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1.
Chem Commun (Camb) ; 60(61): 7894-7897, 2024 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-38979952

RESUMO

nH-Perfluoroalkyl carboxylic acids (nH-PFCAs) are emerging pollutants. Their identification by ion mobility is frustrated by the nH-PFCAs having unexpectedly small collision cross sections (CCS). Theory and experiment agree that this is because nH-PFCA ions undergo internal hydrogen bridging, and this insight will help guide the creation of more accurate methods for pollutant identification.

2.
Anal Chem ; 96(31): 12667-12675, 2024 08 06.
Artigo em Inglês | MEDLINE | ID: mdl-39068664

RESUMO

In vivo NMR is evolving into an important tool to understand biological processes and environmental responses. Current approaches use flow systems to sustain the organisms with oxygenated water and food (e.g., algae) inside the NMR. However, such systems have the potential to leak and clog (potentially damaging costly hardware), require large volumes of media, and multiple expensive HPLC pumps. The proposed "oxygenation system", uses a simple "double slit" adapter and a single air/oxygen flow line into the NMR. The design is especially suited to larger diameter probes given that standard flow systems would require higher flow rates thus amplifying the potential and impact of leaks/clogs. Traditionally, in vivo NMR of small organisms (e.g., Daphnia) have required 2D NMR in combination with 13C enrichment to overcome susceptibility distortions and provide information rich metabolic profiles. Here Daphnia magna, Eisenia fetida and Artemia franciscana are used to demonstrate the potential of the oxygenation system. Survivability tests and 1H time-resolved monitoring were first performed on D. magna, while E. fetida contained enough biomass to permit 1H-13C HSQC, 13C-1H HETCOR and 31P NMR without isotopic enrichment. Finally, STOCSY of 1D 13C NMR was used to follow the growth of A. franciscana (without 13C enrichment) for 48 h after birth, which helps visualize trends across a series of 1D in vivo data. In summary, application of the oxygenation system toward larger diameter probes allows the collection of NMR data without enrichment, offering a promising solution to better understand processes in vivo.


Assuntos
Artemia , Daphnia , Espectroscopia de Ressonância Magnética , Oxigênio , Animais , Oxigênio/metabolismo , Oxigênio/química , Oxigênio/análise , Oligoquetos/metabolismo , Análise Custo-Benefício , Soluções
3.
Innovation (Camb) ; 5(4): 100612, 2024 Jul 01.
Artigo em Inglês | MEDLINE | ID: mdl-38756954

RESUMO

Environmental pollution is escalating due to rapid global development that often prioritizes human needs over planetary health. Despite global efforts to mitigate legacy pollutants, the continuous introduction of new substances remains a major threat to both people and the planet. In response, global initiatives are focusing on risk assessment and regulation of emerging contaminants, as demonstrated by the ongoing efforts to establish the UN's Intergovernmental Science-Policy Panel on Chemicals, Waste, and Pollution Prevention. This review identifies the sources and impacts of emerging contaminants on planetary health, emphasizing the importance of adopting a One Health approach. Strategies for monitoring and addressing these pollutants are discussed, underscoring the need for robust and socially equitable environmental policies at both regional and international levels. Urgent actions are needed to transition toward sustainable pollution management practices to safeguard our planet for future generations.

4.
Environ Toxicol Chem ; 43(6): 1339-1351, 2024 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-38661510

RESUMO

Pharmaceuticals are found in aquatic environments due to their widespread use and environmental persistence. To date, a range of impairments to aquatic organisms has been reported with exposure to pharmaceuticals; however, further comparisons of their impacts across different species on the molecular level are needed. In the present study, the crustacean Daphnia magna and the freshwater fish Japanese medaka, common model organisms in aquatic toxicity, were exposed for 48 h to the common analgesics acetaminophen (ACT), diclofenac (DCF), and ibuprofen (IBU) at sublethal concentrations. A targeted metabolomic-based approach, using liquid chromatography-tandem mass spectrometry to quantify polar metabolites from individual daphnids and fish was used. Multivariate analyses and metabolite changes identified differences in the metabolite profile for D. magna and medaka, with more metabolic perturbations for D. magna. Pathway analyses uncovered disruptions to pathways associated with protein synthesis and amino acid metabolism with D. magna exposure to all three analgesics. In contrast, medaka exposure resulted in disrupted pathways with DCF only and not ACT and IBU. Overall, the observed perturbations in the biochemistry of both organisms were different and consistent with assessments using other endpoints reporting that D. magna is more sensitive to pollutants than medaka in short-term studies. Our findings demonstrate that molecular-level responses to analgesic exposure can reflect observations of other endpoints, such as immobilization and mortality. Thus, environmental metabolomics can be a valuable tool for selecting sentinel species for the biomonitoring of freshwater ecosystems while also uncovering mechanistic information. Environ Toxicol Chem 2024;43:1339-1351. © 2024 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.


