Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143538
J.M. Sanchez , J. Oliva , C. Gomez-Solis , E. Puentes-Prado , E. Montes , I. Juárez-Ramírez , C.R. Garcia , J. Moreno Palmerin
This work reports the synthesis of Fe2O3 (FeO) microparticles using the Pechini method and their use to remove microplastics from tap water. The analysis by electronic microscopy revealed that the FeO microparticles (FeMicroPs) have a porous structure and are formed by interconnected grains with sizes of 80–120 nm. In addition, the X-ray diffraction analysis pointed out that the FeMicroPs are composed of γ- Fe2O3 and α- Fe2O3 phases. To remove the PS and PET microplastics with sizes of 0.1–3 μm from the tap water, FeO was added to the contaminated water and the mixture of FeO + microplastics was irradiated with focused NIR light (980 nm). This provoked the melting of the microplastics on the FeO surface. Later, the FeMicroPs with adsorbed microplastics was recovered with magnets. This last procedure permitted a high removal of microplastics from the tap water, and the adsorption capacity was 1000 mg/g. In the next step, the microplastics adsorbed on the FeO were irradiated with NIR light to induce its thermal decomposition by photothermal irradiation, this in turn, produced the elimination of the microplastics from the FeO surface and allowed its reuse to remove more microplastics from the tap water. The elimination of the microplastics from the FeO surface was confirmed by the FTIR and Raman techniques, since the vibrational peaks associated with the microplastics disappeared from the FeO surface after the photothermal irradiation. Thus, the results of this investigation suggest that the photothermal irradiation with NIR light not only facilitates the removal of microplastics from the tap water, but also, it was useful to degrade the microplastics definitively without producing more contamination. This technique could be used to remove microplastics in water treatment plants.
{"title":"High removal of PS and PET microplastics from tap water by using Fe2O3 porous microparticles and photothermal irradiation with NIR light","authors":"J.M. Sanchez , J. Oliva , C. Gomez-Solis , E. Puentes-Prado , E. Montes , I. Juárez-Ramírez , C.R. Garcia , J. Moreno Palmerin","doi":"10.1016/j.chemosphere.2024.143538","DOIUrl":"10.1016/j.chemosphere.2024.143538","url":null,"abstract":"<div><div>This work reports the synthesis of Fe<sub>2</sub>O<sub>3</sub> (FeO) microparticles using the Pechini method and their use to remove microplastics from tap water. The analysis by electronic microscopy revealed that the FeO microparticles (FeMicroPs) have a porous structure and are formed by interconnected grains with sizes of 80–120 nm. In addition, the X-ray diffraction analysis pointed out that the FeMicroPs are composed of γ- Fe<sub>2</sub>O<sub>3</sub> and α- Fe<sub>2</sub>O<sub>3</sub> phases. To remove the PS and PET microplastics with sizes of 0.1–3 μm from the tap water, FeO was added to the contaminated water and the mixture of FeO + microplastics was irradiated with focused NIR light (980 nm). This provoked the melting of the microplastics on the FeO surface. Later, the FeMicroPs with adsorbed microplastics was recovered with magnets. This last procedure permitted a high removal of microplastics from the tap water, and the adsorption capacity was 1000 mg/g. In the next step, the microplastics adsorbed on the FeO were irradiated with NIR light to induce its thermal decomposition by photothermal irradiation, this in turn, produced the elimination of the microplastics from the FeO surface and allowed its reuse to remove more microplastics from the tap water. The elimination of the microplastics from the FeO surface was confirmed by the FTIR and Raman techniques, since the vibrational peaks associated with the microplastics disappeared from the FeO surface after the photothermal irradiation. Thus, the results of this investigation suggest that the photothermal irradiation with NIR light not only facilitates the removal of microplastics from the tap water, but also, it was useful to degrade the microplastics definitively without producing more contamination. This technique could be used to remove microplastics in water treatment plants.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143538"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142483096","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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}
Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143624
Hannah Flach, Sarah Pfeffer, Petra Dietmann, Michael Kühl, Susanne J. Kühl
The human impact on environmental landscapes, such as land use, climate change or pollution, is threatening global biodiversity and ecosystems maintenance. Pesticides like the herbicide glyphosate have garnered considerable attention due to their well-documented harmful effects on non-target species. During application, the active ingredient glyphosate is utilized in various formulations, each containing different additive adjuvants. However, the possible effects of these formulations on amphibians - the group with the highest decline rates among vertebrates - remain largely unknown.
Therefore, the present study investigated the effects of four glyphosate formulations (Glyphosat TF, Durano TF, Helosate 450 TF, Kyleo) on the embryonic development of the model organism Xenopus laevis (South African clawed frog). Embryos at the 2-cell stage were exposed to various concentrations of glyphosate formulations (glyphosate: 0.01–100 mg/L), and mortality as well as sublethal effects on different organs and tissues were analyzed. The results indicated that the formulations had different effects, particularly on the mortality of Xenopus laevis embryos. At sublethal concentrations, the formulations altered the embryos' external appearance, leading to malformations such as reduced eye and head size. In addition, exposure to formulations impaired heart morphology and function, and the expression of heart-specific genes was altered at a molecular level.
