Pub Date : 2025-12-07DOI: 10.1016/j.chemosphere.2025.144788
Lucas Cassulatti dos Santos , Nathália de Assis Aguilar Duarte , Marília Ladeira de Araújo , Bruno Alves Rocha , Alexey A. Tinkov , Michael Aschner , Fernando Barbosa Jr.
This study investigated the seasonal dynamics of the blood metallome and its relationship with environmental and dietary factors in riverine communities from the Tapajós River region, Brazil. A repeated cross-sectional biomonitoring study was conducted during the dry (October–November 2022) and rainy (April–May 2023) seasons across 13 communities, involving 110 participants assessed in both seasons. Nineteen metals and metalloids were determined in blood samples using inductively coupled plasma mass spectrometry (ICP-MS). Significant seasonal variations were observed, with median arsenic increasing from 3.73 μg/L to 6.95 μg/L, and mercury decreasing from 21.9 μg/L to 16.4 μg/L from the dry to the rainy season. Essential elements such as copper (997 μg/L to 783 μg/L) and zinc (5676 μg/L to 4436 μg/L) also exhibited notable differences. Selenium concentrations remained consistently elevated in both seasons, associated with Brazil nut consumption. Multiple regression analyses revealed significant associations between blood metal levels, dietary patterns, and sociodemographic factors. These findings underscore the importance of considering seasonal variability in biomonitoring studies and health policy development for Amazonian populations.
{"title":"Seasonal and dietary determinants of metal and metalloid exposure in riverine communities of the Brazilian Amazon: A study on temporal variation","authors":"Lucas Cassulatti dos Santos , Nathália de Assis Aguilar Duarte , Marília Ladeira de Araújo , Bruno Alves Rocha , Alexey A. Tinkov , Michael Aschner , Fernando Barbosa Jr.","doi":"10.1016/j.chemosphere.2025.144788","DOIUrl":"10.1016/j.chemosphere.2025.144788","url":null,"abstract":"<div><div>This study investigated the seasonal dynamics of the blood metallome and its relationship with environmental and dietary factors in riverine communities from the Tapajós River region, Brazil. A repeated cross-sectional biomonitoring study was conducted during the dry (October–November 2022) and rainy (April–May 2023) seasons across 13 communities, involving 110 participants assessed in both seasons. Nineteen metals and metalloids were determined in blood samples using inductively coupled plasma mass spectrometry (ICP-MS). Significant seasonal variations were observed, with median arsenic increasing from 3.73 μg/L to 6.95 μg/L, and mercury decreasing from 21.9 μg/L to 16.4 μg/L from the dry to the rainy season. Essential elements such as copper (997 μg/L to 783 μg/L) and zinc (5676 μg/L to 4436 μg/L) also exhibited notable differences. Selenium concentrations remained consistently elevated in both seasons, associated with Brazil nut consumption. Multiple regression analyses revealed significant associations between blood metal levels, dietary patterns, and sociodemographic factors. These findings underscore the importance of considering seasonal variability in biomonitoring studies and health policy development for Amazonian populations.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"394 ","pages":"Article 144788"},"PeriodicalIF":8.1,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145710546","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 : 2025-12-06DOI: 10.1016/j.chemosphere.2025.144794
Harsha S. Rangappa , Samuel Ogechi Eke , Mohit Kumar , Phyu Phyu Cho , Shashidhar Thatikonda , Ch Subrahmanyam , Chuxia Lin
For the past decades, great efforts have been made to beneficially utilize red mud, a hazardous waste material from alumina refining. These include recovery of valuable metals, use as feedstock for making construction materials, and various environmental applications. There have been numerous review articles that evaluated and analyzed the published literature on the adsorption application of red mud for treating contaminated water. However, little effort has been made to synthesize the existing knowledge on red mud application as the feedstock for making coagulants, catalysts, and conditioners despite that there has been increasing published reports on these aspects. To fill this knowledge gap, a systematic review was conducted by initially screening relevant journal articles published within the last 10 years (2015–2025) and subsequently critically analyzing and evaluating the selected articles. The results showed that there was a clear trend that the published work on catalyst application increased over time, especially in the recent 5 years while the published work on coagulation and conditioner applications fluctuated. Red mud-derived catalysts were applied in different types of advanced oxidation processes, mainly including photocatalysis, conventional Fenton oxidation, photo-Fenton oxidation, electro-Fenton oxidation and persulfate oxidation. Through this systematic review, the challenges for red mud applications in making catalysts, coagulants and conditioners were identified and recommendations for further research are made accordingly.
