Pub Date : 2025-11-05DOI: 10.1016/j.chemosphere.2025.144607
Karin Binder , Jervis V. Thevathasan , Miriam Kronfuss , Alice Pedroni , Sarah Prochaska , Soumya S. Daturpalli , Michael Betz , Andreas Kuenkel , Georg M. Guebitz , Doris Ribitsch
Water-soluble polymers have exceptional properties and are therefore used in many applications. Many of these products end up down the drain; therefore biodegradability, especially in wastewater treatment plants, is essential to prevent accumulation in the environment. This study examined recombinant hydrolases PahZ1KT-1 and PahZ2KT-1 from Sphingomonas sp. KT-1 and PahZ1KP-2 from Pedobacter sp. KP-2 for their role in biodegrading water-soluble poly(aspartic acid) (tPAA). Analysis by a turbidity assay and Gel Permeation Chromatography (GPC) revealed highest activity of PahZ1KT-1 and PahZ1KP-2 at pH 8 and 40 °C on tPAA, whereas PahZ2KT-1 showed no activity on the polymer but yet on its oligopeptides with highest values at pH 7 and 55 °C. GPC analysis revealed that PahZ1KT-1 and PahZ1KP-2 hydrolyzed tPAA (MN > 17,000 Da) into oligopeptides (>500 Da), while PahZ2KT-1 further degraded them to α-di(l-aspartic acid) and l-aspartic acid. Combined, these enzymes synergistically decomposed tPAA completely into l-aspartic acid within 24 h. Supplementation of hydrolases into standardized biodegradation test improved biodegradation (54 %) of tPAA after 28 d. Supplementing PahZ1KT-1 or PahZ1KP-2 alone achieved 52 % and 54 % tPAA biodegradation, respectively. Preincubating tPAA with hydrolases boosted degradation to 71 % in 28 d. These findings highlight enzymes' crucial role in breaking down macromolecules into lower molecular weight species for effective tPAA biodegradation.
{"title":"The significance of hydrolase cascades on poly(aspartic) acid biodegradation assessment","authors":"Karin Binder , Jervis V. Thevathasan , Miriam Kronfuss , Alice Pedroni , Sarah Prochaska , Soumya S. Daturpalli , Michael Betz , Andreas Kuenkel , Georg M. Guebitz , Doris Ribitsch","doi":"10.1016/j.chemosphere.2025.144607","DOIUrl":"10.1016/j.chemosphere.2025.144607","url":null,"abstract":"<div><div>Water-soluble polymers have exceptional properties and are therefore used in many applications. Many of these products end up down the drain; therefore biodegradability, especially in wastewater treatment plants, is essential to prevent accumulation in the environment. This study examined recombinant hydrolases PahZ1<sub>KT-1</sub> and PahZ2<sub>KT-1</sub> from <em>Sphingomonas</em> sp. KT-1 and PahZ1<sub>KP-2</sub> from <em>Pedobacter</em> sp. KP-2 for their role in biodegrading water-soluble poly(aspartic acid) (tPAA). Analysis by a turbidity assay and Gel Permeation Chromatography (GPC) revealed highest activity of PahZ1<sub>KT-1</sub> and PahZ1<sub>KP-2</sub> at pH 8 and 40 °C on tPAA, whereas PahZ2<sub>KT-1</sub> showed no activity on the polymer but yet on its oligopeptides with highest values at pH 7 and 55 °C. GPC analysis revealed that PahZ1<sub>KT-1</sub> and PahZ1<sub>KP-2</sub> hydrolyzed tPAA (MN > 17,000 Da) into oligopeptides (>500 Da), while PahZ2<sub>KT-1</sub> further degraded them to α-di(<span>l</span>-aspartic acid) and <span>l</span>-aspartic acid. Combined, these enzymes synergistically decomposed tPAA completely into <span>l</span>-aspartic acid within 24 h. Supplementation of hydrolases into standardized biodegradation test improved biodegradation (54 %) of tPAA after 28 d. Supplementing PahZ1<sub>KT-1</sub> or PahZ1<sub>KP-2</sub> alone achieved 52 % and 54 % tPAA biodegradation, respectively. Preincubating tPAA with hydrolases boosted degradation to 71 % in 28 d. These findings highlight enzymes' crucial role in breaking down macromolecules into lower molecular weight species for effective tPAA biodegradation.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"391 ","pages":"Article 144607"},"PeriodicalIF":8.1,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145454249","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 : 2025-11-03DOI: 10.1016/j.chemosphere.2025.144749
Sunny O. Abarikwu , Ogechukwu E. Ezim , Guilherme M.J. Costa , Samyra M.S.N. Lacerda , Thalita Marcolan Valverde , Vivian Vasconcelos Costa , Oke Aruoren , Vivian E. Monye , Lauritta C. Ndufeiya-Kumasi , Iniobong A. Charles
Here, we investigated the effect of atrazine (ATZ, 50 mg kg−1 body weight) on lipopolysaccharide (LPS)-induced inducible nitric oxide synthase (iNOS) expression, nitric oxide (NO) production, tissue weights and oxidative stress variables (thiobarbituric acid reactive substances; (TBARS; measured as malondialdehyde) and catalase activity) in the testis, liver, epididymis, and prostate of BALB/c mice. In vitro, we examined the effects of ATZ (1–200 μM) on LPS-induced oxidative stress markers and NO production in RAW 264.7 macrophages, and cytokine responses (tumor necrosis factor-α: TNF-α and interleukin-1β: IL-1β) in differentiated THP-1 human macrophages after 48 h. The liver, testis, and prostate of ATZ + LPS animals had low NO concentrations relative to the LPS values. Interestingly, TBARS was increased in the ATZ + LPS-exposed mice in liver, epididymis and prostate compared to the LPS-treated mice. ATZ + LPS co-exposure also decreased the weight of the testis, epididymis, and prostate and altered the expression of iNOS in all the tissues. In vitro, ATZ alters the responses of RAW264.7 macrophages to inflammatory stimuli (LPS) by suppressing NO production. In differentiated THP-1 human macrophages, ATZ diminished TNF and IL-1β production following LPS stimulation. Altogether, our data indicate that atrazine suppresses immunological response in LPS-stimulated BALB/c mice and macrophage cell lines.