Assuntos
Acetaminofen , Daphnia , Diclofenaco , Ibuprofeno , Metabolômica , Oryzias , Poluentes Químicos da Água , Animais , Oryzias/metabolismo , Daphnia/efeitos dos fármacos , Daphnia/metabolismo , Acetaminofen/toxicidade , Ibuprofeno/toxicidade , Poluentes Químicos da Água/toxicidade , Diclofenaco/toxicidade , Daphnia magna
5.
Chemosphere ; 356: 141923, 2024 May.
Artigo em Inglês | MEDLINE | ID: mdl-38599328

RESUMO

Poly- and perfluoroalkyl substances (PFAS) are a group of compounds with uses in industry and many consumer products. Concerns about the potential health effects of these compounds resulted in regulation by the Stockholm Convention on the use of three of the most common PFAS, including perfluorooctanoic acid (PFOA). Thousands of PFAS remain in production that are unregulated and for which their toxicity is unknown. Our group recently identified a new class of PFAS, fluorotelomer ethoxylates (FTEOs), in indoor dust and industrial wastewater. In this study, we investigated the effect of PFAS on placental metabolism by exposing healthy, pregnant CD-1 mice to PFOA or FTEOs at one of three concentrations (0 ng/L (controls), 5 ng/L, 100 ng/L) (n = 7-8/group). While PFOA is banned and PFOA concentrations in human blood are decreasing, we hypothesize that FTEOs will cause adverse pregnancy outcomes similar to PFOA, the compounds they were meant to replace. Placental tissue samples were collected at embryonic day 17.5 and 1H solid-state magic angle spinning nuclear magnetic resonance spectroscopy was used to determine the relative concentration of placental metabolites (n = 18-20/group). At the highest concentration, the relative concentrations of glucose and threonine were increased and the relative concentration of creatine was decreased in the PFOA-exposed placentas compared to controls (p < 0.05). In contrast, the relative concentrations of asparagine and lysine were decreased and the relative concentration of creatine was increased in the FTEOs-exposed placentas compared to controls (p < 0.05). Partial least squares - discriminant analysis showed the FTEOs-exposed and control groups were significantly separated (p < 0.005) and pathway analysis found four biochemical pathways were perturbed following PFOA exposure, while one pathway was altered following FTEOs exposure. Maternal exposure to PFOA and FTEOs had a significant impact on the placental metabolome, with the effect depending on the pollutant. This work motivates further studies to determine exposure levels and evaluate associations with adverse outcomes in human pregnancies.


Assuntos
Caprilatos , Fluorocarbonos , Placenta , Fluorocarbonos/toxicidade , Feminino , Animais , Gravidez , Caprilatos/toxicidade , Camundongos , Placenta/metabolismo , Placenta/efeitos dos fármacos , Poluentes Ambientais/toxicidade
6.
J Am Soc Mass Spectrom ; 35(4): 775-783, 2024 Apr 03.
Artigo em Inglês | MEDLINE | ID: mdl-38498916

RESUMO

In cyclic ion mobility (cIMS), ions are permitted to travel multiple passes around the drift cell, increasing the distance traveled and the relative separation between ions. This study tests the hypothesis that multiple passes around the cell can also result in improved precision when measuring an ion's mobility and the collision cross section (TWCCS) derived therefrom. Experiments were performed with a diverse set of compounds, including 16 polycyclic aromatic hydrocarbons using gas chromatographic atmospheric pressure chemical ionization and a set of drug molecules by direct infusion electrospray ionization. The average periodic drift time, viz., the average time required for the ion to travel around the cIMS cell once, shifts dramatically, approaching part-per-million (ppm) precision as the number of passes increases to ∼100. Extrapolation of the precision of the CCS values with respect to the number of passes led to the prediction that the precision will reach 1000 ppm after 50 passes, 100 ppm after 100 passes, and <10 ppm after 150 passes. Experiments wherein the number of passes exceeded 100 produced TWCCS values having within-run precisions ranging between 15 and 117 ppm. The improved precision with an increasing number of passes may be a consequence of mitigating space-charge effects by allowing the ions to occupy a larger region of the cIMS cell. A method is proposed to enable practical measurements of TWCCS with ppm precision and is demonstrated to characterize an unknown drug mixture.