{"title":"A systematic review on the uses of red mud as feedstock to make catalysts, coagulants and conditioners for treatment of contaminated water","authors":"Harsha S. Rangappa , Samuel Ogechi Eke , Mohit Kumar , Phyu Phyu Cho , Shashidhar Thatikonda , Ch Subrahmanyam , Chuxia Lin","doi":"10.1016/j.chemosphere.2025.144794","DOIUrl":"10.1016/j.chemosphere.2025.144794","url":null,"abstract":"<div><div>For the past decades, great efforts have been made to beneficially utilize red mud, a hazardous waste material from alumina refining. These include recovery of valuable metals, use as feedstock for making construction materials, and various environmental applications. There have been numerous review articles that evaluated and analyzed the published literature on the adsorption application of red mud for treating contaminated water. However, little effort has been made to synthesize the existing knowledge on red mud application as the feedstock for making coagulants, catalysts, and conditioners despite that there has been increasing published reports on these aspects. To fill this knowledge gap, a systematic review was conducted by initially screening relevant journal articles published within the last 10 years (2015–2025) and subsequently critically analyzing and evaluating the selected articles. The results showed that there was a clear trend that the published work on catalyst application increased over time, especially in the recent 5 years while the published work on coagulation and conditioner applications fluctuated. Red mud-derived catalysts were applied in different types of advanced oxidation processes, mainly including photocatalysis, conventional Fenton oxidation, photo-Fenton oxidation, electro-Fenton oxidation and persulfate oxidation. Through this systematic review, the challenges for red mud applications in making catalysts, coagulants and conditioners were identified and recommendations for further research are made accordingly.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"394 ","pages":"Article 144794"},"PeriodicalIF":8.1,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691792","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}
A silver-containing industrial plating effluent was upcycled as silver source for synthesize Ag-decorated WO3 catalysts for photocatalytic dye removal. WO3 was first synthesized via acid precipitation and calcination, and subsequently decorated by silver species from plating effluent by photodeposition. Through the proposed procedure, the upcycled silver species were identified as Ag/Ag2S, resulting in the formation of Ag-WO3 catalysts with enhanced light absorption capacity, increased defect density, and improved charge separation efficiency compared to pristine WO3. Content of Ag/Ag2S decorated on WO3 surface played crucial role in enhancing the activity of WO3 for methylene blue (MB) removal. Among all synthesized Ag-WO3 catalysts, the 4.8 Ag-WO3 sample demonstrated the highest photocatalytic efficiency, achieving over 99 % MB removal within 90 min under visible light irradiation. Photogenerated h+ and O2•- exhibited an essential role in MB removal using the Ag-WO3 catalysts. The results of this study highlight a promising and sustainable strategy for synthesizing the waste-derived, silver-based photocatalysts from industrial silver-containing wastewater. This approach aligns with the principles of green synthesis, offers strong potential for scalability, and supports the concept of a circular economy by promoting waste reduction through a simple, cost-effective method for addressing wastewater.
{"title":"Upcycling industrial plating effluent for rapid synthesis of Ag-decorated defective WO3 with enhanced photocatalytic activity","authors":"Patcharapa Youyencharoen , Premsinee Junchum , Naphat Posachayanan , Auttawit Thoumrungroj , Pimchanok Longchin , Mali Hunsom","doi":"10.1016/j.chemosphere.2025.144793","DOIUrl":"10.1016/j.chemosphere.2025.144793","url":null,"abstract":"<div><div>A silver-containing industrial plating effluent was upcycled as silver source for synthesize Ag-decorated WO<sub>3</sub> catalysts for photocatalytic dye removal. WO<sub>3</sub> was first synthesized via acid precipitation and calcination, and subsequently decorated by silver species from plating effluent by photodeposition. Through the proposed procedure, the upcycled silver species were identified as Ag/Ag<sub>2</sub>S, resulting in the formation of Ag-WO<sub>3</sub> catalysts with enhanced light absorption capacity, increased defect density, and improved charge separation efficiency compared to pristine WO<sub>3</sub>. Content of Ag/Ag<sub>2</sub>S decorated on WO<sub>3</sub> surface played crucial role in enhancing the activity of WO<sub>3</sub> for methylene blue (MB) removal. Among all synthesized Ag-WO<sub>3</sub> catalysts, the 4.8 Ag-WO<sub>3</sub> sample demonstrated the highest photocatalytic efficiency, achieving over 99 % MB removal within 90 min under visible light irradiation. Photogenerated h<sup>+</sup> and O<sub>2</sub><sup>•-</sup> exhibited an essential role in MB removal using the Ag-WO<sub>3</sub> catalysts. The results of this study highlight a promising and sustainable strategy for synthesizing the waste-derived, silver-based photocatalysts from industrial silver-containing wastewater. This approach aligns with the principles of green synthesis, offers strong potential for scalability, and supports the concept of a circular economy by promoting waste reduction through a simple, cost-effective method for addressing wastewater.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"394 ","pages":"Article 144793"},"PeriodicalIF":8.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691791","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 : 2025-12-05DOI: 10.1016/j.chemosphere.2025.144790
Rajaa Kholssi , Juan Rodríguez-Márquez , María Úbeda-Manzanaro , Marta Sendra , Ignacio Moreno-Garrido , Ana Bartual , María J. Ortega
The sensitivity of marine microalgae to metal contamination, particularly copper (Cu), is well recognized in ecotoxicology, providing key insights into predicting marine pollution impacts. This study examined the combined effects of Cu toxicity and salinity on the diatom Chaetoceros calcitrans under controlled laboratory conditions. Toxicity assays were conducted using two environmentally relevant Cu concentrations (2 and 5 μg L−1) and three salinity levels (33, 36, and 39) over 96 h, with cell responses analyzed via flow cytometry. Specific growth rate (SGR), chlorophyll fluorescence, fatty acid methyl ester (FAME) composition, polyunsaturated aldehydes (PUAs), and reactive oxygen species (ROS) production were evaluated. Results showed that SGR increased from 1.7 d−1 at salinity 33 to 1.9 d−1 at 39, indicating enhanced growth at higher salinity. However, Cu exposure significantly reduced SGR, particularly under 5 μg L−1 Cu at salinity 33, where SGR dropped to 0.86 d−1. ROS levels were highest under the combined low salinity (33) and 5 μg L−1 Cu treatment, suggesting strong oxidative stress. PUA profiles shifted with Cu and salinity, with stress-related compounds such as 2E,4E/Z-decadienal and 2E,4E/Z,7Z-decatrienal increasing at low salinity. Fatty acid analysis revealed marked rises in saturated fatty acids, especially palmitic acid (C16:0) and myristic acid (C14:0), under Cu exposure. In the Cu2/39 treatment, C16:0 reached 1.34 × 104 fmol cell−1 compared to 1.36 × 103 fmol cell−1 in the control. Monounsaturated fatty acids, notably palmitoleic acid (C16:1), also increased, reaching 7. 46 × 103 fmol cell−1 versus 1.71 × 103 fmol cell−1 in the control. Conversely, polyunsaturated fatty acids, including arachidonic acid (C20:4) and eicosapentaenoic acid (C20:5 n-3), decreased significantly following Cu exposure. Overall, elevated salinity mitigated Cu-induced growth inhibition but intensified oxidative and biochemical stress, underscoring the complex, endpoint-specific responses of C. calcitrans to multiple environmental stressors.