{"title":"Atrazine alters nitric oxide secretion and cytokines production in LPS-stimulated BalB/c mice, RAW264.7 macrophage and THP-1 cell lines","authors":"Sunny O. Abarikwu , Ogechukwu E. Ezim , Guilherme M.J. Costa , Samyra M.S.N. Lacerda , Thalita Marcolan Valverde , Vivian Vasconcelos Costa , Oke Aruoren , Vivian E. Monye , Lauritta C. Ndufeiya-Kumasi , Iniobong A. Charles","doi":"10.1016/j.chemosphere.2025.144749","DOIUrl":"10.1016/j.chemosphere.2025.144749","url":null,"abstract":"<div><div>Here, we investigated the effect of atrazine (ATZ, 50 mg kg<sup>−1</sup> body weight) on lipopolysaccharide (LPS)-induced inducible nitric oxide synthase (iNOS) expression, nitric oxide (NO) production, tissue weights and oxidative stress variables (thiobarbituric acid reactive substances; (TBARS; measured as malondialdehyde) and catalase activity) in the testis, liver, epididymis, and prostate of BALB/c mice. In vitro, we examined the effects of ATZ (1–200 μM) on LPS-induced oxidative stress markers and NO production in RAW 264.7 macrophages, and cytokine responses (tumor necrosis factor-α: TNF-α and interleukin-1β: IL-1β) in differentiated THP-1 human macrophages after 48 h. The liver, testis, and prostate of ATZ + LPS animals had low NO concentrations relative to the LPS values. Interestingly, TBARS was increased in the ATZ + LPS-exposed mice in liver, epididymis and prostate compared to the LPS-treated mice. ATZ + LPS co-exposure also decreased the weight of the testis, epididymis, and prostate and altered the expression of iNOS in all the tissues. In vitro, ATZ alters the responses of RAW264.7 macrophages to inflammatory stimuli (LPS) by suppressing NO production. In differentiated THP-1 human macrophages, ATZ diminished TNF and IL-1β production following LPS stimulation. Altogether, our data indicate that atrazine suppresses immunological response in LPS-stimulated BALB/c mice and macrophage cell lines.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144749"},"PeriodicalIF":8.1,"publicationDate":"2025-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145446875","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 : 2025-11-03DOI: 10.1016/j.chemosphere.2025.144753
Nguyen Thi Phuong Thao , Nguyen Le The Quang , Pham Thi Le Na , Bao-Trong Dang
Marine macroalgae are rich in nitrogen and oxygen functional groups, making their pyrolysis products promising adsorbents for antibiotic removal. This study investigated the brown algae biochar (SW400, SW600) for its ability to remove fluoroquinolones (FQs) and sulfamethoxazole (SMX) from water under various pH levels (3-10) and temperatures (20–32 °C). Nonlinear adsorption constants and thermodynamic parameters were estimated using Bayesian inference, while unsupervised pattern recognition revealed different adsorption mechanisms. Time-dependent adsorption was quantified via batch kinetic and continuous-flow fixed-bed breakthrough experiments, interpreted using six independent nonlinear models. Results found that SW400 maintained high concentrations of total phenolic and carboxylic groups (∼2.21 mmol g−1), while SW600 exhibited a fivefold reduction in these functional groups. As the pH shifts from 3 to 7, the sorption FQs transitions from cation exchange and cation-π interactions to π–π EDA interactions, corresponding with a reduction in cationic species distribution. Hydrogen bonding is the primary mechanism for SMX sorption, with SW400 sorption surpassing biochar derived from land-based biomass by 7–26 times. Sorption is characterized as an endothermic and entropy-driven process. The sorption kinetics were primarily affected by the ionization, steric structure, and hydration state of the antibiotics rather than the properties of the biochar types. In continuous-flow fixed-bed columns, the kinetic sorption was predicted using the Chu–Hashim model and aligned closely with batch kinetics. Our findings demonstrate that seaweed biochar provides an environmentally sustainable method for the removal of antibiotics, thereby contributing to the advancement of Sustainable Development Goals 6, 7, 12, and 14 b.