Our results confirmed that glyphosate formulations had a stronger effect on Xenopus laevis embryogenesis than pure glyphosate. Therefore, it is crucial to evaluate the active ingredient and the co-formulations independently, as well as the combined, commercially available products, during pesticide risk assessments and renewal procedures of agrochemicals. The severe global decline of amphibians, partly due to herbicide use, highlights the need for strict and efficient monitoring of environmental pesticide loads and application areas.
{"title":"Glyphosate formulations cause mortality and diverse sublethal defects during embryonic development of the amphibian Xenopus laevis","authors":"Hannah Flach, Sarah Pfeffer, Petra Dietmann, Michael Kühl, Susanne J. Kühl","doi":"10.1016/j.chemosphere.2024.143624","DOIUrl":"10.1016/j.chemosphere.2024.143624","url":null,"abstract":"<div><div>The human impact on environmental landscapes, such as land use, climate change or pollution, is threatening global biodiversity and ecosystems maintenance. Pesticides like the herbicide glyphosate have garnered considerable attention due to their well-documented harmful effects on non-target species. During application, the active ingredient glyphosate is utilized in various formulations, each containing different additive adjuvants. However, the possible effects of these formulations on amphibians - the group with the highest decline rates among vertebrates - remain largely unknown.</div><div>Therefore, the present study investigated the effects of four glyphosate formulations (Glyphosat TF, Durano TF, Helosate 450 TF, Kyleo) on the embryonic development of the model organism <em>Xenopus laevis</em> (South African clawed frog). Embryos at the 2-cell stage were exposed to various concentrations of glyphosate formulations (glyphosate: 0.01–100 mg/L), and mortality as well as sublethal effects on different organs and tissues were analyzed. The results indicated that the formulations had different effects, particularly on the mortality of <em>Xenopus laevis</em> embryos. At sublethal concentrations, the formulations altered the embryos' external appearance, leading to malformations such as reduced eye and head size. In addition, exposure to formulations impaired heart morphology and function, and the expression of heart-specific genes was altered at a molecular level.</div><div>Our results confirmed that glyphosate formulations had a stronger effect on <em>Xenopus laevis</em> embryogenesis than pure glyphosate. Therefore, it is crucial to evaluate the active ingredient and the co-formulations independently, as well as the combined, commercially available products, during pesticide risk assessments and renewal procedures of agrochemicals. The severe global decline of amphibians, partly due to herbicide use, highlights the need for strict and efficient monitoring of environmental pesticide loads and application areas.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143624"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142514668","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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}
Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143616
Yanting Li , Lihua Deng , Yaxi Jiang , Xinhui Jiang
Dimetridazole (DMZ) is commonly used as a veterinary drug, resulting in high emissions and environmental pollution and DMZ residues are carcinogenic, genotoxic, and mutagenic to humans. Therefore, it is essential to construct a fast, sensitive and simple sensor to monitor DMZ. In this study, samarium molybdate nanosheets modified multi-walled carbon nanotube composites (SmM/MWCNT) were synthesized to modify GCE for detecting DMZ. The SmM/MWCNT material was also characterized by various analytical and spectroscopic techniques, such as FE-SEM, HRTEM, FT-IR, Raman spectroscopy, XRD, elemental mapping and XPS, to demonstrate the successful synthesis of the composite. Besides, the electrochemical behavior of SmM/MWCNT/GCE for DMZ was also investigated using CV and DPV, and the modified electrode showed good electrochemical sensing performance for DMZ with a low detection limit (0.08 μM), a wide linear range (0.1∼1000 μM), and excellent selectivity. Finally, the SmM/MWCNT/GCE was successfully applied to detect DMZ in environmental and biological samples, and satisfactory recoveries (95%∼105%) were obtained. To the best of our knowledge, the synthesis of SmM/MWCNT and its application in electrochemical sensors are reported for the first time, which demonstrates that it can provide a new route for real-time monitoring of environmental pollutants.