{"title":"Copper toxicity as stressor in Chaetoceros calcitrans under different salinity levels: Growth inhibition, ROS accumulation, and alterations in fatty acid and PUA profiles","authors":"Rajaa Kholssi , Juan Rodríguez-Márquez , María Úbeda-Manzanaro , Marta Sendra , Ignacio Moreno-Garrido , Ana Bartual , María J. Ortega","doi":"10.1016/j.chemosphere.2025.144790","DOIUrl":"10.1016/j.chemosphere.2025.144790","url":null,"abstract":"<div><div>The sensitivity of marine microalgae to metal contamination, particularly copper (Cu), is well recognized in ecotoxicology, providing key insights into predicting marine pollution impacts. This study examined the combined effects of Cu toxicity and salinity on the diatom <em>Chaetoceros calcitrans</em> under controlled laboratory conditions. Toxicity assays were conducted using two environmentally relevant Cu concentrations (2 and 5 μg L<sup>−1</sup>) and three salinity levels (33, 36, and 39) over 96 h, with cell responses analyzed via flow cytometry. Specific growth rate (SGR), chlorophyll fluorescence, fatty acid methyl ester (FAME) composition, polyunsaturated aldehydes (PUAs), and reactive oxygen species (ROS) production were evaluated. Results showed that SGR increased from 1.7 d<sup>−1</sup> at salinity 33 to 1.9 d<sup>−1</sup> at 39, indicating enhanced growth at higher salinity. However, Cu exposure significantly reduced SGR, particularly under 5 μg L<sup>−1</sup> Cu at salinity 33, where SGR dropped to 0.86 d<sup>−1</sup>. ROS levels were highest under the combined low salinity (33) and 5 μg L<sup>−1</sup> Cu treatment, suggesting strong oxidative stress. PUA profiles shifted with Cu and salinity, with stress-related compounds such as 2<em>E</em>,4<em>E</em>/<em>Z</em>-decadienal and 2<em>E</em>,4<em>E</em>/<em>Z</em>,7<em>Z</em>-decatrienal increasing at low salinity. Fatty acid analysis revealed marked rises in saturated fatty acids, especially palmitic acid (C16:0) and myristic acid (C14:0), under Cu exposure. In the Cu2/39 treatment, C16:0 reached 1.34 × 10<sup>4</sup> fmol cell<sup>−1</sup> compared to 1.36 × 10<sup>3</sup> fmol cell<sup>−1</sup> in the control. Monounsaturated fatty acids, notably palmitoleic acid (C16:1), also increased, reaching 7. 46 × 10<sup>3</sup> fmol cell<sup>−1</sup> versus 1.71 × 10<sup>3</sup> fmol cell<sup>−1</sup> in the control. Conversely, polyunsaturated fatty acids, including arachidonic acid (C20:4) and eicosapentaenoic acid (C20:5 n-3), decreased significantly following Cu exposure. Overall, elevated salinity mitigated Cu-induced growth inhibition but intensified oxidative and biochemical stress, underscoring the complex, endpoint-specific responses of <em>C. calcitrans</em> to multiple environmental stressors.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"394 ","pages":"Article 144790"},"PeriodicalIF":8.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145691692","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 : 2025-12-03DOI: 10.1016/j.chemosphere.2025.144787
Wenxia (Wendy) Fan , Kim N. Dirks , Alessandro F. Gualtieri , Paul G. Young , Ayrton Hamilton , Janki P. Patel , Timothy D. Christopher , Jennifer A. Salmond
Naturally occurring fibrous minerals, including erionite and amphiboles, are classified as Group 1 carcinogens, and pose an environmental health risk when inhaled in respirable sizes. In volcaniclastic regions, road cuttings that disturb and expose fibre-bearing formations can release airborne fibres through weathering and human activities. To investigate this process, this study collected surface dust and rock samples from roadside environments in a New Zealand volcaniclastic setting and analysed fibre abundance, characteristics, and the connection between rock sources and airborne fibres.