{"title":"Bayesian and unsupervised learning insights into pH- and temperature-driven sorption of fluoroquinolones and sulfonamides on marine algal biochar","authors":"Nguyen Thi Phuong Thao , Nguyen Le The Quang , Pham Thi Le Na , Bao-Trong Dang","doi":"10.1016/j.chemosphere.2025.144753","DOIUrl":"10.1016/j.chemosphere.2025.144753","url":null,"abstract":"<div><div>Marine macroalgae are rich in nitrogen and oxygen functional groups, making their pyrolysis products promising adsorbents for antibiotic removal. This study investigated the brown algae biochar (SW400, SW600) for its ability to remove fluoroquinolones (FQs) and sulfamethoxazole (SMX) from water under various pH levels (3-10) and temperatures (20–32 °C). Nonlinear adsorption constants and thermodynamic parameters were estimated using Bayesian inference, while unsupervised pattern recognition revealed different adsorption mechanisms. Time-dependent adsorption was quantified via batch kinetic and continuous-flow fixed-bed breakthrough experiments, interpreted using six independent nonlinear models. Results found that SW400 maintained high concentrations of total phenolic and carboxylic groups (∼2.21 mmol g<sup>−1</sup>), while SW600 exhibited a fivefold reduction in these functional groups. As the pH shifts from 3 to 7, the sorption FQs transitions from cation exchange and cation-π interactions to π–π EDA interactions, corresponding with a reduction in cationic species distribution. Hydrogen bonding is the primary mechanism for SMX sorption, with SW400 sorption surpassing biochar derived from land-based biomass by 7–26 times. Sorption is characterized as an endothermic and entropy-driven process. The sorption kinetics were primarily affected by the ionization, steric structure, and hydration state of the antibiotics rather than the properties of the biochar types. In continuous-flow fixed-bed columns, the kinetic sorption was predicted using the Chu–Hashim model and aligned closely with batch kinetics. Our findings demonstrate that seaweed biochar provides an environmentally sustainable method for the removal of antibiotics, thereby contributing to the advancement of Sustainable Development Goals 6, 7, 12, and 14 b.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144753"},"PeriodicalIF":8.1,"publicationDate":"2025-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145446889","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}
Infiltration of pharmaceuticals into marine ecosystems has emerged as a critical yet underexplored dimension of coastal pollution, with profound implications for biodiversity, ecosystem stability, and human health. This review synthesizes global and Indian perspectives on the sources, pathways, occurrence, and ecotoxicological impacts of Environmentally Persistent Pharmaceutical Pollutants (EPPPs) in marine environments, with emphasis on India's ecologically sensitive and economically vital 7500 km coastline. Marine pharmaceutical pollution has emerged as a significant environmental concern, with residues of antibiotics, NSAIDs, antidepressants, hormones, and anticancer drugs detected at concentrations ranging from 0.1 to 180 μg/L in coastal waters, sediments, and biota across Indian marine ecosystems. Sources include hospital and urban effluents, aquaculture and agricultural runoff, pharmaceutical manufacturing discharges, and improper disposal. Persistent pharmaceuticals, classified as Environmentally Persistent Pharmaceutical Pollutants (EPPPs), exhibit low degradability, bioaccumulate through trophic levels, and disrupt endocrine, neurological, and reproductive processes in marine flora and fauna. Chronic exposure promotes antimicrobial resistance, alters microbial community composition, reduces primary productivity in phytoplankton and macroalgae, and impairs fish behavior, immunity, and reproduction. Advanced analytical methods such as LC-MS/MS, UHPLC-QTOF-MS, FTIR, and SPE-LC-MS/MS enable detection of trace-level residues (<0.03–0.5 μg/L) in complex matrices. Sustainable mitigation strategies including microbial and algal bioremediation, enzymatic degradation, and carbonand biopolymer-based nanomaterials show promise for efficient pharmaceutical removal. Integrating multi-omics approaches, AI-driven predictive modeling, and policy frameworks is essential for evidence-based, scalable, and eco-efficient management of marine pharmaceutical pollution.