{"title":"Hydrothermal synthesis and characterization of samarium molybdate nanosheets modified multi-walled carbon nanotubes: Real-time analysis of dimetridazole in environmental and biological samples","authors":"Yanting Li , Lihua Deng , Yaxi Jiang , Xinhui Jiang","doi":"10.1016/j.chemosphere.2024.143616","DOIUrl":"10.1016/j.chemosphere.2024.143616","url":null,"abstract":"<div><div>Dimetridazole (DMZ) is commonly used as a veterinary drug, resulting in high emissions and environmental pollution and DMZ residues are carcinogenic, genotoxic, and mutagenic to humans. Therefore, it is essential to construct a fast, sensitive and simple sensor to monitor DMZ. In this study, samarium molybdate nanosheets modified multi-walled carbon nanotube composites (SmM/MWCNT) were synthesized to modify GCE for detecting DMZ. The SmM/MWCNT material was also characterized by various analytical and spectroscopic techniques, such as FE-SEM, HRTEM, FT-IR, Raman spectroscopy, XRD, elemental mapping and XPS, to demonstrate the successful synthesis of the composite. Besides, the electrochemical behavior of SmM/MWCNT/GCE for DMZ was also investigated using CV and DPV, and the modified electrode showed good electrochemical sensing performance for DMZ with a low detection limit (0.08 μM), a wide linear range (0.1∼1000 μM), and excellent selectivity. Finally, the SmM/MWCNT/GCE was successfully applied to detect DMZ in environmental and biological samples, and satisfactory recoveries (95%∼105%) were obtained. To the best of our knowledge, the synthesis of SmM/MWCNT and its application in electrochemical sensors are reported for the first time, which demonstrates that it can provide a new route for real-time monitoring of environmental pollutants.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143616"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142514670","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143602
Hui Li , Benjamin Atkins , Benjamin Reinhart , Elizabeth Herndon
Catechol and hydroquinone are widely present hydroxybenzene isomers in the natural environment that induce environmental toxicities. These hydroxybenzene compounds can be effectively removed by manganese (Mn)-oxides via sorption and oxidative degradation processes. In the present study, we investigated the structure–reactivity relationships in the sorption and oxidation of catechol and hydroquinone on Mn-oxide surfaces. Two widely present Mn-oxides, including hydrous Mn oxide (HMO) and cryptomelane, comprised of layer and tunnel structures, respectively, are specifically studied. Effects of Mn-oxide structures and environmental pH conditions on the removal efficiency of these hydroxybenzene compounds, via sorption and oxidative degradation, are investigated. Cryptomelane, which has a higher specific surface area than HMO, possesses a higher sorption and oxidation capacity. The complexation mechanisms of catechol and hydroquinone vary due to their structure-induced difference in reactivity. Catechol reduced and dissolved more Mn from Mn-oxides than hydroquinone, accompanied by a higher C loss of catechol-C, suggesting a higher reactivity of catechol. Structural changes occurred in the Mn-oxides resulting from reaction with catechol and hydroquinone: reduction of Mn(IV), corresponding formation of Mn(III) and Mn(II) in the mineral, and free Mn2+ ions released into the suspension. These insights could help us better understand and predict the fate of hydroxybenzene compounds in Mn-oxide-rich soils and wastewater treatment systems that generate Mn-oxides via Mn removal and the associated environmental toxicity.
{"title":"Structure–reactivity relationships in the removal efficiency of catechol and hydroquinone by structurally diverse Mn-oxides","authors":"Hui Li , Benjamin Atkins , Benjamin Reinhart , Elizabeth Herndon","doi":"10.1016/j.chemosphere.2024.143602","DOIUrl":"10.1016/j.chemosphere.2024.143602","url":null,"abstract":"<div><div>Catechol and hydroquinone are widely present hydroxybenzene isomers in the natural environment that induce environmental toxicities. These hydroxybenzene compounds can be effectively removed by manganese (Mn)-oxides via sorption and oxidative degradation processes. In the present study, we investigated the structure–reactivity relationships in the sorption and oxidation of catechol and hydroquinone on Mn-oxide surfaces. Two widely present Mn-oxides, including hydrous Mn oxide (HMO) and cryptomelane, comprised of layer and tunnel structures, respectively, are specifically studied. Effects of Mn-oxide structures and environmental pH conditions on the removal efficiency of these hydroxybenzene compounds, via sorption and oxidative degradation, are investigated. Cryptomelane, which has a higher specific surface area than HMO, possesses a higher sorption and oxidation capacity. The complexation mechanisms of catechol and hydroquinone vary due to their structure-induced difference in reactivity. Catechol reduced and dissolved more Mn from Mn-oxides than hydroquinone, accompanied by a higher C loss of catechol-C, suggesting a higher reactivity of catechol. Structural changes occurred in the Mn-oxides resulting from reaction with catechol and hydroquinone: reduction of Mn(IV), corresponding formation of Mn(III) and Mn(II) in the mineral, and free Mn<sup>2+</sup> ions released into the suspension. These insights could help us better understand and predict the fate of hydroxybenzene compounds in Mn-oxide-rich soils and wastewater treatment systems that generate Mn-oxides via Mn removal and the associated environmental toxicity.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143602"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142514678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143648
Treavor H. Boyer , Emily Briese , Lucas Crane , Jehangir Bhadha , Douglas F. Call , Eric S. McLamore , Bruce Rittmann , Shea Tuberty , Paul Westerhoff , Owen W. Duckworth
Phosphorus (P) removal from water and recovery into useable forms is a critical component of creating a sustainable P cycle, although mature technologies for P removal and recovery are still lacking. The goal of this paper was to advance the testing of novel materials for P removal and recovery from water by providing guidance on the development of more realistic aqueous matrices used during materials development. Literature reports of “new” materials to remove P from water are often difficult to compare in terms of performance because authors use a myriad of water chemistries containing P concentrations, pH, and competing ions. Moreover, many tests are conducted in simplified matrices that do not reflect conditions in real systems. To address this critical gap, the research herein developed a systematic approach of identifying aqueous matrices relevant to P recovery, including key components in the aqueous matrices having the greatest influence on the mechanisms of P removal with emphasis on phosphate precipitation and phosphate adsorption, and providing guidelines on relevant “recipes” for aqueous solutions for testing novel materials. Key components in the aqueous matrices included hydrogen ion (i.e., pH), multivalent metal cations, and dissolved organic matter due to their influence on phosphate precipitation and adsorption mechanisms. Recipes for buffer solution and synthetic groundwater, surface water, anaerobic digestate, and stored urine are discussed in the context of P removal and recovery processes. Wherein the adoption of standard matrices in other fields have permitted direct comparison of processes or materials, it is anticipated that adoption of relevant aqueous matrix recipes for P removal and recovery will improve the ability to directly compare novel materials and processes.