Fibrous particles were detected in surface leaf dust on both sides of the road at all 11 sampling sites, with fibre abundance ranging from 462 to 61,595 fibres/cm2. Of the 338 fibres measured, 93 % were within the respirable size range (geometric diameter <3 μm), and 15 % met the WHO criteria for hazardous fibres (length ≥5 μm, width <3 μm, aspect ratio >3:1). Chemical analysis indicated that most fibres had Si/(Si + Al) ratios consistent with mordenite, while crystallographic data confirmed 84 % mordenite, 13 % erionite, and 3 % amphibole. Mordenite was also the dominant crystalline phase in the rock samples, and fibre abundance in surface dust correlated moderately with mordenite concentrations in the corresponding bulk samples (Kendall's tau = 0.49, p = 0.04).
These findings reveal an under-recognised environmental exposure pathway of respirable mineral fibres from roadside exposed volcanic outcrops, and highlight the need for further monitoring and health risk evaluation in volcanic regions where fibrous zeolite and amphibole minerals are naturally occurring and disturbed.
天然存在的纤维矿物，包括铁钙石和角闪石，被列为1类致癌物，当以可吸入的大小吸入时，会对环境健康构成风险。在火山碎屑区，道路岩屑会破坏和暴露含纤维地层，并通过风化和人类活动将纤维释放到空气中。为了研究这一过程，本研究从新西兰火山碎屑环境的路边环境中收集了表面灰尘和岩石样本，并分析了纤维的丰度、特征以及岩石来源和空气纤维之间的联系。在所有11个采样点的道路两侧的表面叶尘中检测到纤维颗粒，纤维丰度从462到61,595纤维/cm2不等。在测量的338根纤维中，93%在可呼吸的尺寸范围内（几何直径3:1）。化学分析表明，大多数纤维的Si/(Si + Al)比例与丝光沸石一致，而晶体学数据证实84%是丝光沸石，13%是绒线沸石，3%是角闪石。丝光沸石也是岩石样品中的主要结晶相，表面尘埃中的纤维丰度与相应样品中的丝光沸石浓度适度相关（Kendall's tau = 0.49, p = 0.04）。这些发现揭示了路边暴露的火山露头可吸入矿物纤维的环境暴露途径尚未得到充分认识，并强调了在纤维状沸石和角闪孔矿物自然产生和受到干扰的火山地区进行进一步监测和健康风险评估的必要性。
{"title":"Respirable mineral fibres in leaf surface dust: Micro-characterisation and evidence of a geogenic origin","authors":"Wenxia (Wendy) Fan , Kim N. Dirks , Alessandro F. Gualtieri , Paul G. Young , Ayrton Hamilton , Janki P. Patel , Timothy D. Christopher , Jennifer A. Salmond","doi":"10.1016/j.chemosphere.2025.144787","DOIUrl":"10.1016/j.chemosphere.2025.144787","url":null,"abstract":"<div><div>Naturally occurring fibrous minerals, including erionite and amphiboles, are classified as <em>Group 1</em> carcinogens, and pose an environmental health risk when inhaled in respirable sizes. In volcaniclastic regions, road cuttings that disturb and expose fibre-bearing formations can release airborne fibres through weathering and human activities. To investigate this process, this study collected surface dust and rock samples from roadside environments in a New Zealand volcaniclastic setting and analysed fibre abundance, characteristics, and the connection between rock sources and airborne fibres.</div><div>Fibrous particles were detected in surface leaf dust on both sides of the road at all 11 sampling sites, with fibre abundance ranging from 462 to 61,595 fibres/cm<sup>2</sup>. Of the 338 fibres measured, 93 % were within the respirable size range (geometric diameter <3 μm), and 15 % met the WHO criteria for hazardous fibres (length ≥5 μm, width <3 μm, aspect ratio >3:1). Chemical analysis indicated that most fibres had Si/(Si + Al) ratios consistent with mordenite, while crystallographic data confirmed 84 % mordenite, 13 % erionite, and 3 % amphibole. Mordenite was also the dominant crystalline phase in the rock samples, and fibre abundance in surface dust correlated moderately with mordenite concentrations in the corresponding bulk samples (Kendall's tau = 0.49, <em>p</em> = 0.04).</div><div>These findings reveal an under-recognised environmental exposure pathway of respirable mineral fibres from roadside exposed volcanic outcrops, and highlight the need for further monitoring and health risk evaluation in volcanic regions where fibrous zeolite and amphibole minerals are naturally occurring and disturbed.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"394 ","pages":"Article 144787"},"PeriodicalIF":8.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145679538","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 : 2025-12-03DOI: 10.1016/j.chemosphere.2025.144789
María de la Paz Pollicelli , Federico Márquez , Yanina L. Idaszkin
Lead (Pb) and zinc (Zn) pollution are major environmental concerns in salt marshes affected by anthropogenic inputs. This study aims to enhance our understanding of the impact of Pb and Zn increases, individually and in combination, on Limonium brasiliense and Atriplex vulgatissima by examining accumulation patterns and combining morphological, physiological, and biochemical biomarkers, summarized using the Integrated Biological Response index (IBRv2). Our findings showed leaf-shape plasticity in L. brasiliense, whereas in A. vulgatissima a canalized morphology across treatments, a trend reflected in most biomarkers. Both species survived and maintained biomass, indicating tolerance to metal-induced stress. In L. brasiliense, variations in water content, leaf size, pigment concentration, photosynthetic efficiency, and ascorbate peroxidase activity highlighted a significant role of Zn in disrupting physiological function. In A. vulgatissima, most biomarkers, except leaf size and the activities of superoxide dismutase and guaiacol peroxidase, remained unchanged after treatments. Under Pb + Zn treatment, L. brasiliense accumulated Pb in roots and Zn in shoots, with a reduction in absorption efficiency (AE), whereas A. vulgatissima showed root-restricted accumulation of both metals and an increased AE. The IBRv2 indicated greater stress under Pb + Zn treatment in L. brasiliense and under Zn treatment in A. vulgatissima. Thus, these results suggest that L. brasiliense is more suitable for Pb phytostabilization and Zn phytoextraction, while A. vulgatissima may contribute to phytostabilization of both metals, showing distinct strategies: plasticity and modulation versus inherent tolerance, respectively. The findings highlight species-specific differences in metal tolerance, accumulation, and stress responses, directly impacting phytoremediation and biomonitoring in metal-contaminated environments.