{"title":"Exploring the silent threats of pharmaceutical contaminants in indian seas: Monitoring, biological impact, and sustainable mitigation","authors":"Krishnamoorthy Santhosh , Pavithra Thiraviyam , Pauline Christupaul Roseline , Kamala Kannan , Dhanraj Ganapathy , Pitchiah Sivaperumal","doi":"10.1016/j.chemosphere.2025.144750","DOIUrl":"10.1016/j.chemosphere.2025.144750","url":null,"abstract":"<div><div>Infiltration of pharmaceuticals into marine ecosystems has emerged as a critical yet underexplored dimension of coastal pollution, with profound implications for biodiversity, ecosystem stability, and human health. This review synthesizes global and Indian perspectives on the sources, pathways, occurrence, and ecotoxicological impacts of Environmentally Persistent Pharmaceutical Pollutants (EPPPs) in marine environments, with emphasis on India's ecologically sensitive and economically vital 7500 km coastline. Marine pharmaceutical pollution has emerged as a significant environmental concern, with residues of antibiotics, NSAIDs, antidepressants, hormones, and anticancer drugs detected at concentrations ranging from 0.1 to 180 μg/L in coastal waters, sediments, and biota across Indian marine ecosystems. Sources include hospital and urban effluents, aquaculture and agricultural runoff, pharmaceutical manufacturing discharges, and improper disposal. Persistent pharmaceuticals, classified as Environmentally Persistent Pharmaceutical Pollutants (EPPPs), exhibit low degradability, bioaccumulate through trophic levels, and disrupt endocrine, neurological, and reproductive processes in marine flora and fauna. Chronic exposure promotes antimicrobial resistance, alters microbial community composition, reduces primary productivity in phytoplankton and macroalgae, and impairs fish behavior, immunity, and reproduction. Advanced analytical methods such as LC-MS/MS, UHPLC-QTOF-MS, FTIR, and SPE-LC-MS/MS enable detection of trace-level residues (<0.03–0.5 μg/L) in complex matrices. Sustainable mitigation strategies including microbial and algal bioremediation, enzymatic degradation, and carbonand biopolymer-based nanomaterials show promise for efficient pharmaceutical removal. Integrating multi-omics approaches, AI-driven predictive modeling, and policy frameworks is essential for evidence-based, scalable, and eco-efficient management of marine pharmaceutical pollution.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144750"},"PeriodicalIF":8.1,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414805","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 : 2025-11-01DOI: 10.1016/j.chemosphere.2025.144744
Tiziana Di Lorenzo , Sanda Iepure , Mattia Di Cicco , Diana Maria Paola Galassi , Walter Dario Di Marzio
Pharmaceutical pollution is a growing concern for aquatic ecosystems, yet the extent of contamination in groundwater and its ecological consequences remain poorly understood. This knowledge gap stems in part from the lack of mandatory monitoring of pharmaceutical compounds in groundwater across most regions of the world and from the lack of ecotoxicological tests on obligate groundwater-dwelling fauna. In this study, we applied the European Medicines Agency guidelines for groundwater environmental risk assessment (ERA) of diltiazem - a calcium channel blocker – introducing methodological adaptations to better reflect the characteristics of groundwater communities. We compared the sensitivity of the standard test species Daphnia magna and that of the facultative groundwater copepod Diacyclops crassicaudis crassicaudis, and we validated the predicted no-effect concentration (PNEC) of diltiazem by assessing its sublethal effects on oxygen consumption rates. We also reviewed the global literature to compile measured environmental concentrations of diltiazem in freshwater systems and, finally, estimated the potential risk to groundwater. Our study showed that D. crassicaudis crassicaudis is more sensitive to diltiazem than D. magna, supporting its use as surrogate species for groundwater ERA. Moreover, short-term exposure (48 h) to a sublethal concentration (54 μg/L) significantly increased oxygen consumption in D. crassicaudis crassicaudis, indicating the need for a groundwater PNEC at least one order of magnitude lower than that applied to surface waters. These findings highlight a negligible environmental risk from diltiazem in groundwater and stress the need to revise current regulatory thresholds by incorporating sublethal endpoints, ultimately promoting more realistic ERA for groundwater ecosystems.
{"title":"Refining environmental risk assessment of diltiazem in groundwater through better surrogate selection and sublethal endpoints","authors":"Tiziana Di Lorenzo , Sanda Iepure , Mattia Di Cicco , Diana Maria Paola Galassi , Walter Dario Di Marzio","doi":"10.1016/j.chemosphere.2025.144744","DOIUrl":"10.1016/j.chemosphere.2025.144744","url":null,"abstract":"<div><div>Pharmaceutical pollution is a growing concern for aquatic ecosystems, yet the extent of contamination in groundwater and its ecological consequences remain poorly understood. This knowledge gap stems in part from the lack of mandatory monitoring of pharmaceutical compounds in groundwater across most regions of the world and from the lack of ecotoxicological tests on obligate groundwater-dwelling fauna. In this study, we applied the European Medicines Agency guidelines for groundwater environmental risk assessment (ERA) of diltiazem - a calcium channel blocker – introducing methodological adaptations to better reflect the characteristics of groundwater communities. We compared the sensitivity of the standard test species <em>Daphnia magna</em> and that of the facultative groundwater copepod <em>Diacyclops crassicaudis crassicaudis</em>, and we validated the predicted no-effect concentration (PNEC) of diltiazem by assessing its sublethal effects on oxygen consumption rates. We also reviewed the global literature to compile measured environmental concentrations of diltiazem in freshwater systems and, finally, estimated the potential risk to groundwater. Our study showed that <em>D. crassicaudis crassicaudis</em> is more sensitive to diltiazem than <em>D. magna</em>, supporting its use as surrogate species for groundwater ERA. Moreover, short-term exposure (48 h) to a sublethal concentration (54 μg/L) significantly increased oxygen consumption in <em>D. crassicaudis crassicaudis</em>, indicating the need for a groundwater PNEC at least one order of magnitude lower than that applied to surface waters. These findings highlight a negligible environmental risk from diltiazem in groundwater and stress the need to revise current regulatory thresholds by incorporating sublethal endpoints, ultimately promoting more realistic ERA for groundwater ecosystems.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144744"},"PeriodicalIF":8.1,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414806","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 : 2025-10-31DOI: 10.1016/j.chemosphere.2025.144748
