Pub Date : 2024-11-01DOI: 10.1016/j.chemosphere.2024.143665
Mathieu Verhille , Robert Hausler
Perfluorooctanoic acid (PFOA) is a pervasive environmental contaminant with well-documented toxic effects on both humans and animals, attracting significant scientific concern. Due to its affinity for proteins, research has predominantly focused on PFOA's interactions with biological macromolecules. However, the specific role of smaller molecules, such as amino acids, remains underexplored. This study uniquely evaluates the potential of l-tryptophan (L-Trp) to mitigate PFOA toxicity and investigates the interaction mechanisms involved. Results indicate that the presence of L-Trp in PFOA-contaminated water reduces acute toxicity in Daphnia magna, with an optimal molar ratio of approximately 1:2 (Trp:PFOA). The findings reveal that non-covalent interactions, particularly van der Waals forces and hydrogen bonds, are central to the Trp–PFOA complex formation. Additional contributions from hydrophobic interactions at the indole group and electrostatic forces between carbonyl and amine groups further stabilize the complex. These interactions likely reduce PFOA's toxicity by altering its bioavailability and distribution. While this study offers valuable insights into the binding mechanisms between L-Trp and PFOA, it raises important questions about the reversibility of this interaction and its applicability to other per- and polyfluoroalkyl substances (PFASs).
{"title":"Evaluation of the impact of L-Tryptophan on the toxicology of Perfluorooctanoic acid in Daphnia magna: Characterization and perspectives","authors":"Mathieu Verhille , Robert Hausler","doi":"10.1016/j.chemosphere.2024.143665","DOIUrl":"10.1016/j.chemosphere.2024.143665","url":null,"abstract":"<div><div>Perfluorooctanoic acid (PFOA) is a pervasive environmental contaminant with well-documented toxic effects on both humans and animals, attracting significant scientific concern. Due to its affinity for proteins, research has predominantly focused on PFOA's interactions with biological macromolecules. However, the specific role of smaller molecules, such as amino acids, remains underexplored. This study uniquely evaluates the potential of <span>l</span>-tryptophan (L-Trp) to mitigate PFOA toxicity and investigates the interaction mechanisms involved. Results indicate that the presence of L-Trp in PFOA-contaminated water reduces acute toxicity in <em>Daphnia magna</em>, with an optimal molar ratio of approximately 1:2 (Trp:PFOA). The findings reveal that non-covalent interactions, particularly van der Waals forces and hydrogen bonds, are central to the Trp–PFOA complex formation. Additional contributions from hydrophobic interactions at the indole group and electrostatic forces between carbonyl and amine groups further stabilize the complex. These interactions likely reduce PFOA's toxicity by altering its bioavailability and distribution. While this study offers valuable insights into the binding mechanisms between L-Trp and PFOA, it raises important questions about the reversibility of this interaction and its applicability to other per- and polyfluoroalkyl substances (PFASs).</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143665"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142570618","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}
Bisphenol A diglycidyl ether (BADGE) is a pre-polymer of BPA widely used in manufacturing of epoxy resins and plastics; due to its high reactivity, unintended by-products, such as chlorinated and hydrolysed products, can reach the human body. This research integrates multiple approaches such as computational predictions, chromatographic experiments, biological assays, and human biomonitoring studies to comprehensively evaluate the toxicological profiles of the parent compound and its derivatives. In silico predictions were first utilized to estimate the toxicological properties and interactions of BADGE derivatives, providing insights into their bioactivity. Biomimetic liquid chromatography was then used to simulate membrane permeability and biodistribution, predicting how these chemicals might cross biological membranes and accumulate in tissues. In vitro experiments assessed cellular toxicity through viability assays, identifying BADGE·2HCl as the most cytotoxic derivative. Reactive Oxygen Species (ROS) production evaluation was performed to assess the oxidative stress induced by these compounds, revealing elevated ROS levels in cells exposed to BADGE and BADGE·2HCl with a consequent significant oxidative damage. Similarly, BADGE and BADGE·2HCl were able to induce cellular death by apoptosis activation. Human serum analysis in a population sample (N = 96), showed BADGE·2H2O as the most frequently detected metabolite, indicating a considerable human exposure and metabolic processes. The findings highlight a toxicity of BADGE derivatives similar to that of BADGE; BADGE·2HCl resulted particularly cytotoxic and BADGE·2H2O is the most frequent detected in human serum, underscoring the need for regulatory measures to mitigate potential health risks associated with these compounds.
