Chemical safety assessment requires the inclusion of information on potential transformation products.Such information is often lacking for chemicals considered as alternatives making a comprehensive safety assessment...Chemical safety assessment requires the inclusion of information on potential transformation products.Such information is often lacking for chemicals considered as alternatives making a comprehensive safety assessment for chemical substitution challenging.To address this challenge a methodological framework for investigating the environmental transformation of alternative chemicals is presented.The developed methodology involves the combined use of in silico tools,biodegradation testing and suspect screening analysis for the prediction and identification of environmental transformation pathways and products.The proposed framework was applied on three emerging alternative plasticizers to phthalate esters(i.e.,DINCH,DEHA and ATBC)under which major first-,second-and third-step transformation products predicted in silico were also successfully identified experimentally.This allowed for a preliminary evaluation of the performance of in silico tools in terms of the predicted transformation pathways and their likelihood of occurrence.At the same time the fast chemical degradation method showed good potential in identifying the key transformation products.The proposed framework can be used to support safety assessments for chemical substitution.Further application of the developed methodology on different chemical groups along with proper optimization of the individual method components is recommended to showcase its efficacy over a larger application area.展开更多
Over the past century,anthropic activities in industrialized countries have generated exposure to a vast array of environmental chemical families.Many of these may have harmful effects on human health,and xenobiotic e...Over the past century,anthropic activities in industrialized countries have generated exposure to a vast array of environmental chemical families.Many of these may have harmful effects on human health,and xenobiotic exposure during the fetal period is particularly concerning.Large-scale,open-ended characterization of the chemical exposome is increasingly investigated using non-targeted screening(NTS)and suspect screening(SS)approaches.The aim of this study was to increase knowledge of fetal exposure to xenobiotics by using NTS and SS to identify the presence of chemicals of emerging concern(CECs)in human placenta samples.After comparing the performances of salt-assisted liquid-liquid extraction plus dispersive liquid-liquid microextraction(SALLE-DLLME)and enhanced matrix removal(EMR)as sample preparation techniques,EMR was applied in 65 placenta samples from the BAZA Spanish cohort.Twenty-one compounds from various chemical classes were identified,including ag-rochemicals,preservatives,plasticizers,cosmetics,fabric dyes,fragrances,additives,industrial in-termediates,and drugs,and some of these have not previously been reported in placenta samples.The findings confirm the crucial value of non-targeted methodologies for the comprehensive assessment of human exposure during the prenatal period and their potential to unveil previously unknown or overlooked exposures.展开更多
The presence of Contaminants of Emerging Concern(CECs)in the environment poses significant concern,yet their occurrence,sources,and fate remain not fully understood.This study provides the first investigation of a bro...The presence of Contaminants of Emerging Concern(CECs)in the environment poses significant concern,yet their occurrence,sources,and fate remain not fully understood.This study provides the first investigation of a broad range of CECs,including active pharmaceutical ingredients(APIs),plant protection products(PPPs),and personal care products(PCPs),across raw and treated wastewater,surface water,and sediment in the Venice Lagoon and selected tributaries.Using a suspect screening analysis methodology based on high-resolution mass spectrometry(HRMs),14 sampling stations were selected to identify contamination patterns and potential emission sources.APIs were the most frequently detected class of compounds(150 compounds),with flecainide,harman,carbamazepine,and venlafaxine found in more than 80%of sampling stations.Analgesics were the dominant therapeutic class,followed by antidepressants and cardiovascular drugs.Among PCPs(17 compounds),icaridin,and climbazole were the most prevalent,detected at 11 and 9 sampling stations,respectively.PPPs(26 compounds)were also detected,with diuron being the most widespread as it was found at 10 sampling stations.To the best of the authors'knowledge,92 compounds(68 APIs,17 PCPs,and 7 PPPs)were qualitatively identified for the first time in the Venice Lagoon,although many of them are known to occur in natural waters worldwide.The results highlight rivers and treated wastewater as major contributors to CEC emissions in the lagoon.These findings offer valuable insights for future research and targeted monitoring strategies,advancing the understanding of unmonitored contaminants in vulnerable aquatic environments.展开更多