从水中去除磷(P)并将其回收为可用形式是建立可持续磷循环的重要组成部分,但目前仍缺乏成熟的磷去除和回收技术。本文的目的是通过为材料开发过程中使用的更符合实际的水基质的开发提供指导,推进用于从水中去除和回收磷的新型材料的测试。有关从水中去除 P 的 "新型 "材料的文献报告通常很难在性能方面进行比较,因为作者使用了大量含有 P 浓度、pH 值和竞争离子的水化学成分。此外,许多测试都是在简化的基质中进行的,不能反映真实系统的条件。为了弥补这一重大缺陷,本文的研究开发了一种系统方法,用于确定与磷回收相关的水基质,包括对磷去除机制影响最大的水基质中的关键成分,重点是磷酸盐沉淀和磷酸盐吸附,并为测试新型材料提供相关水溶液 "配方 "指南。水基质中的关键成分包括氢离子(即 pH 值)、多价金属阳离子和溶解有机物,因为它们对磷酸盐沉淀和吸附机制有影响。结合磷的去除和回收过程,讨论了缓冲溶液和合成地下水、地表水、厌氧沼渣和储存尿液的配方。在其他领域采用标准基质可以对工艺或材料进行直接比较,而在去除和回收磷方面采用相关的水基质配方预计将提高对新型材料和工艺进行直接比较的能力。
{"title":"Guidance on aqueous matrices for evaluating novel precipitants and adsorbents for phosphorus removal and recovery","authors":"Treavor H. Boyer , Emily Briese , Lucas Crane , Jehangir Bhadha , Douglas F. Call , Eric S. McLamore , Bruce Rittmann , Shea Tuberty , Paul Westerhoff , Owen W. Duckworth","doi":"10.1016/j.chemosphere.2024.143648","DOIUrl":"10.1016/j.chemosphere.2024.143648","url":null,"abstract":"<div><div>Phosphorus (P) removal from water and recovery into useable forms is a critical component of creating a sustainable P cycle, although mature technologies for P removal and recovery are still lacking. The goal of this paper was to advance the testing of novel materials for P removal and recovery from water by providing guidance on the development of more realistic aqueous matrices used during materials development. Literature reports of “new” materials to remove P from water are often difficult to compare in terms of performance because authors use a myriad of water chemistries containing P concentrations, pH, and competing ions. Moreover, many tests are conducted in simplified matrices that do not reflect conditions in real systems. To address this critical gap, the research herein developed a systematic approach of identifying aqueous matrices relevant to P recovery, including key components in the aqueous matrices having the greatest influence on the mechanisms of P removal with emphasis on phosphate precipitation and phosphate adsorption, and providing guidelines on relevant “recipes” for aqueous solutions for testing novel materials. Key components in the aqueous matrices included hydrogen ion (i.e., pH), multivalent metal cations, and dissolved organic matter due to their influence on phosphate precipitation and adsorption mechanisms. Recipes for buffer solution and synthetic groundwater, surface water, anaerobic digestate, and stored urine are discussed in the context of P removal and recovery processes. Wherein the adoption of standard matrices in other fields have permitted direct comparison of processes or materials, it is anticipated that adoption of relevant aqueous matrix recipes for P removal and recovery will improve the ability to directly compare novel materials and processes.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143648"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142549444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143654
Jianzheng Wang , Chunying Liu , Ziao Di , Jiayu Huang , Hongjun Wei , Minjie Guo , Xiaoliang Yu , Nan Li , Jin Zhao , Bowen Cheng
Developing novel electrode materials plays a crucial role in enhancing the electrochemical sensing performance of chemically modified electrodes. This research presents a composite electrode material based on polyimide incorporated with multiwalled carbon nanotubes (PI-MWCNT) for the simultaneous detection of three nitrophenol isomers (NPs). First, the composite was prepared and characterized using microscopies, spectroscopic techniques, and electrochemical experiments. The results indicated that the PI-MWCNT exhibited porosity and roughness, which facilitated the enhancement of its sensing performance. Afterward, the detection capabilities of PI-MWCNT towards NPs were evaluated through voltammetry experiments under optimal conditions. The differential pulse voltammetry (DPV) curves revealed three distinct anodic peaks in the NPs solution, with linear ranges of 1–300 μM for 2-NP, 0.25–250 μM for 3-NP, and 0.25–400 μM for 4-NP. The limits of detection (LOD) were 0.50 μM for both 2-NP and 3-NP, and 0.64 μM for 4-NP. Furthermore, the proposed electrode material was successfully applied to real samples, achieving recovery rates ranging from 92.9% to 106%. This study could contribute to the development of more efficient and sensitive electrochemical sensors.