7.
Sci Rep ; 14(1): 399, 2024 01 03.
Artigo em Inglês | MEDLINE | ID: mdl-38172192

RESUMO

While microplastics have been recently detected in human blood and the placenta, their impact on human health is not well understood. Using a mouse model of environmental exposure during pregnancy, our group has previously reported that exposure to polystyrene micro- and nanoplastics throughout gestation results in fetal growth restriction. While polystyrene is environmentally relevant, polyethylene is the most widely produced plastic and amongst the most commonly detected microplastic in drinking water and human blood. In this study, we investigated the effect of maternal exposure to polyethylene micro- and nanoplastics on fetal growth and placental function. Healthy, pregnant CD-1 dams were divided into three groups: 106 ng/L of 740-4990 nm polyethylene with surfactant in drinking water (n = 12), surfactant alone in drinking water (n = 12) or regular filtered drinking water (n = 11). At embryonic day 17.5, high-frequency ultrasound was used to investigate the placental and fetal hemodynamic responses following exposure. While maternal exposure to polyethylene did not impact fetal growth, there was a significant effect on placental function with a 43% increase in umbilical artery blood flow in the polyethylene group compared to controls (p < 0.01). These results suggest polyethylene has the potential to cause adverse pregnancy outcomes through abnormal placental function.


Assuntos
Água Potável , Placenta , Humanos , Gravidez , Feminino , Placenta/irrigação sanguínea , Microplásticos , Plásticos , Exposição Materna/efeitos adversos , Polietileno/toxicidade , Poliestirenos , Desenvolvimento Fetal , Resultado da Gravidez , Hemodinâmica , Retardo do Crescimento Fetal , Tensoativos
8.
J Am Soc Mass Spectrom ; 35(2): 275-284, 2024 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-38239096

RESUMO

Humans are exposed to differing levels of micro/nanoplastics (MNPs) through inhalation, but few studies have attempted to measure <1 µm MNPs in air, in part due to a paucity of analytical methods. We developed an approach to identify and quantify MNPs in indoor air using a novel pyrolysis gas chromatographic cyclic ion mobility mass spectrometer (pyr-GCxcIMS). Four common plastic types were targeted for identification, namely, (polystyrene (PS), polyethylene (PE), polypropylene (PP), and polymethyl methacrylate (PMMA). The method was applied to size-resolved particulate (56 nm to 18 µm) collected from two different indoor environments using a Micro-Orifice Uniform Deposit Impactors (MOUDI) model 110 cascade impactor. Comprehensive two-dimensional separation by GCxcIMS also enabled the retrospective analysis of other polymers and plastic additives. The mean concentrations of MNP particles with diameters of <10 µm and <2.5 µm in the laboratory were estimated to be 47 ± 5 and 27 ± 4 µg/m3, respectively. In the private residence, the estimated concentrations were 24 ± 3 and 16 ± 2 µg/m3. PS was the most abundant MNP type in both locations. Nontargeted screening revealed the presence of plastic additives, such as TDCPP (tris(1,3-dichloro-2-propyl)phosphate) whose abundance correlated with that of polyurethane (PU). This is consistent with their use as flame retardants in PU-based upholstered furniture and building insulation. This study provides evidence of indoor exposure to MNPs and underlines the need for further study of this route of exposure to MNPs and the plastic additives carried with them.

9.
Biol Reprod ; 110(1): 211-218, 2024 Jan 13.
Artigo em Inglês | MEDLINE | ID: mdl-37724921

RESUMO

Maternal exposure to microplastics and nanoplastics has been shown to result in fetal growth restriction in mice. In this study, we investigated the placental and fetal hemodynamic responses to plastics exposure in mice using high-frequency ultrasound. Healthy, pregnant CD-1 dams were given either 106 ng/L of 5 µm polystyrene microplastics or 106 ng/L of 50 nm polystyrene nanoplastics in drinking water throughout gestation and were compared with controls. Maternal exposure to both microplastics and nanoplastics resulted in evidence of placental dysfunction that was highly dependent on the particle size. The umbilical artery blood flow increased by 48% in the microplastic-exposed group and decreased by 25% in the nanoplastic-exposed group compared to controls (p < 0.05). The microplastic- and nanoplastic-exposed fetuses showed a significant decrease in the middle cerebral artery pulsatility index of 10% and 13%, respectively, compared to controls (p < 0.05), indicating vasodilation of the cerebral circulation, a fetal adaptation that is part of the brain sparing response to preserve oxygen delivery. Hemodynamic markers of placental dysfunction and fetal hypoxia were more pronounced in the group exposed to polystyrene nanoplastics, suggesting nanoplastic exposure during human pregnancy has the potential to disrupt fetal brain development, which in turn may cause suboptimal neurodevelopmental outcomes.