{"title":"The combined use of biological investigations, bio chromatographic and in silico methods to solve the puzzle of badge and its derivative's toxicity","authors":"Ilaria Neri , Marialuisa Piccolo , Giacomo Russo , Maria Grazia Ferraro , Vincenzo Marotta , Rita Santamaria , Lucia Grumetto","doi":"10.1016/j.chemosphere.2024.143640","DOIUrl":"10.1016/j.chemosphere.2024.143640","url":null,"abstract":"<div><div>Bisphenol A diglycidyl ether (BADGE) is a pre-polymer of BPA widely used in manufacturing of epoxy resins and plastics; due to its high reactivity, unintended by-products, such as chlorinated and hydrolysed products, can reach the human body. This research integrates multiple approaches such as computational predictions, chromatographic experiments, biological assays, and human biomonitoring studies to comprehensively evaluate the toxicological profiles of the parent compound and its derivatives. <em>In silico</em> predictions were first utilized to estimate the toxicological properties and interactions of BADGE derivatives, providing insights into their bioactivity. Biomimetic liquid chromatography was then used to simulate membrane permeability and biodistribution, predicting how these chemicals might cross biological membranes and accumulate in tissues. <em>In vitro</em> experiments assessed cellular toxicity through viability assays, identifying BADGE·2HCl as the most cytotoxic derivative. Reactive Oxygen Species (ROS) production evaluation was performed to assess the oxidative stress induced by these compounds, revealing elevated ROS levels in cells exposed to BADGE and BADGE·2HCl with a consequent significant oxidative damage. Similarly, BADGE and BADGE·2HCl were able to induce cellular death by apoptosis activation. Human serum analysis in a population sample (N = 96), showed BADGE·2H<sub>2</sub>O as the most frequently detected metabolite, indicating a considerable human exposure and metabolic processes. The findings highlight a toxicity of BADGE derivatives similar to that of BADGE; BADGE·2HCl resulted particularly cytotoxic and BADGE·2H<sub>2</sub>O is the most frequent detected in human serum, underscoring the need for regulatory measures to mitigate potential health risks associated with these compounds.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143640"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142570659","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.2024.143424
Usman Rasheed , Qurat Ul Ain , Bin Liu
Enzymatic degradation of aflatoxins in food commodities has gained significant attention. However, enzyme denaturation in organic media discourages their direct use in oils to remove aflatoxins. For that, enzymes are immobilized or encapsulated for improved stability and reusability under unfavorable conditions. We sandwiched the laccase between a carrier and an outer protective layer. We used spent-mushroom-substrate (SMS) derived porous magnetic biochar as the laccase carrier and coated it with an iron MOF to create a biocomposite, Fe-BTC@Lac@FB. The immobilized laccase demonstrated enhanced chemical, thermal, and storage stability and proficient reusability. Fe-BTC@Lac@FB exhibited 11 times enhanced aflatoxin B1 (AFB1) degradation compared to free laccase (FL). In addition, thermally inactivated Fe-BTC@Lac@FB could adsorb 11.2 mg/g of AFB1 from peanut oil. Multi-aflatoxin removal also proved promising, while Fe-BTC@Lac@FB could retain >85 % of AFB1 removal efficacy after five reusability cycles. Fe-BTC@Lac@FB treatment did not affect peanut oil quality as indicated by different oil quality parameters and proved essentially non-cytotoxic. All these aspects helped recognize Fe-BTC@Lac@FB as an excellent laccase-carrying material with exceptionally higher stability, activity, and reusability.
{"title":"Integration of Fe-MOF-laccase-magnetic biochar: From Rational Designing of a biocatalyst to aflatoxin B1 decontamination of peanut oil","authors":"Usman Rasheed , Qurat Ul Ain , Bin Liu","doi":"10.1016/j.chemosphere.2024.143424","DOIUrl":"10.1016/j.chemosphere.2024.143424","url":null,"abstract":"<div><div>Enzymatic degradation of aflatoxins in food commodities has gained significant attention. However, enzyme denaturation in organic media discourages their direct use in oils to remove aflatoxins. For that, enzymes are immobilized or encapsulated for improved stability and reusability under unfavorable conditions. We sandwiched the laccase between a carrier and an outer protective layer. We used spent-mushroom-substrate (SMS) derived porous magnetic biochar as the laccase carrier and coated it with an iron MOF to create a biocomposite, Fe-BTC@Lac@FB. The immobilized laccase demonstrated enhanced chemical, thermal, and storage stability and proficient reusability. Fe-BTC@Lac@FB exhibited 11 times enhanced aflatoxin B<sub>1</sub> (AFB<sub>1</sub>) degradation compared to free laccase (FL). In addition, thermally inactivated Fe-BTC@Lac@FB could adsorb 11.2 mg/g of AFB<sub>1</sub> from peanut oil. Multi-aflatoxin removal also proved promising, while Fe-BTC@Lac@FB could retain >85 % of AFB<sub>1</sub> removal efficacy after five reusability cycles. Fe-BTC@Lac@FB treatment did not affect peanut oil quality as indicated by different oil quality parameters and proved essentially non-cytotoxic. All these aspects helped recognize Fe-BTC@Lac@FB as an excellent laccase-carrying material with exceptionally higher stability, activity, and reusability.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143424"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142378698","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.2024.143516
Shalini Saggu , Ritesh K. Srivastava , Lisa McCormick , Anupam Agarwal , Mohammad Moshahid Khan , Mohammad Athar
Unused warfare chemical agents, developed in World Wars I/II dumped in the ocean or buried at various sites across the world, pose significant environmental and human health risks. This review provides description of the neurotoxicity of arsenic-based warfare chemicals known as arsenicals. We specifically described the neuropathogenesis of diphenylarsinic acid (DPAA), a chemical warfare-related organoarsenicals and a degradation product of diphenylchloroarsine (DA), diphenylcyanoarsine (DC), also known as Clark I and Clark II respectively. These arsenicals are potent emetics, which were buried at a former naval base in the town of Kamisu, Japan. Several decades after burial, their environmental decay led to contamination of underground water table. Consumption of the contaminated water by the residents manifested a neurological syndrome, which was associated with damage to the cerebellum and brainstem as well as behavioral deficits. We summarized the chronology of this damage as recorded by monitoring the exposed population over time (∼15 years). Several simulating animal studies in primates and murine models demonstrate that DPAA caused this syndrome.