{"title":"Polyimide-multiwalled carbon nanotubes composite as electrochemical sensing platform for the simultaneous detection of nitrophenol isomers","authors":"Jianzheng Wang , Chunying Liu , Ziao Di , Jiayu Huang , Hongjun Wei , Minjie Guo , Xiaoliang Yu , Nan Li , Jin Zhao , Bowen Cheng","doi":"10.1016/j.chemosphere.2024.143654","DOIUrl":"10.1016/j.chemosphere.2024.143654","url":null,"abstract":"<div><div>Developing novel electrode materials plays a crucial role in enhancing the electrochemical sensing performance of chemically modified electrodes. This research presents a composite electrode material based on polyimide incorporated with multiwalled carbon nanotubes (PI-MWCNT) for the simultaneous detection of three nitrophenol isomers (NPs). First, the composite was prepared and characterized using microscopies, spectroscopic techniques, and electrochemical experiments. The results indicated that the PI-MWCNT exhibited porosity and roughness, which facilitated the enhancement of its sensing performance. Afterward, the detection capabilities of PI-MWCNT towards NPs were evaluated through voltammetry experiments under optimal conditions. The differential pulse voltammetry (DPV) curves revealed three distinct anodic peaks in the NPs solution, with linear ranges of 1–300 μM for 2-NP, 0.25–250 μM for 3-NP, and 0.25–400 μM for 4-NP. The limits of detection (LOD) were 0.50 μM for both 2-NP and 3-NP, and 0.64 μM for 4-NP. Furthermore, the proposed electrode material was successfully applied to real samples, achieving recovery rates ranging from 92.9% to 106%. This study could contribute to the development of more efficient and sensitive electrochemical sensors.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143654"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142565336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143623
Changhee Han , Md-Mafizur Rahman , Juil Kim , Bettina Lueke , Ralf Nauen
For over a decade, diamide insecticides have been effective against lepidopteran pests like beet armyworm, Spodoptera exigua (Hübner, 1808). However, the evolution of resistance poses a challenge to their sustainable use. We identified an I4790 M mutation in the S. exigua ryanodine receptor (RyR) gene, but its correlation with resistance varied across the field-collected Korean populations of S. exigua. RNA sequencing and differential gene expression analysis were performed to investigate other resistance mechanisms. Diamide-resistant and susceptible strains and F1 hybrids were compared by mapping RNA-seq reads to the S. exigua reference genome. CYP9A40 was identified as a critical gene in diamide resistance due to its high expression in the resistant strains. Synergist bioassays with piperonyl butoxide supported the role of P450s in diamide metabolic resistance in S. exigua. A strong positive correlation between CYP9A40 over-expression levels (up to 80-fold) and diamide LC50 values was obtained for field-collected populations uniformly showing a 100% frequency of the RyR I4790 M target-site resistance allele. To validate the function of CYP9A40 in diamide detoxification, we recombinantly expressed the gene and tested its ability to bind and degrade chlorantraniliprole as a substrate. The results confirmed its catalytic role in diamide metabolism. CYP9A40 has been identified and validated to confer metabolic resistance in Korean S. exigua populations. It works alongside the RyR target-site I4790 M mutation to enhance diamide resistance. These mechanisms offer insights for resistance monitoring and support insecticide resistance management programs to improve control strategies for S. exigua.
十多年来,二酰胺类杀虫剂一直对甜菜夜蛾等鳞翅目害虫有效。然而,抗药性的演变对其可持续使用构成了挑战。我们在 S. exigua 的雷诺丁受体(RyR)基因中发现了一个 I4790M 突变,但在田间采集的韩国 S. exigua 种群中,该突变与抗性的相关性各不相同。为了研究其他抗性机制,进行了 RNA 测序和差异基因表达分析。通过将 RNA-seq 读数映射到 S. exigua 参考基因组,对二胺抗性和易感株系及 F1 杂交种进行了比较。由于 CYP9A40 在抗性菌株中的高表达,它被确定为二酰胺抗性的关键基因。用胡椒基丁醚进行的增效剂生物测定证实了 P450s 在 S. exigua 的二酰胺代谢抗性中的作用。在田间采集的种群中,CYP9A40的过量表达水平(高达80倍)与二酰胺的半致死浓度值之间存在很强的正相关性,这些种群中RyR I4790M靶位抗性等位基因的频率均为100%。为了验证 CYP9A40 在二酰胺解毒中的功能,我们重组表达了该基因,并测试了其结合和降解作为底物的氯虫苯甲酰胺的能力。结果证实了它在二酰胺代谢中的催化作用。经鉴定和验证,CYP9A40 在韩国 S. exigua 群体中具有代谢抗性。它与 RyR 靶位点 I4790M 突变一起增强了二酰胺的抗性。这些机制为抗药性监测提供了启示,并支持杀虫剂抗药性管理计划,以改进对 S. exigua 的控制策略。