Environmental pollution from synthetic chemical mixtures has significant adverse impacts on marine ecosystems.However,identifying the main constituents of chemical mixtures that pose ecological threats is challenging ...Environmental pollution from synthetic chemical mixtures has significant adverse impacts on marine ecosystems.However,identifying the main constituents of chemical mixtures that pose ecological threats is challenging due to the necessity of an integrated workflow for comprehensive identification and toxicological prioritization of pollutants.Here,an all-in-one mass spectrometric strategy integrating target,suspect,and nontarget analysis was used to investigate organic pollutants of concern in fishing port sediments,with 355 pollutants(32 from target analysis,118 from suspect screening and 205 from nontarget analysis)identified in 11 categories.The chemical classes of polycyclic aromatic hydrocarbons(PAHs),pesticides,and intermediates were the extensively detected chemical classes.The ecological risks of absolutely quantified pollutants(i.e.,16 parent PAHs,7 organophosphate esters(OPEs),10 pesticides and 4 benzotriazole ultraviolet absorbers)were assessed using toxicity-weighted concentration ranking,with o,p’-DDT being the major contributor.Under the toxicological priority index(ToxPi)framework,an extended ranking of all identified pollutants was achieved by combining instrument response and detection frequency,with a priority control list of 15 pollutants obtained,of which benzo[ghi]perylene(BghiP)and p,p’-DDE had the highest risk priority.Due to frequent detection rates and significant environmental risks,routine monitoring of petroleum pollutants is considered essential.This study presents a general workflow that includes comprehensive identification and prioritization of pollutants,facilitating chemical management and ecological risk assessment.展开更多
The discovery of the hazardous effects associated with the polymer additives 1,3-diphenyl guanidine(DPG)and 1,3-di-o-tolylguanidine(DTG)has prompted the need for biomonitoring studies to detect human exposure.However,...The discovery of the hazardous effects associated with the polymer additives 1,3-diphenyl guanidine(DPG)and 1,3-di-o-tolylguanidine(DTG)has prompted the need for biomonitoring studies to detect human exposure.However,limited information is available about their metabolism.To address this gap,this study investigates the Phase I and II in-vitro biotransformation of both chemicals using human liver microsomes and cytosol.The samples were analyzed using liquid chromatography coupled to high resolution-(tandem)mass spectrometry through suspect(of in-silico predicted metabolites)and nontarget screening.The analysis revealed four Phase I and two Phase II metabolic products for both DPG and DTG.Hydroxylation of the benzene ring led to the tentative identification of mono-and dihydroxylated metabolites.Subsequent Phase I deamination followed by oxidation resulted in the formation of hydroxy-phenylurea and an intramolecular cyclization resulted in the formation of hydroxycyclic products.Furthermore,N-glucuronidation and O-glucuronidation products were identified for the first time.After performing urinalysis,DPG and DTG could be quantified in the 0.020.23μg L^(−1) range,and DPG-227(mono-hydroxylated DPG)was estimated to be present at ca.0.010.10μg L^(−1) range,using DPG response as quantification surrogate.Finally,toxicity assessment using an in-silico tool indicated the need to consider these human metabolites in(eco)toxicological assessments,as they may have the same or even greater effects on humans and the environment.展开更多
Atmospheric particulate matter(PM)is considered a health hazard;however,the inadequate identification of the components of PM limits our understanding of its specific toxic pollutants.Herein,by combining three extract...Atmospheric particulate matter(PM)is considered a health hazard;however,the inadequate identification of the components of PM limits our understanding of its specific toxic pollutants.Herein,by combining three extraction solvents with different polarities(dichloromethane,hexane,and acetonitrile)and three ionization modes(electron ionization and the positive and negative modes of electrospray ionization),we comprehensively analyzed the organic chemicals in the PM_(2.5)and PM_(10)samples collected during summer and winter in Beijing.Suspect screening was facilitated by comparison with the mzCloud and the National Institute of Standards and Technology databases for tentatively characterizing chemical identities.Results showed that more compounds were identified in the winter PM_(2.5)/PM_(10)samples than in the summer samples and that PM_(2.5)contained a greater number of chemicals than PM_(10).Based on peak areas of compounds,the predominant pollutants in the winter PM_(2.5)/PM_(10)samples were phenols,amines,and aromatic compounds;however,significantly high responses of one phenol and two ester compounds were detected in the summer PM_(2.5)/PM_(10)samples.Based on the Tox21 toxicological database,a total of 60 identified pollutants were associated with 28 biological targets,and∼50%of the active compounds were phenolic and aromatic compounds.The biological targets most affected by these pollutants were related to metabolic homeostasis,reproduction,and developmental functions.This study underscores the importance of a multiapproach analysis in comprehensively identifying environmental pollutants and highlights the potential health risks posed by PM.展开更多
基金supported by the‘Safe and Efficient Chemistry by Design(SafeChem)’project funded by the Swedish Foundation for Strategic Environmental Research,MISTRA(grant no.DIA 2018/11).