第一次/第二次世界大战中研制的未使用的战争化学剂被倾倒在海洋中或掩埋在世界各地的不同地点，对环境和人类健康构成了重大风险。本综述介绍了以砷为基础的战争化学制剂（又称砷剂）的神经毒性。我们特别介绍了二苯基胂酸（DPAA）的神经发病机理，这是一种与化学战有关的有机胂，也是二苯基氯胂（DA）和二苯基氰胂（DC）的降解产物，分别称为克拉克 I 和克拉克 II。这些砷化物是强效催吐剂，被埋在日本上须镇的一个前海军基地。掩埋几十年后，它们在环境中腐烂，导致地下水位受到污染。居民饮用受污染的水后出现了神经系统综合征，与小脑和脑干受损以及行为障碍有关。我们总结了通过长期（∼15 年）监测暴露人群所记录的这种损害的时间顺序。在灵长类动物和小鼠模型中进行的几项模拟动物研究表明，DPAA 会导致这种综合症。
{"title":"Neurotoxicology of warfare arsenical, diphenylarsinic acid in humans and experimental models","authors":"Shalini Saggu , Ritesh K. Srivastava , Lisa McCormick , Anupam Agarwal , Mohammad Moshahid Khan , Mohammad Athar","doi":"10.1016/j.chemosphere.2024.143516","DOIUrl":"10.1016/j.chemosphere.2024.143516","url":null,"abstract":"<div><div>Unused warfare chemical agents, developed in World Wars I/II dumped in the ocean or buried at various sites across the world, pose significant environmental and human health risks. This review provides description of the neurotoxicity of arsenic-based warfare chemicals known as arsenicals. We specifically described the neuropathogenesis of diphenylarsinic acid (DPAA), a chemical warfare-related organoarsenicals and a degradation product of diphenylchloroarsine (DA), diphenylcyanoarsine (DC), also known as Clark I and Clark II respectively. These arsenicals are potent emetics, which were buried at a former naval base in the town of Kamisu, Japan. Several decades after burial, their environmental decay led to contamination of underground water table. Consumption of the contaminated water by the residents manifested a neurological syndrome, which was associated with damage to the cerebellum and brainstem as well as behavioral deficits. We summarized the chronology of this damage as recorded by monitoring the exposed population over time (∼15 years). Several simulating animal studies in primates and murine models demonstrate that DPAA caused this syndrome.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143516"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142402343","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.2024.143736
Gooya Banaei , Doaa Abass , Alireza Tavakolpournegari , Joan Martín-Pérez , Javier Gutiérrez , Guyu Peng , Thorsten Reemtsma , Ricard Marcos , Alba Hernández , Alba García-Rodríguez
The potential health implications of environmental micro/nanoplastics (MNPLs) are increasingly concerning. Beyond environmental exposure, other sources such as food packaging, including herbal/teabags, may also be significant. This study investigates the release of MNPLs from three commercially available teabags. By simulating tea preparation, MNPL samples were extracted and characterized using a range of analytical techniques: scanning electron microscopy (SEM), transmission electron microscopy (TEM), attenuated total reflectance/Fourier transform infrared spectroscopy (ATR-FTIR), dynamic light scattering (DLS), laser Doppler velocimetry (LDV), and nanoparticle tracking analysis (NTA). The results confirmed that the teabags were made of nylon-6 (NY6), polypropylene (PP), and cellulose (CL) and that microfibers and nano-range particles (NPLs) were present in the leachates. NTA data revealed that the number of released NPLs was 1.20 × 109/mL (PP; 136.7 nm), 1.35 × 108/mL (CL; 244 nm), and 8.18 × 106/mL (NY6; 138.4). The leachate particles were then stained with iDye Poly-Pink and used to expose three human intestine-derived cell types (Caco-2, HT29, and HT29-MTX) to assess their biointeractions and the role of the mucosubstances in vitro. The results demonstrated that after 24 h of exposure to 100 μg/mL NPLs, there was significant uptake of PP-NPLs in HT29-MTX cells, as a model of cells segregating high amount of mucus. A similar uptake was observed for CL-NPLs in HT29 and HT29-MTX cells, while NY6-NPLs were internalized preferentially in Caco-2 cells. These findings underscore the importance of identifying new environmentally relevant MNPL exposure sources, for developing realistic MNPLs samples, and further investigating their potential human health effects.