Juliette Bedrossiantz , Sergi Pujol , Josep M. Porta , Juan C. Carrizo , M. Silvia Diaz-Cruz , Carlos Barata
Modern imaging enables real-time observation of behavior under stress. Light is a major stressor for fish larvae and aquatic invertebrates, yet the effects of different wavelengths and intensities on behavior remain poorly understood. The freshwater zooplankton Daphnia magna, a key model species, typically displays negative vertical phototaxis to avoid predation. This study applied a high-throughput video-tracking system to assess chromatic phototactic responses in D. magna exposed to two common UV filters, octocrylene (OC) and benzophenone-3 (BP-3), at concentrations from 0.1 to 1000 μg/L. A custom chamber was designed with two experimental setups: (i) a horizontal rack of six 30 mL arenas to examine vertical phototaxis across wavelengths, and (ii) a 200 mL arena to test color preference. Illumination was provided by five LEDs (red, green, blue, UV-A, white) with infrared backlighting, and tracking performed using an infrared GigE camera with Python-based analysis. Control assays showed adult D. magna preferred blue and white light, followed by green, red, and UV. The strongest negative phototaxis occurred under UV-A, the weakest under red. Locomotor activity was greatest under white and lowest under red. Chemical exposure altered these patterns: OC at 10 μg/L increased negative phototaxis and reduced movement, whereas BP-3 at 100–1000 μg/L enhanced both. UV filters also shifted color preference, increasing selection of UV over other wavelengths, blue over white, and green over blue. Such behavioral disruptions could influence diel vertical migration, foraging, and trophic interactions, potentially increasing zooplankton predation and reducing algae grazing. This platform provides a robust high-throughput approach to evaluate locomotor responses of aquatic organisms under varying light conditions, offering new opportunities to uncover how chemical pollutants disrupt visual perception and behavior in aquatic ecosystems.
{"title":"An automated high-throughput platform reveals chromatic phototactic disruption in Daphnia magna exposed to the UV filters benzophenone-3 and octocrylene","authors":"Juliette Bedrossiantz , Sergi Pujol , Josep M. Porta , Juan C. Carrizo , M. Silvia Diaz-Cruz , Carlos Barata","doi":"10.1016/j.chemosphere.2025.144748","DOIUrl":"10.1016/j.chemosphere.2025.144748","url":null,"abstract":"<div><div>Modern imaging enables real-time observation of behavior under stress. Light is a major stressor for fish larvae and aquatic invertebrates, yet the effects of different wavelengths and intensities on behavior remain poorly understood. The freshwater zooplankton <em>Daphnia magna</em>, a key model species, typically displays negative vertical phototaxis to avoid predation. This study applied a high-throughput video-tracking system to assess chromatic phototactic responses in <em>D. magna</em> exposed to two common UV filters, octocrylene (OC) and benzophenone-3 (BP-3), at concentrations from 0.1 to 1000 μg/L. A custom chamber was designed with two experimental setups: (i) a horizontal rack of six 30 mL arenas to examine vertical phototaxis across wavelengths, and (ii) a 200 mL arena to test color preference. Illumination was provided by five LEDs (red, green, blue, UV-A, white) with infrared backlighting, and tracking performed using an infrared GigE camera with Python-based analysis. Control assays showed adult <em>D. magna</em> preferred blue and white light, followed by green, red, and UV. The strongest negative phototaxis occurred under UV-A, the weakest under red. Locomotor activity was greatest under white and lowest under red. Chemical exposure altered these patterns: OC at 10 μg/L increased negative phototaxis and reduced movement, whereas BP-3 at 100–1000 μg/L enhanced both. UV filters also shifted color preference, increasing selection of UV over other wavelengths, blue over white, and green over blue. Such behavioral disruptions could influence diel vertical migration, foraging, and trophic interactions, potentially increasing zooplankton predation and reducing algae grazing. This platform provides a robust high-throughput approach to evaluate locomotor responses of aquatic organisms under varying light conditions, offering new opportunities to uncover how chemical pollutants disrupt visual perception and behavior in aquatic ecosystems.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144748"},"PeriodicalIF":8.1,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414751","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 : 2025-10-31DOI: 10.1016/j.chemosphere.2025.144751
Weslei dos Santos Cunha , Carlos Henrique Martins de Menezes , Thaiany Moreira Alvarenga , Angelica Plata-Rueda , José Eduardo Serrão , Jose Cola Zanuncio , Luis Carlos Martínez
Podisus fuscescens (Hemiptera: Pentatomidae) is a predator that feeds on defoliating caterpillars in agricultural and forest crops. However, P. fuscescens often consumes prey that are commonly controlled by broad-spectrum insecticides, posing a threat to this predator. Mortality, survival, behavior, food consumption, and digestibility were evaluated in P. fuscescens after exposure to the insecticide chlorpyrifos via contact and ingestion. The lethal concentration (LC50 = 0.50 g L−1) of chlorpyrifos for P. fuscescens was determined after 48 h of exposure. During this period, survival rates for adults were 36.6 %, 21.1 %, 16.7 %, and 4.6 % at LC25 = 0.28, LC50 = 0.50, LC75 = 0.90, and LC90 = 1.52 g L−1, respectively. Movement behavior, including walking distance and resting time, decreased following exposure to the insecticide, while meandering behavior increased. Chlorpyrifos did not affect the prey preference of P. fuscescens. However, food consumption decreased when the stinkbug inserted its stylets into chlorpyrifos-contaminated prey, compared to the control group. Although the insecticide did not damage the salivary glands, it affected the digestive cells, potentially impairing the insect's digestibility. These findings suggest that chlorpyrifos can negatively impact the predatory activity of this biocontrol agent.