{"title":"Integrative biomarker assessment of lead and zinc stress in Limonium brasiliense and Atriplex vulgatissima from Patagonian salt marshes","authors":"María de la Paz Pollicelli , Federico Márquez , Yanina L. Idaszkin","doi":"10.1016/j.chemosphere.2025.144789","DOIUrl":"10.1016/j.chemosphere.2025.144789","url":null,"abstract":"<div><div>Lead (Pb) and zinc (Zn) pollution are major environmental concerns in salt marshes affected by anthropogenic inputs. This study aims to enhance our understanding of the impact of Pb and Zn increases, individually and in combination, on <em>Limonium brasiliense</em> and <em>Atriplex vulgatissima</em> by examining accumulation patterns and combining morphological, physiological, and biochemical biomarkers, summarized using the Integrated Biological Response index (IBRv2). Our findings showed leaf-shape plasticity in <em>L. brasiliense,</em> whereas in <em>A. vulgatissima</em> a canalized morphology across treatments, a trend reflected in most biomarkers. Both species survived and maintained biomass, indicating tolerance to metal-induced stress. In <em>L. brasiliense</em>, variations in water content, leaf size, pigment concentration, photosynthetic efficiency, and ascorbate peroxidase activity highlighted a significant role of Zn in disrupting physiological function. In <em>A. vulgatissima</em>, most biomarkers, except leaf size and the activities of superoxide dismutase and guaiacol peroxidase, remained unchanged after treatments. Under Pb + Zn treatment, <em>L. brasiliense</em> accumulated Pb in roots and Zn in shoots, with a reduction in absorption efficiency (AE), whereas <em>A. vulgatissima</em> showed root-restricted accumulation of both metals and an increased AE. The IBRv2 indicated greater stress under Pb + Zn treatment in <em>L. brasiliense</em> and under Zn treatment in <em>A. vulgatissima</em>. Thus, these results suggest that <em>L. brasiliense</em> is more suitable for Pb phytostabilization and Zn phytoextraction, while <em>A. vulgatissima</em> may contribute to phytostabilization of both metals, showing distinct strategies: plasticity and modulation versus inherent tolerance, respectively. The findings highlight species-specific differences in metal tolerance, accumulation, and stress responses, directly impacting phytoremediation and biomonitoring in metal-contaminated environments.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"394 ","pages":"Article 144789"},"PeriodicalIF":8.1,"publicationDate":"2025-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145679609","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 : 2025-12-02DOI: 10.1016/j.chemosphere.2025.144779
Mathieu Martinez , Markus Lenz
Selenium (Se) is an essential yet toxic trace element; it has one of the narrowest nutritional optimums of all elements. The speciation of Se significantly influences its mobility, toxicity, bioavailability, and bioaccumulation. Se environmental cycling has been generally understood as a sequence of bidirectional redox processes of Se species. Elemental Se (Se0) is considered a central species that is thermodynamically favoured in the redox conditions found in most environments. This study reports the identification of a novel group of dissolved species called polyselenylsulfides (with the general formula SexSy2−). These species form upon the reaction of Se0 with sulfide. Using derivatisation and ultrahigh-performance liquid chromatography electrospray ionisation quadrupole time-of-flight mass spectrometry, polysulfides (Sx2−, x = 2–6), selenide (Se2−), polyselenides (Sex2−, x = 2–3), and previously undetected polyselenylsulfides (SeS2−, SeS22−, Se2S2−, and SeS32−) were identified. The reaction was spontaneous and proceeded rapidly at alkaline pH (completed within <24 h). A slower and incomplete reaction was observed at circumneutral pH. The fast and spontaneous reaction down to circumneutral pH suggests the ubiquitous importance of polyselenylsulfides in sulfidic environments and calls for revising the environmental fate of Se. The existence of polyselenylsulfides challenges the traditional ‘selenocentric’ view, which focuses on specific, bidirectional redox reactions that only involve Se species. Moreover, the perception of Se0 as a terminal, insoluble species in many anoxic environments is questioned. The adoption of a ‘chalcogenic’ perspective is proposed, wherein the selenium and sulfur cycles are closely interconnected and the fate of Se is governed by the presence of sulfide.