{"title":"Genome-wide analysis of detoxification genes conferring diamide insecticide resistance in Spodoptera exigua identifies CYP9A40","authors":"Changhee Han , Md-Mafizur Rahman , Juil Kim , Bettina Lueke , Ralf Nauen","doi":"10.1016/j.chemosphere.2024.143623","DOIUrl":"10.1016/j.chemosphere.2024.143623","url":null,"abstract":"<div><div>For over a decade, diamide insecticides have been effective against lepidopteran pests like beet armyworm, <em>Spodoptera exigua</em> (Hübner, 1808). However, the evolution of resistance poses a challenge to their sustainable use. We identified an I4790 M mutation in the <em>S. exigua</em> ryanodine receptor (RyR) gene, but its correlation with resistance varied across the field-collected Korean populations of <em>S. exigua</em>. RNA sequencing and differential gene expression analysis were performed to investigate other resistance mechanisms. Diamide-resistant and susceptible strains and F1 hybrids were compared by mapping RNA-seq reads to the <em>S. exigua</em> reference genome. <em>CYP9A40</em> was identified as a critical gene in diamide resistance due to its high expression in the resistant strains. Synergist bioassays with piperonyl butoxide supported the role of P450s in diamide metabolic resistance in <em>S. exigua</em>. A strong positive correlation between <em>CYP9A40</em> over-expression levels (up to 80-fold) and diamide LC<sub>50</sub> values was obtained for field-collected populations uniformly showing a 100% frequency of the RyR I4790 M target-site resistance allele. To validate the function of <em>CYP9A40</em> in diamide detoxification, we recombinantly expressed the gene and tested its ability to bind and degrade chlorantraniliprole as a substrate. The results confirmed its catalytic role in diamide metabolism. <em>CYP9A40</em> has been identified and validated to confer metabolic resistance in Korean <em>S. exigua</em> populations. It works alongside the RyR target-site I4790 M mutation to enhance diamide resistance. These mechanisms offer insights for resistance monitoring and support insecticide resistance management programs to improve control strategies for <em>S. exigua</em>.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143623"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142559736","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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}
Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143701
Lu Liu , Younes Ahmadi , Ki-Hyun Kim , Deepak Kukkar , Jan Szulejko
This research has been carried out to investigate unique relationships in adsorption behavior between polar and non-polar volatile organic compounds (VOCs: formaldehyde (FA) versus toluene) using commercial macadamia nutshell (MNS)-based microporous activated carbon (i.e., Procarb-900: namely, P900). The breakthrough (BT) volume, adsorption capacity, and partition coefficient of P900 are estimated for 100 ppm FA as a single component and as a binary phase with 100 ppm toluene. The contrasting features of adsorption (such as interfering/synergistic relationships) for VOC mixtures with different polarities are accounted for in terms of interaction between the key variables (e.g., pore size distribution, adsorbent particle size, surface element compositions, and sorbent bed mass). Accordingly, the powdered P900 (0.212–0.6 mm: 150 mg) exhibits an adsorption capacity of 5.7 mg g−1 and a partition coefficient of 0.19 mol kg−1 Pa−1 for single-phase FA at the 10% BT level. Interestingly, its FA adsorption performance is synergistically improved in the presence of toluene (e.g., > 150%) in the early stage of adsorption (e.g., 10% BT), although their competition reduced its performance at 99% BT. The apparent synergistic trend in the early BT stage may possibly reflect diffusion resistance of the adsorbent (e.g., small particle size and developed ultra-micropore structure) and natural attributes of FA (e.g., low affinity and smaller kinetic diameter). The overall results of this study are expected to offer a better understanding of the mechanisms underlying the interactions between the mixed VOC system and microporous adsorbents.
本研究使用基于商用澳洲坚果壳(MNS)的微孔活性炭(即 Procarb-900:即 P900),对极性和非极性挥发性有机化合物(VOC:甲醛(FA)和甲苯)之间的吸附行为的干扰/协同关系进行了研究。我们估算了 P900 在 100 ppm FA 作为单组分和 100 ppm 甲苯作为二元相时的突破 (BT) 量、吸附容量和分配系数。从关键变量(如孔径分布、吸附剂粒度、表面元素组成和吸附剂床层质量)之间的相互作用角度,说明了 P900 吸附剂对 FA 吸附的基本特征。因此,粉末状 P900(0.212-0.6 毫米:150 毫克)的吸附容量为 5.7 毫克 g-1,在 10% BT 水平下,对单相 FA 的分配系数为 0.19 摩尔 kg-1 Pa-1。有趣的是,在吸附的早期阶段(如 10% BT),当甲苯存在时(如 >150%),它的性能得到了协同改善,这可能反映了吸附剂的扩散阻力(如小粒径和发达的超微孔结构)和 FA 的天然属性(如低亲和力和较小的动力学直径)。这项研究的总体结果有望让人们更好地了解混合挥发性有机化合物体系与微孔吸附剂之间的相互作用机制。