文摘Chemical safety assessment requires the inclusion of information on potential transformation products.Such information is often lacking for chemicals considered as alternatives making a comprehensive safety assessment for chemical substitution challenging.To address this challenge a methodological framework for investigating the environmental transformation of alternative chemicals is presented.The developed methodology involves the combined use of in silico tools,biodegradation testing and suspect screening analysis for the prediction and identification of environmental transformation pathways and products.The proposed framework was applied on three emerging alternative plasticizers to phthalate esters(i.e.,DINCH,DEHA and ATBC)under which major first-,second-and third-step transformation products predicted in silico were also successfully identified experimentally.This allowed for a preliminary evaluation of the performance of in silico tools in terms of the predicted transformation pathways and their likelihood of occurrence.At the same time the fast chemical degradation method showed good potential in identifying the key transformation products.The proposed framework can be used to support safety assessments for chemical substitution.Further application of the developed methodology on different chemical groups along with proper optimization of the individual method components is recommended to showcase its efficacy over a larger application area.
基金F.Vela-Soria received a Miguel Servet postdoctoral research contract(CP21/00128)from Instituto de Salud CarlosⅢ(Spain)and“Fondo Europeo de Desarrollo Regional”(ISCⅢ/FEDER).V.Mustieles was supported by a Sara Borrell postdoctoral research contract(CD22/00176)granted by Instituto de Salud CarlosⅢ(Spain)and NextGenerationEU funds.
文摘Over the past century,anthropic activities in industrialized countries have generated exposure to a vast array of environmental chemical families.Many of these may have harmful effects on human health,and xenobiotic exposure during the fetal period is particularly concerning.Large-scale,open-ended characterization of the chemical exposome is increasingly investigated using non-targeted screening(NTS)and suspect screening(SS)approaches.The aim of this study was to increase knowledge of fetal exposure to xenobiotics by using NTS and SS to identify the presence of chemicals of emerging concern(CECs)in human placenta samples.After comparing the performances of salt-assisted liquid-liquid extraction plus dispersive liquid-liquid microextraction(SALLE-DLLME)and enhanced matrix removal(EMR)as sample preparation techniques,EMR was applied in 65 placenta samples from the BAZA Spanish cohort.Twenty-one compounds from various chemical classes were identified,including ag-rochemicals,preservatives,plasticizers,cosmetics,fabric dyes,fragrances,additives,industrial in-termediates,and drugs,and some of these have not previously been reported in placenta samples.The findings confirm the crucial value of non-targeted methodologies for the comprehensive assessment of human exposure during the prenatal period and their potential to unveil previously unknown or overlooked exposures.
文摘The presence of Contaminants of Emerging Concern(CECs)in the environment poses significant concern,yet their occurrence,sources,and fate remain not fully understood.This study provides the first investigation of a broad range of CECs,including active pharmaceutical ingredients(APIs),plant protection products(PPPs),and personal care products(PCPs),across raw and treated wastewater,surface water,and sediment in the Venice Lagoon and selected tributaries.Using a suspect screening analysis methodology based on high-resolution mass spectrometry(HRMs),14 sampling stations were selected to identify contamination patterns and potential emission sources.APIs were the most frequently detected class of compounds(150 compounds),with flecainide,harman,carbamazepine,and venlafaxine found in more than 80%of sampling stations.Analgesics were the dominant therapeutic class,followed by antidepressants and cardiovascular drugs.Among PCPs(17 compounds),icaridin,and climbazole were the most prevalent,detected at 11 and 9 sampling stations,respectively.PPPs(26 compounds)were also detected,with diuron being the most widespread as it was found at 10 sampling stations.To the best of the authors'knowledge,92 compounds(68 APIs,17 PCPs,and 7 PPPs)were qualitatively identified for the first time in the Venice Lagoon,although many of them are known to occur in natural waters worldwide.The results highlight rivers and treated wastewater as major contributors to CEC emissions in the lagoon.These findings offer valuable insights for future research and targeted monitoring strategies,advancing the understanding of unmonitored contaminants in vulnerable aquatic environments.
基金supported by the National Key Research and Development Program(2022YFC3105500)the National Natural Science Foundation of China(42206159)the Dalian Young Star of Science and Technology Project(2022RQ052).