硒（Se）是人体必需但又有毒的微量元素；它是所有元素中营养含量最低的。硒的形态显著影响其流动性、毒性、生物利用度和生物积累。硒的环境循环通常被理解为一系列硒的双向氧化还原过程。元素硒（Se0）被认为是在大多数环境中发现的氧化还原条件下热力学有利的中心物种。本研究报告鉴定了一种新的溶解物质，称为聚硒基硫化物（通式为SexSy2-）。这些物质是由Se0与硫化物反应形成的。利用衍生化和超高效液相色谱电喷雾电离四极杆飞行时间质谱法，鉴定了多硫化物（Sx2-, x = 2-6）、硒化物（Se2-）、多硒化物（Sex2-, x = 2-3）和以前未检测到的多硒基硫化物（SeS2-、SeS22-、Se2S2-和SeS32-）。反应是自发的，在碱性条件下迅速进行（在0内完成），作为一个终端，在许多缺氧环境中不溶的物种受到质疑。建议采用“产硫”的观点，其中硒和硫循环紧密相连，硒的命运由硫化物的存在所控制。
{"title":"Polyselenylsulfides as neglected central intermediates in Selenium cycling","authors":"Mathieu Martinez , Markus Lenz","doi":"10.1016/j.chemosphere.2025.144779","DOIUrl":"10.1016/j.chemosphere.2025.144779","url":null,"abstract":"<div><div>Selenium (Se) is an essential yet toxic trace element; it has one of the narrowest nutritional optimums of all elements. The speciation of Se significantly influences its mobility, toxicity, bioavailability, and bioaccumulation. Se environmental cycling has been generally understood as a sequence of bidirectional redox processes of Se species. Elemental Se (Se<sup>0</sup>) is considered a central species that is thermodynamically favoured in the redox conditions found in most environments. This study reports the identification of a novel group of dissolved species called polyselenylsulfides (with the general formula Se<sub>x</sub>S<sub>y</sub><sup>2−</sup>). These species form upon the reaction of Se<sup>0</sup> with sulfide. Using derivatisation and ultrahigh-performance liquid chromatography electrospray ionisation quadrupole time-of-flight mass spectrometry, polysulfides (S<sub>x</sub><sup>2−</sup>, x = 2–6), selenide (Se<sup>2−</sup>), polyselenides (Se<sub>x</sub><sup>2−</sup>, x = 2–3), and previously undetected polyselenylsulfides (SeS<sup>2−</sup>, SeS<sub>2</sub><sup>2−</sup>, Se<sub>2</sub>S<sup>2−</sup>, and SeS<sub>3</sub><sup>2−</sup>) were identified. The reaction was spontaneous and proceeded rapidly at alkaline pH (completed within <24 h). A slower and incomplete reaction was observed at circumneutral pH. The fast and spontaneous reaction down to circumneutral pH suggests the ubiquitous importance of polyselenylsulfides in sulfidic environments and calls for revising the environmental fate of Se. The existence of polyselenylsulfides challenges the traditional ‘selenocentric’ view, which focuses on specific, bidirectional redox reactions that only involve Se species. Moreover, the perception of Se<sup>0</sup> as a terminal, insoluble species in many anoxic environments is questioned. The adoption of a ‘chalcogenic’ perspective is proposed, wherein the selenium and sulfur cycles are closely interconnected and the fate of Se is governed by the presence of sulfide.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"394 ","pages":"Article 144779"},"PeriodicalIF":8.1,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145673025","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 : 2025-12-02DOI: 10.1016/j.chemosphere.2025.144786
Mohammed Yusuf , Zannatun Naim , Md. Mebtahul Jannat , Mahfuzul Islam , Nafis Rahman Sayeem , Md. Monjurul Islam , Md. Hafezur Rahaman
The pervasive occurrence of antibiotic residues in aquatic environments has emerged as a pressing global environmental concern. These contaminants originate predominantly from pharmaceutical manufacturing effluents, hospital discharges, and agricultural runoff. Their persistent release fosters the proliferation and horizontal transfer of antibiotic-resistant bacteria and resistance genes. Reported abundances in pharmaceutical wastewater can reach up to 2.36 × 107 copies/mL, significantly exceeding those observed in municipal effluents. Conventional treatments achieve variable removal efficiencies (e.g., 45–98 % for membrane bioreactors, >90 % for ozonation, and 62–86 % for anaerobic digestion) but often fail to remove structurally complex and persistent antibiotics, particularly under real wastewater conditions. Metal–organic frameworks (MOFs), with surface areas exceeding 2000 m2/g, tunable porosity, and diverse functional groups, have emerged as advanced adsorbents. Zr-based MOFs such as PCN-777 and MOF-525 exhibit exceptional adsorption capacities, 442.48 mg/g for cephalexin and up to 860 mg/g for tetracycline, surpassing conventional adsorbents like activated carbon. This review integrates experimental findings and density functional theory modelling to elucidate dominant antibiotic-MOF interaction mechanisms, including electrostatic attraction, π–π stacking, hydrogen bonding, Lewis acid-base coordination, and hydrophobic effects, offering molecular-level insight into adsorption phenomena. Key challenges, including hydrolytic instability, metal ion leaching, performance reduction in complex matrices, regeneration inefficiencies, and the limited representativeness of single-compound studies in predicting field-scale behavior, are critically evaluated. By linking mechanistic understanding with operational challenges, this work provides a targeted roadmap for developing water-stable, regenerable MOFs capable of delivering scalable and sustainable antibiotic remediation in diverse and challenging wastewater environments.
