Pub Date : 2025-11-06DOI: 10.1016/j.chemosphere.2025.144758
Mona Farhani , Alice Grgicak-Mannion , Paul Weidman , Todd Leadley , Nargis Ismail , Ken G. Drouillard
Temporal trends of bioavailable PCB water concentrations from a long running mussel biomonitoring program (1998–2023) in the Detroit River, Ontario, Canada. Bioavailable sum PCB10 concentrations exhibited long term declines at two biomonitoring locations but such declines were influenced by changes in water levels and showed different responses among individual congeners. Temporal declines in PCBs were highest rising water levels, PCBs reverted to an increasing trend for all congeners at the upstream biomonitoring location. At the midstream location, only PCBs 28 + 31 and 52 changed their temporal trajectories, while other PCBs slowed their decline relative to the constant water level regime. A deep neural network (DNN) model was trained to the data. The parsimony optimized model identified sediment PCB concentrations, chemical KOW, mean annual water level and year as the most important predictors of PCB water concentrations and explained more than double the variation compared to a multiple regression model. Overall, both empirical and modeled results show that hydrological fluctuations significantly affected bioavailable PCB concentrations and their temporal trends in this system. As water levels continue to decline in the Detroit River, PCBs are expected to resume their previous decreasing trend in the coming years.
{"title":"An artificial neural network model reveals water level changes alter bioavailable PCB concentrations in the Detroit River","authors":"Mona Farhani , Alice Grgicak-Mannion , Paul Weidman , Todd Leadley , Nargis Ismail , Ken G. Drouillard","doi":"10.1016/j.chemosphere.2025.144758","DOIUrl":"10.1016/j.chemosphere.2025.144758","url":null,"abstract":"<div><div>Temporal trends of bioavailable PCB water concentrations from a long running mussel biomonitoring program (1998–2023) in the Detroit River, Ontario, Canada. Bioavailable sum PCB10 concentrations exhibited long term declines at two biomonitoring locations but such declines were influenced by changes in water levels and showed different responses among individual congeners. Temporal declines in PCBs were highest rising water levels, PCBs reverted to an increasing trend for all congeners at the upstream biomonitoring location. At the midstream location, only PCBs 28 + 31 and 52 changed their temporal trajectories, while other PCBs slowed their decline relative to the constant water level regime. A deep neural network (DNN) model was trained to the data. The parsimony optimized model identified sediment PCB concentrations, chemical KOW, mean annual water level and year as the most important predictors of PCB water concentrations and explained more than double the variation compared to a multiple regression model. Overall, both empirical and modeled results show that hydrological fluctuations significantly affected bioavailable PCB concentrations and their temporal trends in this system. As water levels continue to decline in the Detroit River, PCBs are expected to resume their previous decreasing trend in the coming years.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144758"},"PeriodicalIF":8.1,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464400","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 : 2025-11-06DOI: 10.1016/j.chemosphere.2025.144755
Fatima Ezzahra Arhouni , Maged Ahmed Saleh Abdo , Saad Ouakkas , Aziz Boukhair
Morocco holds the world's largest reserves of phosphate rock, which play a pivotal role in its economy through fertilizer production and global export. However, the presence of naturally occurring radionuclides, particularly uranium and its decay products, poses significant environmental and radiological challenges. This review synthesizes current knowledge on uranium concentrations in Moroccan phosphate rock and its industrial derivatives, drawing on recent studies that quantify radioactivity levels and their implications. We emphasize underexplored issues such as uranium speciation, its redistribution during processing, long-term accumulation in agricultural soils, and potential health risks. Additionally, we address gaps in current research, including the lack of nationwide monitoring programs, insufficient data on uranium mobility, and potential recovery opportunities from waste streams. By identifying these knowledge gaps, this review proposes future research directions to support sustainable phosphate exploitation while informing radiological risks and ensuring environmental and public health protection.