{"title":"Teabag-derived micro/nanoplastics (true-to-life MNPLs) as a surrogate for real-life exposure scenarios","authors":"Gooya Banaei , Doaa Abass , Alireza Tavakolpournegari , Joan Martín-Pérez , Javier Gutiérrez , Guyu Peng , Thorsten Reemtsma , Ricard Marcos , Alba Hernández , Alba García-Rodríguez","doi":"10.1016/j.chemosphere.2024.143736","DOIUrl":"10.1016/j.chemosphere.2024.143736","url":null,"abstract":"<div><div>The potential health implications of environmental micro/nanoplastics (MNPLs) are increasingly concerning. Beyond environmental exposure, other sources such as food packaging, including herbal/teabags, may also be significant. This study investigates the release of MNPLs from three commercially available teabags. By simulating tea preparation, MNPL samples were extracted and characterized using a range of analytical techniques: scanning electron microscopy (SEM), transmission electron microscopy (TEM), attenuated total reflectance/Fourier transform infrared spectroscopy (ATR-FTIR), dynamic light scattering (DLS), laser Doppler velocimetry (LDV), and nanoparticle tracking analysis (NTA). The results confirmed that the teabags were made of nylon-6 (NY6), polypropylene (PP), and cellulose (CL) and that microfibers and nano-range particles (NPLs) were present in the leachates. NTA data revealed that the number of released NPLs was 1.20 × 10<sup>9</sup>/mL (PP; 136.7 nm), 1.35 × 10<sup>8</sup>/mL (CL; 244 nm), and 8.18 × 10<sup>6</sup>/mL (NY6; 138.4). The leachate particles were then stained with iDye Poly-Pink and used to expose three human intestine-derived cell types (Caco-2, HT29, and HT29-MTX) to assess their biointeractions and the role of the mucosubstances <em>in vitro</em>. The results demonstrated that after 24 h of exposure to 100 μg/mL NPLs, there was significant uptake of PP-NPLs in HT29-MTX cells, as a model of cells segregating high amount of mucus. A similar uptake was observed for CL-NPLs in HT29 and HT29-MTX cells, while NY6-NPLs were internalized preferentially in Caco-2 cells. These findings underscore the importance of identifying new environmentally relevant MNPL exposure sources, for developing realistic MNPLs samples, and further investigating their potential human health effects.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"368 ","pages":"Article 143736"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142634418","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}
Building materials are the major sources of Volatile and Semi-Volatile Organic Compounds (VOCs and SVOCs) in indoor air. Measurements of emission rates of these compounds are likely to be influenced by variation in certain environmental factors resulting in intra-specimen variability. This study aims to (i) evaluate the reproducibility of measurements between specimens and (ii) evaluate the impact of storage on VOC and SVOC emissions from antifungal acrylic paint (applied on polyester-cellulose). For this purpose, 15 discs of tested materials (1.63 ± 0.04 g) were prepared. From these, the emissions rates (ER) of 5 samples were analyzed simultaneously during three measurement campaigns (October 2021, January 2022 and March 2022). Between each campaign, specimens were stored in the dark at ambient temperature (25 ± 4 °C) and relative humidity (50 ± 20 %). Measurements were performed using the field and laboratory emission cell (FLEC) and characterized by gas chromatography (TD-GC-MS/FID) and liquid chromatography (HPLC). Intra-specimen reproducibility was assessed by comparing 5 ER of different specimens collected simultaneously. The impact of storage was evaluated by comparing the average VOC/SVOC ER between each campaign. The results show, concerning the reproducibility of the measurements, that the first measurement campaign provides ER with high variability (10–36 %) compared to the second and third measurement campaigns, which show lower intra-specimen variability (5–24 % and 8–20 % respectively). However, weakly emitted compounds (ER < 10 μg m−2 h−1) such as aromatics and aldehydes show large variabilities (6–100 % of variation) in all measurement campaigns. Regarding the effect of the 5-months storage a significant decrease in the ER of individual VOC/SVOCs (37–85 %) and of TVOCs (74 %) was noted, except for aldehydes, aromatic hydrocarbons, isopropylacetone and vinyl crotonate, which showed a stability or eventual increase (up to 100 %) in the ER over time, depending on the type of emitted compound.