{"title":"Unraveling the potential of metal–organic frameworks for antibiotic remediation: From molecular interactions to real-world challenges","authors":"Mohammed Yusuf , Zannatun Naim , Md. Mebtahul Jannat , Mahfuzul Islam , Nafis Rahman Sayeem , Md. Monjurul Islam , Md. Hafezur Rahaman","doi":"10.1016/j.chemosphere.2025.144786","DOIUrl":"10.1016/j.chemosphere.2025.144786","url":null,"abstract":"<div><div>The pervasive occurrence of antibiotic residues in aquatic environments has emerged as a pressing global environmental concern. These contaminants originate predominantly from pharmaceutical manufacturing effluents, hospital discharges, and agricultural runoff. Their persistent release fosters the proliferation and horizontal transfer of antibiotic-resistant bacteria and resistance genes. Reported abundances in pharmaceutical wastewater can reach up to 2.36 × 10<sup>7</sup> copies/mL, significantly exceeding those observed in municipal effluents. Conventional treatments achieve variable removal efficiencies (e.g., 45–98 % for membrane bioreactors, >90 % for ozonation, and 62–86 % for anaerobic digestion) but often fail to remove structurally complex and persistent antibiotics, particularly under real wastewater conditions. Metal–organic frameworks (MOFs), with surface areas exceeding 2000 m<sup>2</sup>/g, tunable porosity, and diverse functional groups, have emerged as advanced adsorbents. Zr-based MOFs such as PCN-777 and MOF-525 exhibit exceptional adsorption capacities, 442.48 mg/g for cephalexin and up to 860 mg/g for tetracycline, surpassing conventional adsorbents like activated carbon. This review integrates experimental findings and density functional theory modelling to elucidate dominant antibiotic-MOF interaction mechanisms, including electrostatic attraction, π–π stacking, hydrogen bonding, Lewis acid-base coordination, and hydrophobic effects, offering molecular-level insight into adsorption phenomena. Key challenges, including hydrolytic instability, metal ion leaching, performance reduction in complex matrices, regeneration inefficiencies, and the limited representativeness of single-compound studies in predicting field-scale behavior, are critically evaluated. By linking mechanistic understanding with operational challenges, this work provides a targeted roadmap for developing water-stable, regenerable MOFs capable of delivering scalable and sustainable antibiotic remediation in diverse and challenging wastewater environments.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"394 ","pages":"Article 144786"},"PeriodicalIF":8.1,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145673067","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 : 2025-12-01DOI: 10.1016/j.chemosphere.2025.144781
Dina H. Elsalamony , Ibrahim Maamoun , Osama Eljamal
Nano zero-valent manganese and nano zero-valent iron were chemically combined to form a bimetallic composite (nZVMI). The synthesized materials were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction, along with kinetics, thermodynamics, and isotherm studies. Their capability, performance, and fundamental mechanisms for adsorbing phosphorus were investigated. Comparative tests demonstrated the synergistic superiority of nZVMI overusing both nZVM and nZVI alone. It was found that the analyzed bimetal acts as a composite with a core-shell structure that can adsorb up to 346.50 mg/g of phosphorus at 0.2 g/L of adsorbent dosage at a pH of 5 and for a 50 mg/L phosphorus solution. The reaction mechanisms of phosphorus using nZVMI were probably described as adsorption, surface complexation, co-precipitation, and electrostatic sorption. The adsorption mechanisms of the synthesized adsorbents fit the second-order pseudo-kinetic model. This study presents a new method for effectively removing phosphorus from water and improves the understanding of phosphorus interactions between nZVM and nZVMI. This bimetallic composite has a sustainable potential for effectively removing phosphorus from real river water with 99.5 % removal efficiency, providing phosphorus recovery, which is one of the priority agendas for global food security.
{"title":"Synergistic phosphorus removal from water using core–shell manganese–iron nanocomposites: Adsorption performance and recovery potential","authors":"Dina H. Elsalamony , Ibrahim Maamoun , Osama Eljamal","doi":"10.1016/j.chemosphere.2025.144781","DOIUrl":"10.1016/j.chemosphere.2025.144781","url":null,"abstract":"<div><div>Nano zero-valent manganese and nano zero-valent iron were chemically combined to form a bimetallic composite (nZVMI). The synthesized materials were characterized using scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction, along with kinetics, thermodynamics, and isotherm studies. Their capability, performance, and fundamental mechanisms for adsorbing phosphorus were investigated. Comparative tests demonstrated the synergistic superiority of nZVMI overusing both nZVM and nZVI alone. It was found that the analyzed bimetal acts as a composite with a core-shell structure that can adsorb up to 346.50 mg/g of phosphorus at 0.2 g/L of adsorbent dosage at a pH of 5 and for a 50 mg/L phosphorus solution. The reaction mechanisms of phosphorus using nZVMI were probably described as adsorption, surface complexation, co-precipitation, and electrostatic sorption. The adsorption mechanisms of the synthesized adsorbents fit the second-order pseudo-kinetic model. This study presents a new method for effectively removing phosphorus from water and improves the understanding of phosphorus interactions between nZVM and nZVMI. This bimetallic composite has a sustainable potential for effectively removing phosphorus from real river water with 99.5 % removal efficiency, providing phosphorus recovery, which is one of the priority agendas for global food security.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"394 ","pages":"Article 144781"},"PeriodicalIF":8.1,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145662854","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 : 2025-12-01DOI: 10.1016/j.chemosphere.2025.144775