文摘Environmental pollution from synthetic chemical mixtures has significant adverse impacts on marine ecosystems.However,identifying the main constituents of chemical mixtures that pose ecological threats is challenging due to the necessity of an integrated workflow for comprehensive identification and toxicological prioritization of pollutants.Here,an all-in-one mass spectrometric strategy integrating target,suspect,and nontarget analysis was used to investigate organic pollutants of concern in fishing port sediments,with 355 pollutants(32 from target analysis,118 from suspect screening and 205 from nontarget analysis)identified in 11 categories.The chemical classes of polycyclic aromatic hydrocarbons(PAHs),pesticides,and intermediates were the extensively detected chemical classes.The ecological risks of absolutely quantified pollutants(i.e.,16 parent PAHs,7 organophosphate esters(OPEs),10 pesticides and 4 benzotriazole ultraviolet absorbers)were assessed using toxicity-weighted concentration ranking,with o,p’-DDT being the major contributor.Under the toxicological priority index(ToxPi)framework,an extended ranking of all identified pollutants was achieved by combining instrument response and detection frequency,with a priority control list of 15 pollutants obtained,of which benzo[ghi]perylene(BghiP)and p,p’-DDE had the highest risk priority.Due to frequent detection rates and significant environmental risks,routine monitoring of petroleum pollutants is considered essential.This study presents a general workflow that includes comprehensive identification and prioritization of pollutants,facilitating chemical management and ecological risk assessment.
基金funded by the Spanish Agencia Estatal de Investigacion MCIN/AEI/10.13039/501100011033(PID2020-117686RB-C32,CNS2024-154426 and TED2021-129200B-C41(co)funded by the EU through NextGeneration EU/PRTR funds)Conselleria de Cultura de Galicia,Educacion e Universidades(ED481A-2020/258,ED431C-2025/21and ED481B-2025/042).
文摘The discovery of the hazardous effects associated with the polymer additives 1,3-diphenyl guanidine(DPG)and 1,3-di-o-tolylguanidine(DTG)has prompted the need for biomonitoring studies to detect human exposure.However,limited information is available about their metabolism.To address this gap,this study investigates the Phase I and II in-vitro biotransformation of both chemicals using human liver microsomes and cytosol.The samples were analyzed using liquid chromatography coupled to high resolution-(tandem)mass spectrometry through suspect(of in-silico predicted metabolites)and nontarget screening.The analysis revealed four Phase I and two Phase II metabolic products for both DPG and DTG.Hydroxylation of the benzene ring led to the tentative identification of mono-and dihydroxylated metabolites.Subsequent Phase I deamination followed by oxidation resulted in the formation of hydroxy-phenylurea and an intramolecular cyclization resulted in the formation of hydroxycyclic products.Furthermore,N-glucuronidation and O-glucuronidation products were identified for the first time.After performing urinalysis,DPG and DTG could be quantified in the 0.020.23μg L^(−1) range,and DPG-227(mono-hydroxylated DPG)was estimated to be present at ca.0.010.10μg L^(−1) range,using DPG response as quantification surrogate.Finally,toxicity assessment using an in-silico tool indicated the need to consider these human metabolites in(eco)toxicological assessments,as they may have the same or even greater effects on humans and the environment.
基金the National Key Research and Development Program of China(Grant No.2023YFA0915100)the National Natural Science Foundation of China(Grant No.22325606,22193050,42377386,21906166,21527901)+1 种基金the Scientific Instrument Developing Project of the Chinese Academy of Sciences(Grant No.GSZXKYZB2024012)Strategy Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0750100,XDB0750300).
文摘Atmospheric particulate matter(PM)is considered a health hazard;however,the inadequate identification of the components of PM limits our understanding of its specific toxic pollutants.Herein,by combining three extraction solvents with different polarities(dichloromethane,hexane,and acetonitrile)and three ionization modes(electron ionization and the positive and negative modes of electrospray ionization),we comprehensively analyzed the organic chemicals in the PM_(2.5)and PM_(10)samples collected during summer and winter in Beijing.Suspect screening was facilitated by comparison with the mzCloud and the National Institute of Standards and Technology databases for tentatively characterizing chemical identities.Results showed that more compounds were identified in the winter PM_(2.5)/PM_(10)samples than in the summer samples and that PM_(2.5)contained a greater number of chemicals than PM_(10).Based on peak areas of compounds,the predominant pollutants in the winter PM_(2.5)/PM_(10)samples were phenols,amines,and aromatic compounds;however,significantly high responses of one phenol and two ester compounds were detected in the summer PM_(2.5)/PM_(10)samples.Based on the Tox21 toxicological database,a total of 60 identified pollutants were associated with 28 biological targets,and∼50%of the active compounds were phenolic and aromatic compounds.The biological targets most affected by these pollutants were related to metabolic homeostasis,reproduction,and developmental functions.This study underscores the importance of a multiapproach analysis in comprehensively identifying environmental pollutants and highlights the potential health risks posed by PM.