{"title":"Measurement reproducibility and storage impact on VOC/SVOC emission rate from decorative materials","authors":"Nouha Zine Filali , Tamara Braish , Yves Andres , Nadine Locoge","doi":"10.1016/j.chemosphere.2024.143607","DOIUrl":"10.1016/j.chemosphere.2024.143607","url":null,"abstract":"<div><div>Building materials are the major sources of Volatile and Semi-Volatile Organic Compounds (VOCs and SVOCs) in indoor air. Measurements of emission rates of these compounds are likely to be influenced by variation in certain environmental factors resulting in intra-specimen variability. This study aims to (i) evaluate the reproducibility of measurements between specimens and (ii) evaluate the impact of storage on VOC and SVOC emissions from antifungal acrylic paint (applied on polyester-cellulose). For this purpose, 15 discs of tested materials (1.63 ± 0.04 g) were prepared. From these, the emissions rates (ER) of 5 samples were analyzed simultaneously during three measurement campaigns (October 2021, January 2022 and March 2022). Between each campaign, specimens were stored in the dark at ambient temperature (25 ± 4 °C) and relative humidity (50 ± 20 %). Measurements were performed using the field and laboratory emission cell (FLEC) and characterized by gas chromatography (TD-GC-MS/FID) and liquid chromatography (HPLC). Intra-specimen reproducibility was assessed by comparing 5 ER of different specimens collected simultaneously. The impact of storage was evaluated by comparing the average VOC/SVOC ER between each campaign. The results show, concerning the reproducibility of the measurements, that the first measurement campaign provides ER with high variability (10–36 %) compared to the second and third measurement campaigns, which show lower intra-specimen variability (5–24 % and 8–20 % respectively). However, weakly emitted compounds (ER < 10 μg m<sup>−2</sup> h<sup>−1</sup>) such as aromatics and aldehydes show large variabilities (6–100 % of variation) in all measurement campaigns. Regarding the effect of the 5-months storage a significant decrease in the ER of individual VOC/SVOCs (37–85 %) and of TVOCs (74 %) was noted, except for aldehydes, aromatic hydrocarbons, isopropylacetone and vinyl crotonate, which showed a stability or eventual increase (up to 100 %) in the ER over time, depending on the type of emitted compound.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143607"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142514673","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.2024.143664
Tatiana V. Plakhova , Maria A. Vyshegorodtseva , Irina F. Seregina , Roman D. Svetogorov , Alexander L. Trigub , Daniil A. Kozlov , Alexander V. Egorov , Maria D. Shaulskaya , Dmitry M. Tsymbarenko , Anna Yu. Romanchuk , Vladimir K. Ivanov , Stepan N. Kalmykov
In the present study, the dissolution and microstructural transformation of CeO2 nanoparticles (NPs) in a phosphate-containing milieu were investigated. The dissolution behaviour of 2 nm and 5 nm CeO2 NPs in phosphate buffer solutions was found to differ markedly from that observed in 0.01 M NaClO4. Through synchrotron X-ray diffraction analysis and X-ray absorption spectroscopy, the interaction between CeO2 NPs and phosphate species was examined, revealing the transformation of the oxide into sodium-cerium double phosphate, with cerium predominantly existing in the Ce(IV) state. According to scanning and transmission electron microscopy observations, thus formed Na-Ce(IV) phosphate consists of spindle-like aggregates of nanocrystalline rods, presumably formed during phosphate anions sorption on the initial CeO2 surface. Pair distribution function analysis revealed that Na-Ce(IV) phosphate has a three-dimensional framework crystal structure, similar to NaTh2(PO4)3, as reported earlier, with large channels along the c-axis containing disordered sodium atoms. This study represents the first detailed analysis of phosphate-induced speciation and microstructural transformation of CeO2 NPs, resulting in the formation of Ce(IV) phosphate. Similar processes may occur in natural ecosystems upon the introduction of CeO2 NPs.