fuscescens（半翅目：蝽科）是一种以农林作物的落叶毛虫为食的捕食者。然而，fuscescens经常消耗通常被广谱杀虫剂控制的猎物，对这种捕食者构成威胁。通过接触和摄入杀虫剂毒死蜱，对fuscescens的死亡率、存活率、行为、食物消耗和消化率进行了评估。暴露48 h后测定毒死蜱对褐梭菌的致死浓度（LC50 = 0.50 g L−1）。在LC25 = 0.28、LC50 = 0.50、LC75 = 0.90和LC90 = 1.52 g L−1时，成虫存活率分别为36.6%、21.1%、16.7%和4.6%。运动行为，包括行走距离和休息时间，在杀虫剂作用下减少，而徘徊行为增加。毒死蜱对褐皮螟的捕食偏好没有影响。然而，与对照组相比，当臭虫将其柱头插入被毒死蜱污染的猎物时，食物消耗量减少了。虽然杀虫剂没有损害唾液腺，但它影响了消化细胞，潜在地损害了昆虫的消化能力。这些结果表明，毒死蜱会对该生物防治剂的捕食性产生负面影响。
{"title":"Effects of the insecticide chlorpyrifos on mortality, survival, behavior, prey consumption, and digestibility of the predatory stinkbug, Podisus fuscescens","authors":"Weslei dos Santos Cunha , Carlos Henrique Martins de Menezes , Thaiany Moreira Alvarenga , Angelica Plata-Rueda , José Eduardo Serrão , Jose Cola Zanuncio , Luis Carlos Martínez","doi":"10.1016/j.chemosphere.2025.144751","DOIUrl":"10.1016/j.chemosphere.2025.144751","url":null,"abstract":"<div><div><em>Podisus fuscescens</em> (Hemiptera: Pentatomidae) is a predator that feeds on defoliating caterpillars in agricultural and forest crops. However, <em>P. fuscescens</em> often consumes prey that are commonly controlled by broad-spectrum insecticides, posing a threat to this predator. Mortality, survival, behavior, food consumption, and digestibility were evaluated in <em>P. fuscescens</em> after exposure to the insecticide chlorpyrifos <em>via</em> contact and ingestion. The lethal concentration (LC<sub>50</sub> = 0.50 g L<sup>−1</sup>) of chlorpyrifos for <em>P. fuscescens</em> was determined after 48 h of exposure. During this period, survival rates for adults were 36.6 %, 21.1 %, 16.7 %, and 4.6 % at LC<sub>25</sub> = 0.28, LC<sub>50</sub> = 0.50, LC<sub>75</sub> = 0.90, and LC<sub>90</sub> = 1.52 g L<sup>−1</sup>, respectively. Movement behavior, including walking distance and resting time, decreased following exposure to the insecticide, while meandering behavior increased. Chlorpyrifos did not affect the prey preference of <em>P. fuscescens</em>. However, food consumption decreased when the stinkbug inserted its stylets into chlorpyrifos-contaminated prey, compared to the control group. Although the insecticide did not damage the salivary glands, it affected the digestive cells, potentially impairing the insect's digestibility. These findings suggest that chlorpyrifos can negatively impact the predatory activity of this biocontrol agent.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144751"},"PeriodicalIF":8.1,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414804","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 : 2025-10-31DOI: 10.1016/j.chemosphere.2025.144742
Daniel Skoczowsky , Jan Philipp Böhmer , Michael Kubicki , Sebastian Zühlke
Large quantities of pesticides are applied globally on agricultural sites, resulting in elevated concentrations of these compounds in soil pore water. A comprehensive understanding of the metabolic detoxification pathways of residual pesticides, following their uptake in crops, as well as the distribution of metabolites, is essential to ensure the safety of food and feed materials and to predict the potential environmental impacts. Therefore, we examined the metabolism of the pesticides metalaxyl (MET) and spirotetramat (SPI) and the distribution of their metabolites in maize plants grown in a hydroponic solution, utilising high-resolution mass spectrometry. While SPI demonstrated extensive biotransformation, MET exhibited a lower degree of metabolism. Significant discrepancies were observed in the distribution of metabolites between roots and shoots. Even stereoisomeric metabolites with nearly identical physicochemical properties showed clearly different translocation factors. The distribution of metabolites in leaves of different growth stages suggests a certain degree of mobility via the phloem of MET acid, hydroxy-MET and hydroxy-MET-glucoside, as well as SPI-enol and desmethyl-SPI-enol. Conversely, the distribution observed for the unmetabolized pesticides MET and SPI indicate that the xylem represents their dominant pathway for transport. MALDI mass spectrometry imaging has enabled to visualize accumulation sites of pesticide metabolites in root and shoot tissues at the micrometer level. The initial translocation from roots to shoots appears to occur mainly via the fast-transporting xylem, with subsequent phloem redistribution in the shoots being a slower process. Direct evidence for different transport and metabolism pathways of various pesticide metabolites has been observed, providing valuable insight into their fate in plants.