{"title":"Assessment of interfering/synergistic effects in the adsorption between polar and non-polar VOCs on a commercial biomass-based microporous carbon","authors":"Lu Liu , Younes Ahmadi , Ki-Hyun Kim , Deepak Kukkar , Jan Szulejko","doi":"10.1016/j.chemosphere.2024.143701","DOIUrl":"10.1016/j.chemosphere.2024.143701","url":null,"abstract":"<div><div>This research has been carried out to investigate unique relationships in adsorption behavior between polar and non-polar volatile organic compounds (VOCs: formaldehyde (FA) versus toluene) using commercial macadamia nutshell (MNS)-based microporous activated carbon (i.e., Procarb-900: namely, P900). The breakthrough (BT) volume, adsorption capacity, and partition coefficient of P900 are estimated for 100 ppm FA as a single component and as a binary phase with 100 ppm toluene. The contrasting features of adsorption (such as interfering/synergistic relationships) for VOC mixtures with different polarities are accounted for in terms of interaction between the key variables (e.g., pore size distribution, adsorbent particle size, surface element compositions, and sorbent bed mass). Accordingly, the powdered P900 (0.212–0.6 mm: 150 mg) exhibits an adsorption capacity of 5.7 mg g<sup>−1</sup> and a partition coefficient of 0.19 mol kg<sup>−1</sup> Pa<sup>−1</sup> for single-phase FA at the 10% BT level. Interestingly, its FA adsorption performance is synergistically improved in the presence of toluene (e.g., > 150%) in the early stage of adsorption (e.g., 10% BT), although their competition reduced its performance at 99% BT. The apparent synergistic trend in the early BT stage may possibly reflect diffusion resistance of the adsorbent (e.g., small particle size and developed ultra-micropore structure) and natural attributes of FA (e.g., low affinity and smaller kinetic diameter). The overall results of this study are expected to offer a better understanding of the mechanisms underlying the interactions between the mixed VOC system and microporous adsorbents.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"368 ","pages":"Article 143701"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142633664","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143673
Arianna Bautista , Maria Björnsdotter , Carmen Sáez , Anna Jurado , Marta Llorca , Estanislao Pujades , Marinella Farré
Climate change impacts the Mediterranean region, transforming it from region with a semi-arid climate to a region with an arid climate. Under this situation, while groundwater is an essential hydric resource, its existence is in danger due to anthropogenic pressures. Persistent mobile organic compounds (PMOCs) have recently been recognised as an emerging problem; however, PMOCs in groundwater need to be better characterised. Here, we present a new analytical method to characterise the profile of PMOCs in groundwater based on two parallel solid-phase extraction (SPE), using weak anion exchange and weak cation exchange. Extracts were analysed by ultraperformance liquid chromatography (UPLC) using mix-mode chromatography for those compounds analysed under negative ionisation conditions and hydrophilic interaction liquid chromatography (HILIC) under positive conditions coupled to high-resolution mass-spectrometry (HRMS) using a Q-Exactive Orbitrap™ analyser. For the suspect screening of PMOCs in groundwater, the acquisition mode was in full scan (FS) by “independent scan of all ion fragmentation”. For the tentative identification, different online databases such as Environmental and Food Safety (EFS) HRAM Compound database, PFAS NIST database, ChemSpider for chemical structural information, MzCloud as a mass spectral database, and an in-house list with 1280 PMOC structures have been used. The performance of the method was assessed with 29 representative PMOCs which were selected based on the previous literature. The recovery rates have been between 63 and 110 % for 90 % of the target compounds and method limits of quantification (MLQ) between 0.3 and 10.5 ng/L.
The optimised approach was applied to assess PMOCs in the Besòs River aquifer, NE Spain, showing 148 tentatively identified structures at confidence levels 1–3. Among them, 66 suspects were tentatively identified at level 3, 54 at level 2, and 28 confirmed at level 1. Most of these compounds were polar and highly polar compounds which are difficult to retain with other extraction approaches. Major detected compounds were pharmaceuticals and personal care products (46), followed by perfluoroalkyl and polyfluoroalkyl substances (PFAS) (32), industrial additives (27), and pesticides (23), among other groups. Some compounds, such as ultrashort chain PFAS and fluorinated betaines, were detected for the first time in groundwaters in Spain.