本研究调查了 CeO2 纳米粒子 (NPs) 在含磷酸盐环境中的溶解和微观结构转变。研究发现，2 nm 和 5 nm CeO2 NPs 在磷酸盐缓冲溶液中的溶解行为与在 0.01 M NaClO4 溶液中的溶解行为明显不同。通过同步辐射 X 射线衍射分析和 X 射线吸收光谱，研究了 CeO2 NPs 与磷酸盐物种之间的相互作用，发现氧化物转变为钠铈双磷酸盐，铈主要以 Ce（IV）态存在。根据扫描和透射电子显微镜观察，由此形成的 Na-Ce(IV)磷酸盐由纺锤形的纳米晶棒聚集体组成，这可能是在最初的 CeO2 表面吸附磷酸盐阴离子时形成的。配位分布函数分析表明，Na-Ce(IV) 磷酸盐具有三维框架晶体结构，类似于早先报道的 NaTh2(PO4)3，沿 c 轴有包含无序钠原子的大通道。本研究首次详细分析了磷酸盐诱导的 CeO2 NPs 分化和微结构转变，从而形成了磷酸铈（IV）。在自然生态系统中引入 CeO2 NPs 时也可能会发生类似的过程。
{"title":"Unexpected nanoscale CeO2 structural transformations induced by ecologically relevant phosphate species","authors":"Tatiana V. Plakhova , Maria A. Vyshegorodtseva , Irina F. Seregina , Roman D. Svetogorov , Alexander L. Trigub , Daniil A. Kozlov , Alexander V. Egorov , Maria D. Shaulskaya , Dmitry M. Tsymbarenko , Anna Yu. Romanchuk , Vladimir K. Ivanov , Stepan N. Kalmykov","doi":"10.1016/j.chemosphere.2024.143664","DOIUrl":"10.1016/j.chemosphere.2024.143664","url":null,"abstract":"<div><div>In the present study, the dissolution and microstructural transformation of CeO<sub>2</sub> nanoparticles (NPs) in a phosphate-containing milieu were investigated. The dissolution behaviour of 2 nm and 5 nm CeO<sub>2</sub> NPs in phosphate buffer solutions was found to differ markedly from that observed in 0.01 M NaClO<sub>4</sub>. Through synchrotron X-ray diffraction analysis and X-ray absorption spectroscopy, the interaction between CeO<sub>2</sub> NPs and phosphate species was examined, revealing the transformation of the oxide into sodium-cerium double phosphate, with cerium predominantly existing in the Ce(IV) state. According to scanning and transmission electron microscopy observations, thus formed Na-Ce(IV) phosphate consists of spindle-like aggregates of nanocrystalline rods, presumably formed during phosphate anions sorption on the initial CeO<sub>2</sub> surface. Pair distribution function analysis revealed that Na-Ce(IV) phosphate has a three-dimensional framework crystal structure, similar to NaTh<sub>2</sub>(PO<sub>4</sub>)<sub>3</sub>, as reported earlier, with large channels along the c-axis containing disordered sodium atoms. This study represents the first detailed analysis of phosphate-induced speciation and microstructural transformation of CeO<sub>2</sub> NPs, resulting in the formation of Ce(IV) phosphate. Similar processes may occur in natural ecosystems upon the introduction of CeO<sub>2</sub> NPs.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"368 ","pages":"Article 143664"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142570665","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.2024.143676
Si Ying Liu , Deng Lai Li , Rui Zhu , Si Tong Meng , Yin Tao Wang , Liang Li , Zhi Yong Yang , Li Fang Wu
This study investigates the impact of polystyrene microplastics (PS-MPs) on the growth, immunity, oxidative stress, mitochondrial function, and intestinal health of Leuciscus waleckii (3.00 ± 0.02 g) juveniles over 8 weeks. Our findings indicate that exposure to PS-MPs negatively affected the growth of Leuciscus waleckii, resulting in digestive disturbances. Furthermore, PS-MPs triggered immune dysfunction and oxidative stress through the activation of the NF-κB pathway and suppression of the Nrf2 signaling cascade. PS-MPs damaged intestinal tissue and compromised the intestinal barrier. Additionally, mitochondrial homeostasis was disrupted, activating endogenous mitochondrial apoptotic pathways, ultimately leading to cell apoptosis. High-throughput 16S rRNA sequencing disclosed that PS-MPs provoked shifts in the intestinal microbiota. Mantel analysis indicates significant correlations between growth parameters and the activities of enzymes related to antioxidant defense, immunity, apoptosis, and mitochondria, as well as with the gut microbiota. In summary, our study reveals that PS-MPs induce intestinal inflammation and oxidative stress in Leuciscus waleckii by activating the NF-κB pathway and the intrinsic mitochondrial apoptotic pathway while repressing the Nrf2 signaling, ultimately leading to cellular apoptosis, mitochondrial dysfunction, intestinal microbiota imbalance, and growth inhibition.