{"title":"Investigation of metabolism and spatial distribution of metabolites of metalaxyl and spirotetramat after root uptake in maize using HPLC-HRMS and MALDI-MSI","authors":"Daniel Skoczowsky , Jan Philipp Böhmer , Michael Kubicki , Sebastian Zühlke","doi":"10.1016/j.chemosphere.2025.144742","DOIUrl":"10.1016/j.chemosphere.2025.144742","url":null,"abstract":"<div><div>Large quantities of pesticides are applied globally on agricultural sites, resulting in elevated concentrations of these compounds in soil pore water. A comprehensive understanding of the metabolic detoxification pathways of residual pesticides, following their uptake in crops, as well as the distribution of metabolites, is essential to ensure the safety of food and feed materials and to predict the potential environmental impacts. Therefore, we examined the metabolism of the pesticides metalaxyl (MET) and spirotetramat (SPI) and the distribution of their metabolites in maize plants grown in a hydroponic solution, utilising high-resolution mass spectrometry. While SPI demonstrated extensive biotransformation, MET exhibited a lower degree of metabolism. Significant discrepancies were observed in the distribution of metabolites between roots and shoots. Even stereoisomeric metabolites with nearly identical physicochemical properties showed clearly different translocation factors. The distribution of metabolites in leaves of different growth stages suggests a certain degree of mobility via the phloem of MET acid, hydroxy-MET and hydroxy-MET-glucoside, as well as SPI-enol and desmethyl-SPI-enol. Conversely, the distribution observed for the unmetabolized pesticides MET and SPI indicate that the xylem represents their dominant pathway for transport. MALDI mass spectrometry imaging has enabled to visualize accumulation sites of pesticide metabolites in root and shoot tissues at the micrometer level. The initial translocation from roots to shoots appears to occur mainly via the fast-transporting xylem, with subsequent phloem redistribution in the shoots being a slower process. Direct evidence for different transport and metabolism pathways of various pesticide metabolites has been observed, providing valuable insight into their fate in plants.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144742"},"PeriodicalIF":8.1,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414752","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 : 2025-10-31DOI: 10.1016/j.chemosphere.2025.144747
Yuch P. Hsieh, Glynnis C. Bugna
Biochar amendment in soil offers multiple benefits, including improved soil health, reduced fertilizer usage and contamination, and sequestered atmospheric carbon. The properties of biochar can vary depending on the type of feedstock and the pyrolysis conditions. Characterizing biochar is therefore essential for biochar research and quality control in production. Characterizing biochar, however, is far from convenient using the traditional methods. In this study, we applied a much simpler Multi-Element Scanning Thermal Analysis (MESTA) technology to characterize biochar and feedstock. We used eight feedstocks and their corresponding 16 biochars, produced at various pyrolysis temperatures. The results showed that MESTA can simultaneously determine the contents of C, N, H, S, and O, as well as the thermal stability of biochar. We also examined the extent of organic C conversion to carbonate due to pyrolysis and loss-on-ignition processes, which may affect the accuracy of biochar organic oxygen determinations. We found that the MESTA thermogram of a feedstock can be used to predict the yield and thermal stability of its biochar, as well as the biochar-to-energy byproduct ratio. We identified a pyrolysis temperature of 400–450 °C for biochar production, which balances the desired biochar properties and energy consumption. This study showed that MESTA is a convenient and powerful tool for biochar research and production.