Assuntos
Microplásticos , Plásticos , Gravidez , Feminino , Humanos , Animais , Camundongos , Poliestirenos/toxicidade , Placenta/irrigação sanguínea , Desenvolvimento Fetal
10.
Environ Res ; 241: 117547, 2024 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-37949288

RESUMO

Industrial wastewater effluents are a major source of chemicals in aquatic environments, and many of these chemicals may negatively impact aquatic life. In this study, the crustacean Daphnia magna, a common model organism in ecotoxicity studies, was exposed for 48 h to nine different industrial effluent samples from manufacturing facilities associated with the production of plastics, polymers, and coating products at a range of dilutions: 10, 25, 50, 100% (undiluted). A targeted metabolomic-based approach using liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used to quantify polar metabolites from individual daphnids that survived the 48 h exposure. Multivariate analyses and metabolite changes revealed metabolic perturbations across all effluent samples studied, with non-monotonic responses and both up and downregulation relative to the unexposed control. Pathway analyses indicated the disruption of similar and distinct pathways, mostly connected to protein synthesis, amino acid metabolism, and antioxidant processes. Overall, we observed disruptions in Daphnia biochemistry that were similar across the effluent samples, but with unique features for each effluent sample. Additionally, non-monotonic heightened responses suggested additive and/or synergistic interactions between the chemicals within the industrial effluents. These findings demonstrate that targeted metabolomic approaches are a powerful tool for the biomonitoring of aquatic ecosystems in the context of complex mixtures, such as industrial wastewater effluents.


Assuntos
Daphnia magna , Poluentes Químicos da Água , Animais , Águas Residuárias/toxicidade , Antioxidantes/metabolismo , Polímeros , Aminoácidos/metabolismo , Cromatografia Líquida , Ecossistema , Espectrometria de Massas em Tandem , Metabolômica , Daphnia , Poluentes Químicos da Água/análise
11.
Environ Int ; 183: 108388, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-38159370

RESUMO

Conceptual density functional theory (CDFT) descriptors were computed to predict the environmental fate of approximately 6,000 widely used industrial chemicals. CDFT descriptors aligned with a molecule's possible bioaccumulation mechanism, i.e., soft chemicals are lipophilic, whereas hard chemicals may bioaccumulate by other mechanisms such as protein binding. The results have provided us with a new "rule of thumb" to guide risk assessment of chemical hazards: suspected persistent organic pollutants are either too hard (η > 0.40 hartree) or too soft (α > 200 Å3). This offers a novel approach to environmental risk assessment using two fundamental properties of a molecule.


Assuntos
Poluentes Ambientais , Poluentes Ambientais/análise , Bioacumulação , Teoria da Densidade Funcional , Indústrias , Poluentes Orgânicos Persistentes
12.
Metabolomics ; 19(12): 96, 2023 Nov 21.
Artigo em Inglês | MEDLINE | ID: mdl-37989919

RESUMO

INTRODUCTION: Plastics used in everyday materials accumulate as waste in the environment and degrade over time. The impacts of the resulting particulate micro- and nanoplastics on human health remain largely unknown. In pregnant mice, we recently demonstrated that exposure to nanoplastics throughout gestation and during lactation resulted in changes in brain structure detected on MRI. One possible explanation for this abnormal postnatal brain development is altered fetal brain metabolism. OBJECTIVES: To determine the effect of maternal exposure to nanoplastics on fetal brain metabolism. METHODS: Healthy pregnant CD-1 mice were exposed to 50 nm polystyrene nanoplastics at a concentration of 106 ng/L through drinking water during gestation. Fetal brain samples were collected at embryonic day 17.5 (n = 18-21 per group per sex) and snap-frozen in liquid nitrogen. Magic angle spinning nuclear magnetic resonance was used to determine metabolite profiles and their relative concentrations in the fetal brain. RESULTS: The relative concentrations of gamma-aminobutyric acid (GABA), creatine and glucose were found to decrease by 40%, 21% and 30% respectively following maternal nanoplastic exposure when compared to the controls (p < 0.05). The change in relative concentration of asparagine with nanoplastic exposure was dependent on fetal sex (p < 0.005). CONCLUSION: Maternal exposure to polystyrene nanoplastics caused abnormal fetal brain metabolism in mice. The present study demonstrates the potential impacts of nanoplastic exposure during fetal development and motivates further studies to evaluate the risk to human pregnancies.