{"title":"Mechanisms underlying mitochondrial dysfunction and intestinal damage induced by ingestion of microplastics in Leuciscus waleckii: The role of the NF-κB/Nrf2 signaling pathway","authors":"Si Ying Liu , Deng Lai Li , Rui Zhu , Si Tong Meng , Yin Tao Wang , Liang Li , Zhi Yong Yang , Li Fang Wu","doi":"10.1016/j.chemosphere.2024.143676","DOIUrl":"10.1016/j.chemosphere.2024.143676","url":null,"abstract":"<div><div>This study investigates the impact of polystyrene microplastics (PS-MPs) on the growth, immunity, oxidative stress, mitochondrial function, and intestinal health of <em>Leuciscus waleckii</em> (3.00 ± 0.02 g) juveniles over 8 weeks. Our findings indicate that exposure to PS-MPs negatively affected the growth of <em>Leuciscus waleckii</em>, resulting in digestive disturbances. Furthermore, PS-MPs triggered immune dysfunction and oxidative stress through the activation of the NF-κB pathway and suppression of the Nrf2 signaling cascade. PS-MPs damaged intestinal tissue and compromised the intestinal barrier. Additionally, mitochondrial homeostasis was disrupted, activating endogenous mitochondrial apoptotic pathways, ultimately leading to cell apoptosis. High-throughput 16S rRNA sequencing disclosed that PS-MPs provoked shifts in the intestinal microbiota. Mantel analysis indicates significant correlations between growth parameters and the activities of enzymes related to antioxidant defense, immunity, apoptosis, and mitochondria, as well as with the gut microbiota. In summary, our study reveals that PS-MPs induce intestinal inflammation and oxidative stress in <em>Leuciscus waleckii</em> by activating the NF-κB pathway and the intrinsic mitochondrial apoptotic pathway while repressing the Nrf2 signaling, ultimately leading to cellular apoptosis, mitochondrial dysfunction, intestinal microbiota imbalance, and growth inhibition.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143676"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142590699","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.2024.143687
Min Young Shin , Hyung Joo Lee
Over the past two decades, ambient O3 air pollution in Seoul, the capital city of South Korea, has increased. As a secondary air pollutant, O3 is affected not only by precursor gas emissions but also by meteorological conditions. This study examined the influence of weather changes in Seoul for 2001–2019 on the long-term daily maximum 8-h O3 concentration (MDA8 O3) trends measured at 25 monitoring sites. As the relationship between O3 and meteorological variables may not be linear, we used a generalized additive model framework to estimate O3 trends, incorporating quantile and logistic regressions for continuous O3 data and O3 exceedance days (>60 ppb), respectively. Over the 19-year period, the O3 concentrations in Seoul increased by 14.7 (SD = 3.2) and 13.1 (SD = 3.1) ppb before and after adjusting for local meteorology, respectively, resulting in an average weather penalty of 1.55 ppb. Seasonal variations in the penalty were substantial, showing a greater penalty (4.5 ppb) during the warm season (May–October) than during the cold season (November–April). Furthermore, the increase in O3 concentration was more pronounced on days with comparatively high O3 levels. During the warm season, the weather penalties on O3 trends reached 3.7–4.0 ppb on high-O3 days (75th, 95th, and 99th percentiles). From 2001 to 2019, the O3 exceedance days started 2.66 days earlier and ended 2.30 days later per year, extending the peak-O3 season by approximately 89 days in total. Weather changes accelerated the upward trend in the odds ratio of O3 exceedance days by 3.8 years. Our findings indicate that O3 exceedance days can occur in nearly all months owing to weather changes. The significant weather penalties on O3 concentrations and exceedance days emphasize the need for a comprehensive O3 air pollution mitigation strategy, considering non-emission factors that are increasingly being recognized in the context of climate change.
{"title":"A comprehensive multi-tiered approach to assessing weather penalties on O3 levels and exceedance days in Seoul using generalized additive models (2001–2019)","authors":"Min Young Shin , Hyung Joo Lee","doi":"10.1016/j.chemosphere.2024.143687","DOIUrl":"10.1016/j.chemosphere.2024.143687","url":null,"abstract":"<div><div>Over the past two decades, ambient O<sub>3</sub> air pollution in Seoul, the capital city of South Korea, has increased. As a secondary air pollutant, O<sub>3</sub> is affected not only by precursor gas emissions but also by meteorological conditions. This study examined the influence of weather changes in Seoul for 2001–2019 on the long-term daily maximum 8-h O<sub>3</sub> concentration (MDA8 O<sub>3</sub>) trends measured at 25 monitoring sites. As the relationship between O<sub>3</sub> and meteorological variables may not be linear, we used a generalized additive model framework to estimate O<sub>3</sub> trends, incorporating quantile and logistic regressions for continuous O<sub>3</sub> data and O<sub>3</sub> exceedance days (>60 ppb), respectively. Over the 19-year period, the O<sub>3</sub> concentrations in Seoul increased by 14.7 (SD = 3.2) and 13.1 (SD = 3.1) ppb before and after adjusting for local meteorology, respectively, resulting in an average weather penalty of 1.55 ppb. Seasonal variations in the penalty were substantial, showing a greater penalty (4.5 ppb) during the warm season (May–October) than during the cold season (November–April). Furthermore, the