{"title":"Characterizing biochar by Multi-Element Scanning Thermal Analysis (MESTA)","authors":"Yuch P. Hsieh, Glynnis C. Bugna","doi":"10.1016/j.chemosphere.2025.144747","DOIUrl":"10.1016/j.chemosphere.2025.144747","url":null,"abstract":"<div><div>Biochar amendment in soil offers multiple benefits, including improved soil health, reduced fertilizer usage and contamination, and sequestered atmospheric carbon. The properties of biochar can vary depending on the type of feedstock and the pyrolysis conditions. Characterizing biochar is therefore essential for biochar research and quality control in production. Characterizing biochar, however, is far from convenient using the traditional methods. In this study, we applied a much simpler Multi-Element Scanning Thermal Analysis (MESTA) technology to characterize biochar and feedstock. We used eight feedstocks and their corresponding 16 biochars, produced at various pyrolysis temperatures. The results showed that MESTA can simultaneously determine the contents of C, N, H, S, and O, as well as the thermal stability of biochar. We also examined the extent of organic C conversion to carbonate due to pyrolysis and loss-on-ignition processes, which may affect the accuracy of biochar organic oxygen determinations. We found that the MESTA thermogram of a feedstock can be used to predict the yield and thermal stability of its biochar, as well as the biochar-to-energy byproduct ratio. We identified a pyrolysis temperature of 400–450 °C for biochar production, which balances the desired biochar properties and energy consumption. This study showed that MESTA is a convenient and powerful tool for biochar research and production.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144747"},"PeriodicalIF":8.1,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414753","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 : 2025-10-30DOI: 10.1016/j.chemosphere.2025.144746
Célio Freire Mariz Jr. , Maria K. Melo Alves , Leticia P. Pontes , Maria Clara A. Sá-Correia , Maianne J. da Silva Santos , Roxanny H. de Arruda-Santos , Eliete Zanardi-Lamardo , Paulo S.M. Carvalho
Between 2019 and 2020, the Brazilian coast was impacted by ∼5400 tons of weathered, emulsified oil, causing widespread ecological and socioeconomic damage. Marine oil spills pose severe threats to aquatic ecosystems, and toxicity can be amplified by environmental factors such as ultraviolet (UV) radiation. This study investigated the photo-enhanced toxicity on Danio rerio early life stages (ELS) exposed to a water accommodated fraction (WAF) of this oil with concurrent UV exposure from natural sunlight (WAF + UV) compared to exposure protected from sunlight (WAF-UV). Concentration of total polycyclic aromatic hydrocarbons (ΣPAH33) in the WAF-100 % was 32.95 μg-ΣPAH33 L−1. Exposure to WAF + UV increased toxicity 3.5-fold from a lethal concentration to 20 % (LC20) of exposed larvae after 168 h of exposure of 29.1 ± 5.8 μg-ΣPAH33 L−1 (WAF-UV) to 8.4 ± 0.7 μg-ΣPAH33 L−1 (WAF + UV). Developmental delays based on the General Morphology Score (GMS) and developmental abnormalities based on the General Teratology Score (GTS) increased based on a fourfold reduction in lowest observed effect concentrations (LOEC) for GMS and GTS under WAF + UV exposures. Morphometric LOECs for reduced total length and eye area decreased 8-fold and 16-fold, respectively. Frequency of larvae with absent cardiac looping increased four-fold and bradycardia increased after WAF + UV exposure, indicating physiological disruption. Biochemical analyses revealed oxidative stress induction, with increased GST, SOD, and LPO levels, correlating with increased developmental abnormalities. These results demonstrated that translucent ELS fish exposed to oil from the 2019 Brazilian spill and natural sunlight suffer enhanced toxicity, highlighting the need to include phototoxic effects in tropical oil spill risk assessments.
{"title":"Tropical sunlight induces the photo-enhanced toxicity of polycyclic aromatic hydrocarbons from the Brazilian oil spill to Danio rerio early life stages.","authors":"Célio Freire Mariz Jr. , Maria K. Melo Alves , Leticia P. Pontes , Maria Clara A. Sá-Correia , Maianne J. da Silva Santos , Roxanny H. de Arruda-Santos , Eliete Zanardi-Lamardo , Paulo S.M. Carvalho","doi":"10.1016/j.chemosphere.2025.144746","DOIUrl":"10.1016/j.chemosphere.2025.144746","url":null,"abstract":"<div><div>Between 2019 and 2020, the Brazilian coast was impacted by ∼5400 tons of weathered, emulsified oil, causing widespread ecological and socioeconomic damage. Marine oil spills pose severe threats to aquatic ecosystems, and toxicity can be amplified by environmental factors such as ultraviolet (UV) radiation. This study investigated the photo-enhanced toxicity on <em>Danio rerio</em> early life stages (ELS) exposed to a water accommodated fraction (WAF) of this oil with concurrent UV exposure from natural sunlight (WAF + UV) compared to exposure protected from sunlight (WAF-UV). Concentration of total polycyclic aromatic hydrocarbons (ΣPAH<sub>33</sub>) in the WAF-100 % was 32.95 μg-ΣPAH<sub>33</sub> L<sup>−1</sup>. Exposure to WAF + UV increased toxicity 3.5-fold from a lethal concentration to 20 % (LC20) of exposed larvae after 168 h of exposure of 29.1 ± 5.8 μg-ΣPAH<sub>33</sub> L<sup>−1</sup> (WAF-UV) to 8.4 ± 0.7 μg-ΣPAH<sub>33</sub> L<sup>−1</sup> (WAF + UV). Developmental delays based on the General Morphology Score (GMS) and developmental abnormalities based on the General Teratology Score (GTS) increased based on a fourfold reduction in lowest observed effect concentrations (LOEC) for GMS and GTS under WAF + UV exposures. Morphometric LOECs for reduced total length and eye area decreased 8-fold and 16-fold, respectively. Frequency of larvae with absent cardiac looping increased four-fold and bradycardia increased after WAF + UV exposure, indicating physiological disruption. Biochemical analyses revealed oxidative stress induction, with increased GST, SOD, and LPO levels, correlating with increased developmental abnormalities. These results demonstrated that translucent ELS fish exposed to oil from the 2019 Brazilian spill and natural sunlight suffer enhanced toxicity, highlighting the need to include phototoxic effects in tropical oil spill risk assessments.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144746"},"PeriodicalIF":8.1,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145414755","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}
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