassays and nontargeted analysis, this study contrasted AhR activity and agonist profiles between pooled tissue extracts of endangered SLE and non-threatened Arctic belugas. Tissue extracts of SLE belugas exhibited significantly higher overall AhR activity than that of Arctic belugas, with a 2000s SLE beluga liver extract exerting significantly higher activity than blubber extracts of SLE and Arctic belugas from the same time period. Contrary to our expectations, well-known AhR agonists detected by nontargeted analysis, including polychlorinated biphenyls (PCBs), were only minor contributors to the observed AhR activity. Instead, Tox21 suspect screening identified more polar chemicals, such as dyes and natural indoles, as potential contributors. Notably, the natural product bromoindole was selectively detected in SLE beluga liver at high abundance and was further confirmed as an AhR agonist. These findings highlighted the significance of the AhR-mediated toxicity pathway in belugas and underscored the importance of novel AhR agonists, particularly polar compounds, in its induction.</p>","PeriodicalId":74,"journal":{"name":"Environmental Science: Processes & Impacts","volume":" 9","pages":" 1451-1464"},"PeriodicalIF":4.3,"publicationDate":"2024-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141430961","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"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}