increase in O<sub>3</sub> concentration was more pronounced on days with comparatively high O<sub>3</sub> levels. During the warm season, the weather penalties on O<sub>3</sub> trends reached 3.7–4.0 ppb on high-O<sub>3</sub> days (75<sup>th</sup>, 95<sup>th</sup>, and 99<sup>th</sup> percentiles). From 2001 to 2019, the O<sub>3</sub> exceedance days started 2.66 days earlier and ended 2.30 days later per year, extending the peak-O<sub>3</sub> season by approximately 89 days in total. Weather changes accelerated the upward trend in the odds ratio of O<sub>3</sub> exceedance days by 3.8 years. Our findings indicate that O<sub>3</sub> exceedance days can occur in nearly all months owing to weather changes. The significant weather penalties on O<sub>3</sub> concentrations and exceedance days emphasize the need for a comprehensive O<sub>3</sub> air pollution mitigation strategy, considering non-emission factors that are increasingly being recognized in the context of climate change.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"368 ","pages":"Article 143687"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142607757","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}
The determination of metal-containing additives in plastic materials via acid digestion protocols has attracted growing interest to address potential environmental implications. However, the lack of protocol harmonization hinders data comparability within the literature. Here, six acid digestion protocols were employed to determine the metal(loid) content in plastics: these included three different acid mixtures (HNO3 combined with H2SO4, HCl or H2O2) for microwave-assisted digestion, with or without an additional room-temperature digestion step with H2O2.
Each protocol was first validated for seven metal(loid)s (As, Cd, Cr, Pb, Sb, Sn and Zn) using a low-density polyethylene (LDPE) certified reference material (ERM®-EC681m). Then, validated protocols were applied on end-use materials, including conventional (i.e., LDPE) and compostable (i.e., PBAT/TPS) plastics.
The combination of H2SO4 and HNO3 with a further digestion step with H2O2 was the most suitable protocol: it successfully passed validation thresholds for all metal(loid)s (recoveries in the range 98.6–101.0 %) and yielded the highest concentrations in end-use materials. All other protocols resulted in a less efficient digestion of the sample matrix, leading to lower recoveries and the formation of solid residues. Notably, end-use plastics showed a great variability in metal(loid) concentrations, likely due to their additive-rich composition, in contrast to the minimal content of acid-soluble additives of the reference material.
This study represents an initial step towards the harmonization of acid digestion protocols and highlights new challenges in accurately analyzing end-use plastic materials, due to their complex additive composition.
{"title":"Towards harmonization of metal(loid)s determination in conventional and compostable plastics: Comparison of acid digestion protocols in LDPE and PBAT/TPS blends","authors":"Stefano Carnati , Andrea Pozzi , Davide Spanu , Roberta Bettinetti , Luca Nizzetto , Gabriela Kalčíková , Ludovica Botta , Gilberto Binda","doi":"10.1016/j.chemosphere.2024.143581","DOIUrl":"10.1016/j.chemosphere.2024.143581","url":null,"abstract":"<div><div>The determination of metal-containing additives in plastic materials via acid digestion protocols has attracted growing interest to address potential environmental implications. However, the lack of protocol harmonization hinders data comparability within the literature. Here, six acid digestion protocols were employed to determine the metal(loid) content in plastics: these included three different acid mixtures (HNO<sub>3</sub> combined with H<sub>2</sub>SO<sub>4</sub>, HCl or H<sub>2</sub>O<sub>2</sub>) for microwave-assisted digestion, with or without an additional room-temperature digestion step with H<sub>2</sub>O<sub>2</sub>.</div><div>Each protocol was first validated for seven metal(loid)s (As, Cd, Cr, Pb, Sb, Sn and Zn) using a low-density polyethylene (LDPE) certified reference material (ERM®-EC681m). Then, validated protocols were applied on end-use materials, including conventional (i.e., LDPE) and compostable (i.e., PBAT/TPS) plastics.</div><div>The combination of H<sub>2</sub>SO<sub>4</sub> and HNO<sub>3</sub> with a further digestion step with H<sub>2</sub>O<sub>2</sub> was the most suitable protocol: it successfully passed validation thresholds for all metal(loid)s (recoveries in the range 98.6–101.0 %) and yielded the highest concentrations in end-use materials. All other protocols resulted in a less efficient digestion of the sample matrix, leading to lower recoveries and the formation of solid residues. Notably, end-use plastics showed a great variability in metal(loid) concentrations, likely due to their additive-rich composition, in contrast to the minimal content of acid-soluble additives of the reference material.</div><div>This study represents an initial step towards the harmonization of acid digestion protocols and highlights new challenges in accurately analyzing end-use plastic materials, due to their complex additive composition.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"367 ","pages":"Article 143581"},"PeriodicalIF":8.1,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142483119","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}
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