{"title":"Uranium in Moroccan phosphate rock and derivatives: Occurrence, redistribution, and radiological considerations","authors":"Fatima Ezzahra Arhouni , Maged Ahmed Saleh Abdo , Saad Ouakkas , Aziz Boukhair","doi":"10.1016/j.chemosphere.2025.144755","DOIUrl":"10.1016/j.chemosphere.2025.144755","url":null,"abstract":"<div><div>Morocco holds the world's largest reserves of phosphate rock, which play a pivotal role in its economy through fertilizer production and global export. However, the presence of naturally occurring radionuclides, particularly uranium and its decay products, poses significant environmental and radiological challenges. This review synthesizes current knowledge on uranium concentrations in Moroccan phosphate rock and its industrial derivatives, drawing on recent studies that quantify radioactivity levels and their implications. We emphasize underexplored issues such as uranium speciation, its redistribution during processing, long-term accumulation in agricultural soils, and potential health risks. Additionally, we address gaps in current research, including the lack of nationwide monitoring programs, insufficient data on uranium mobility, and potential recovery opportunities from waste streams. By identifying these knowledge gaps, this review proposes future research directions to support sustainable phosphate exploitation while informing radiological risks and ensuring environmental and public health protection.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144755"},"PeriodicalIF":8.1,"publicationDate":"2025-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463983","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}
Cassava starch is a major global starch source, with 80 % of its production generating waste, predominantly cassava bagasse. This study valorized cassava bagasse by developing active packaging films incorporated with nutmeg essential oil (NO) at varying concentrations (1–3% w/w). The integration of NO increased film thickness from 0.38 mm to 0.67 mm, and tensile strength (TS) from 0.66 MPa to 1.19 MPa, while reducing density (1.33–1.21 g cm−3), transparency (75.51–53.62%), and solubility. Films exhibited higher opacity (46.72–58.73%) and enhanced color intensity. SEM images revealed fewer oil droplets and a more microporous structure, indicating improved compatibility. FT-IR confirmed that NO did not alter the film's chemical composition, although XRD indicated enhanced crystallinity. Thermal stability improved as the maximum decomposition temperature increased from 299.28 °C to 301.48 °C. Migration analysis demonstrated enhanced phytochemical release in different solvents, following Fickian-type diffusion. HS-SPME analysis revealed p-cymene, terpinen-4-ol, γ-terpinene, sabinene, and safrole as the dominant volatiles, contributing to antioxidant and antimicrobial activity. Disk diffusion assays showed N03 exhibited the largest inhibition zones against E. coli (20.67 mm) and S. aureus (31.33 mm). Moreover, grapes packed with N03 (NO 3%) film maintained quality for 10 d at room temperature, with reduced weight loss, color variation, and microbial proliferation compared to controls. The findings confirm that NO incorporation significantly enhanced the physicochemical, structural, and bioactive performance of cassava bagasse films, demonstrating strong potential for sustainable food packaging applications.
{"title":"Valorization of cassava starch waste for multifunctional packaging: Optimizing antimicrobial, thermal, mechanical, and functional performance through nutmeg essential oil integration","authors":"Chalani Akmeemana, Dulani Somendrika, Indira Wickramasinghe, Isuru Wijesekara","doi":"10.1016/j.chemosphere.2025.144739","DOIUrl":"10.1016/j.chemosphere.2025.144739","url":null,"abstract":"<div><div>Cassava starch is a major global starch source, with 80 % of its production generating waste, predominantly cassava bagasse. This study valorized cassava bagasse by developing active packaging films incorporated with nutmeg essential oil (NO) at varying concentrations (1–3% w/w). The integration of NO increased film thickness from 0.38 mm to 0.67 mm, and tensile strength (TS) from 0.66 MPa to 1.19 MPa, while reducing density (1.33–1.21 g cm<sup>−3</sup>), transparency (75.51–53.62%), and solubility. Films exhibited higher opacity (46.72–58.73%) and enhanced color intensity. SEM images revealed fewer oil droplets and a more microporous structure, indicating improved compatibility. FT-IR confirmed that NO did not alter the film's chemical composition, although XRD indicated enhanced crystallinity. Thermal stability improved as the maximum decomposition temperature increased from 299.28 °C to 301.48 °C. Migration analysis demonstrated enhanced phytochemical release in different solvents, following Fickian-type diffusion. HS-SPME analysis revealed <em>p</em>-cymene, terpinen-4-ol, γ-terpinene, sabinene, and safrole as the dominant volatiles, contributing to antioxidant and antimicrobial activity. Disk diffusion assays showed N03 exhibited the largest inhibition zones against <em>E. coli</em> (20.67 mm) and <em>S. aureus</em> (31.33 mm). Moreover, grapes packed with N03 (NO 3%) film maintained quality for 10 d at room temperature, with reduced weight loss, color variation, and microbial proliferation compared to controls. The findings confirm that NO incorporation significantly enhanced the physicochemical, structural, and bioactive performance of cassava bagasse films, demonstrating strong potential for sustainable food packaging applications.</div></div>","PeriodicalId":276,"journal":{"name":"Chemosphere","volume":"392 ","pages":"Article 144739"},"PeriodicalIF":8.1,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145460795","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 : 2025-11-05DOI: 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}
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