Abhijeet Pathy , M. Anne Naeth , Scott X. Chang
Hydrocarbon fuel production and use can pose environmental risks, such as spills during extraction and transportation, which can contaminate soil, damage vegetation, adversely affect human and animal health, and contaminate ground water with soluble hydrocarbons, that could spread to surrounding areas. Our study evaluates the simultaneous adsorption capacity of canola straw biochar for 12 hydrocarbon pollutants in ground water from a northern peatland. This approach simulates the simultaneous contamination of multiple hydrocarbon classes in a complex aqueous matrix. In the laboratory, canola straw biochar remediated benzene, toluene, ethylbenzene, and xylene (BTEX), and linear chained and polycyclic aromatic hydrocarbons from ground water. BTEX concentrations significantly decreased with application of 1 g L−1 biochar, achieving a remediation efficiency of over 95 % within 7 days. Increasing application rates enhanced remediation efficiency, exceeding 99 % at a 2 g L−1 application rate. Hydrocarbon adsorption on biochar is a complex process involving surface interactions and diffusion-controlled steps, with the kinetic data fitting well to models indicative of chemisorption. X-ray photoelectron spectroscopy, BET/CO2 porosimetry and Fourier transform infrared spectroscopy corroborated theoretical isotherm and kinetic models, indicating that functional groups on the biochar surface play a crucial role in adsorption, primarily through hydrophobic and π-π interactions. The results enhanced our understanding of adsorption mechanisms for multiple hydrocarbon classes in complex matrices under controlled laboratory conditions, and positioned canola straw biochar as an effective remediation technique for hydrocarbon water treatment. Biochar is made from waste agricultural materials and sequesters carbon, contributing to environmentally sustainable remediation and a circular economy.
碳氢化合物燃料的生产和使用可能带来环境风险，例如在提取和运输过程中泄漏，可能污染土壤，破坏植被，对人类和动物的健康产生不利影响，并使可溶性碳氢化合物污染地下水，并可能蔓延到周围地区。研究了油菜秸秆生物炭对北部泥炭地地下水中12种烃类污染物的同时吸附能力。该方法模拟了复杂水性基质中多种烃类的同时污染。在实验室中，油菜秸秆生物炭修复了地下水中的苯、甲苯、乙苯和二甲苯（BTEX）以及线性链和多环芳烃。施用1 g L−1生物炭后，BTEX浓度显著降低，7天内修复效率达到95%以上。增加施用量可提高修复效率，在2 g L−1施用量下，修复效率超过99%。碳氢化合物在生物炭上的吸附是一个复杂的过程，涉及表面相互作用和扩散控制步骤，动力学数据与化学吸附模型拟合良好。x射线光电子能谱、BET/CO2孔隙度测定和傅里叶变换红外光谱证实了理论等温线和动力学模型，表明生物炭表面的官能团主要通过疏水和π-π相互作用在吸附中起关键作用。研究结果增强了我们对复杂基质中多种烃类在受控实验室条件下的吸附机理的理解，并将油菜秸秆生物炭定位为烃类水处理的有效修复技术。生物炭由废弃的农业材料制成，可以固碳，有助于环境可持续的修复和循环经济。
{"title":"Crop straw biochar enhances hydrocarbon adsorption in ground water","authors":"Abhijeet Pathy , M. Anne Naeth , Scott X. Chang","doi":"10.1016/j.chemosphere.2025.144775","DOIUrl":"10.1016/j.chemosphere.2025.144775","url":null,"abstract":"<div><div>Hydrocarbon fuel production and use can pose environmental risks, such as spills during extraction and transportation, which can contaminate soil, damage vegetation, adversely affect human and animal health, and contaminate ground water with soluble hydrocarbons, that could spread to surrounding areas. Our study evaluates the simultaneous adsorption capacity of canola straw biochar for 12 hydrocarbon pollutants in ground water from a northern peatland. This approach simulates the simultaneous contamination of multiple hydrocarbon classes in a complex aqueous matrix. In the laboratory, canola straw biochar remediated benzene, toluene, ethylbenzene, and xylene (BTEX), and linear chained and polycyclic aromatic hydrocarbons from ground water. BTEX concentrations significantly decreased with application of 1 g L<sup>−1</sup> biochar, achieving a remediation efficiency of over 95 % within 7 days. Increasing application rates enhanced remediation efficiency, exceeding 99 % at a 2 g L<sup>−1</sup> application rate. Hydrocarbon adsorption on biochar is a complex process involving surface interactions and diffusion-controlled steps, with the kinetic data fitting well to models indicative of chemisorption. X-ray photoelectron spectroscopy, BET/CO<sub>2</sub> porosimetry and Fourier transform infrared spectroscopy corroborated theoretical isotherm and kinetic models, indicating that functional groups on the biochar surface play a crucial role in adsorption, primarily through hydrophobic and π-π interactions. The results enhanced our understanding of adsorption mechanisms for multiple hydrocarbon classes in complex matrices under controlled laboratory conditions, and positioned canola straw biochar as an effective remediation technique for hydrocarbon water treatment. Biochar is made from waste agricultural materials and sequesters carbon, contributing to environmentally sustainable remediation and a circular economy.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"393 ","pages":"Article 144775"},"PeriodicalIF":8.1,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621353","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号