{"title":"Determination of persistent and mobile organic compounds in the river–groundwater interface of the Besòs river delta, Spain, using a wide extraction approach","authors":"Arianna Bautista , Maria Björnsdotter , Carmen Sáez , Anna Jurado , Marta Llorca , Estanislao Pujades , Marinella Farré","doi":"10.1016/j.chemosphere.2024.143673","DOIUrl":"10.1016/j.chemosphere.2024.143673","url":null,"abstract":"<div><div>Climate change impacts the Mediterranean region, transforming it from region with a semi-arid climate to a region with an arid climate. Under this situation, while groundwater is an essential hydric resource, its existence is in danger due to anthropogenic pressures. Persistent mobile organic compounds (PMOCs) have recently been recognised as an emerging problem; however, PMOCs in groundwater need to be better characterised. Here, we present a new analytical method to characterise the profile of PMOCs in groundwater based on two parallel solid-phase extraction (SPE), using weak anion exchange and weak cation exchange. Extracts were analysed by ultraperformance liquid chromatography (UPLC) using mix-mode chromatography for those compounds analysed under negative ionisation conditions and hydrophilic interaction liquid chromatography (HILIC) under positive conditions coupled to high-resolution mass-spectrometry (HRMS) using a Q-Exactive Orbitrap™ analyser. For the suspect screening of PMOCs in groundwater, the acquisition mode was in full scan (FS) by “independent scan of all ion fragmentation”. For the tentative identification, different online databases such as Environmental and Food Safety (EFS) HRAM Compound database, PFAS NIST database, ChemSpider for chemical structural information, MzCloud as a mass spectral database, and an in-house list with 1280 PMOC structures have been used. The performance of the method was assessed with 29 representative PMOCs which were selected based on the previous literature. The recovery rates have been between 63 and 110 % for 90 % of the target compounds and method limits of quantification (MLQ) between 0.3 and 10.5 ng/L.</div><div>The optimised approach was applied to assess PMOCs in the Besòs River aquifer, NE Spain, showing 148 tentatively identified structures at confidence levels 1–3. Among them, 66 suspects were tentatively identified at level 3, 54 at level 2, and 28 confirmed at level 1. Most of these compounds were polar and highly polar compounds which are difficult to retain with other extraction approaches. Major detected compounds were pharmaceuticals and personal care products (46), followed by perfluoroalkyl and polyfluoroalkyl substances (PFAS) (32), industrial additives (27), and pesticides (23), among other groups. Some compounds, such as ultrashort chain PFAS and fluorinated betaines, were detected for the first time in groundwaters in Spain.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"368 ","pages":"Article 143673"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142634039","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143699
Lei Wu , Yuan Gao , Siwen Qiu , Zixuan Hu , Changbo Liu , Changsheng Yue , Jun Zhou
The porous and defective structure of biochar (BC) can accelerate surface electron transfer, promote the generation of more reactive oxygen species (ROS) by persulfate (PS), and effectively degrade organic pollutants in the soil. Electron transfer is a crucial link in this process, directly determining its oxidative degradation efficiency. In this study, using a novel strategy of enhancing electron transfer on the surface of BC by loading iron, three Fe-loaded BC activators (Fe-FeOx@BC, Fe2O3@BC and Fe3O4@BC) were synthesized to support the oxidative remediation of benzo(a)pyrene (BaP, Model compound of PAHs)-contaminated soil by PS. The results showed that Fe3O4@BC supported PS oxidation and remediation of BaP-contaminated soil had the best effect among the three BC-based activators, and the reuse effect was stable. Under the conditions of Fe3O4@BC addition of 1.00 wt%, PS addition of 0.75 wt%, reaction temperature of 35 °C, and solid-liquid ratio of 1:2.5, the removal rate of BaP in the soil reached the maximum of 93.84% at 120 min, and the soil toxicity was significantly reduced after remediation. The defect structure, conductive magnetic particles, and active functional groups on the surface of Fe3O4@BC were the key factors for activating PS to degrade BaP. With the combined action of the free radical pathway caused by ROS and the non-free radical pathway caused by 1O2, electron transfer, and active functional groups, BaP was degraded to small molecules such as CO2 and H2O, achieving rapid and efficient remediation of organic contaminated soil.
{"title":"Efficient oxidative remediation of polycyclic aromatic hydrocarbons (PAHs)-contaminated soil: A thorough comprehension of Fe-loaded biochar activated persulfate","authors":"Lei Wu , Yuan Gao , Siwen Qiu , Zixuan Hu , Changbo Liu , Changsheng Yue , Jun Zhou","doi":"10.1016/j.chemosphere.2024.143699","DOIUrl":"10.1016/j.chemosphere.2024.143699","url":null,"abstract":"<div><div>The porous and defective structure of biochar (BC) can accelerate surface electron transfer, promote the generation of more reactive oxygen species (ROS) by persulfate (PS), and effectively degrade organic pollutants in the soil. Electron transfer is a crucial link in this process, directly determining its oxidative degradation efficiency. In this study, using a novel strategy of enhancing electron transfer on the surface of BC by loading iron, three Fe-loaded BC activators (Fe-FeO<sub>x</sub>@BC, Fe<sub>2</sub>O<sub>3</sub>@BC and Fe<sub>3</sub>O<sub>4</sub>@BC) were synthesized to support the oxidative remediation of benzo(<em>a</em>)pyrene (BaP, Model compound of PAHs)-contaminated soil by PS. The results showed that Fe<sub>3</sub>O<sub>4</sub>@BC supported PS oxidation and remediation of BaP-contaminated soil had the best effect among the three BC-based activators, and the reuse effect was stable. Under the conditions of Fe<sub>3</sub>O<sub>4</sub>@BC addition of 1.00 wt%, PS addition of 0.75 wt%, reaction temperature of 35 °C, and solid-liquid ratio of 1:2.5, the removal rate of BaP in the soil reached the maximum of 93.84% at 120 min, and the soil toxicity was significantly reduced after remediation. The defect structure, conductive magnetic particles, and active functional groups on the surface of Fe<sub>3</sub>O<sub>4</sub>@BC were the key factors for activating PS to degrade BaP. With the combined action of the free radical pathway caused by ROS and the non-free radical pathway caused by <sup>1</sup>O<sub>2</sub>, electron transfer, and active functional groups, BaP was degraded to small molecules such as CO<sub>2</sub> and H<sub>2</sub>O, achieving rapid and efficient remediation of organic contaminated soil.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"368 ","pages":"Article 143699"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142634483","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"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}