Assuntos
Microplásticos , Poliestirenos , Gravidez , Humanos , Feminino , Animais , Camundongos , Exposição Materna/efeitos adversos , Metabolômica , Encéfalo
13.
Molecules ; 28(12)2023 Jun 20.
Artigo em Inglês | MEDLINE | ID: mdl-37375418

RESUMO

Environmental metabolomics provides insight into how anthropogenic activities have an impact on the health of an organism at the molecular level. Within this field, in vivo NMR stands out as a powerful tool for monitoring real-time changes in an organism's metabolome. Typically, these studies use 2D 13C-1H experiments on 13C-enriched organisms. Daphnia are the most studied species, given their widespread use in toxicity testing. However, with COVID-19 and other geopolitical factors, the cost of isotope enrichment increased ~6-7 fold over the last two years, making 13C-enriched cultures difficult to maintain. Thus, it is essential to revisit proton-only in vivo NMR and ask, "Can any metabolic information be obtained from Daphnia using proton-only experiments?". Two samples are considered here: living and whole reswollen organisms. A range of filters are tested, including relaxation, lipid suppression, multiple-quantum, J-coupling suppression, 2D 1H-1H experiments, selective experiments, and those exploiting intermolecular single-quantum coherence. While most filters improve the ex vivo spectra, only the most complex filters succeed in vivo. If non-enriched organisms must be used, then, DREAMTIME is recommended for targeted monitoring, while IP-iSQC was the only experiment that allowed non-targeted metabolite identification in vivo. This paper is critically important as it documents not just the experiments that succeed in vivo but also those that fail and demonstrates first-hand the difficulties associated with proton-only in vivo NMR.


Assuntos
COVID-19 , Daphnia , Animais , Daphnia/metabolismo , Prótons , Espectroscopia de Ressonância Magnética , Imageamento por Ressonância Magnética , Metabolômica
14.
J Am Soc Mass Spectrom ; 34(4): 640-648, 2023 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-36942790

RESUMO

Ortho-substituted isomers of tricresyl phosphates (TCPs) and their toxic metabolites (e.g., CBDP: cresyl saligenin phosphate) can cause neurotoxic effects in humans. When TCP is introduced to an atmospheric pressure chemical ionization source using gas chromatography, radical cations M•+ are formed by charge exchange. The mass spectrum of an ortho-substituted isomer displays two intense peaks that are absent in the spectra of non-ortho-substituted isomers, leading us to propose structure-diagnostic ion-molecule reactions between ions M•+ and oxygen species present in the source. However, the mechanisms of these reactions have not yet been established. In this study, we propose a mechanism and provide support through computational and experimental analyses using density functional theory and cyclic ion mobility-mass spectrometry. The mechanism consists of a multistep reaction starting with the rearrangement of the molecular ion into a distonic isomer followed by an oxidation step and then decomposition into [CBDP-H]+. This proposal is consistent with the results obtained from a series of isotopically labeled analogues. Cyclic ion mobility experiments with a tri-o-cresyl phosphate standard reveal the presence of at least two hydrogen shift isomers of the product ion [CBDP-H]+ that are connected by a low-lying barrier. The selectivity of the ion-molecule reactions toward ortho-substituted cresyl TCP isomers provides us with an identification tool that can select potentially neurotoxic triaryl phosphate esters present in complex mixtures that are produced in large volume by industry.

15.
Aquat Toxicol ; 257: 106432, 2023 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-36841068

RESUMO

Phthalic acid esters (PAEs) are a class of chemicals that are usually incorporated as additives in the manufacturing of plastics. PAEs are not covalently bound to the material matrix and can, consequently, be leached into the environment. PAEs have been reported to act as endocrine disruptors, neurotoxins, metabolic stressors, and immunotoxins to aquatic organisms but there is a lack of information regarding the impact of sub-lethal concentrations to target organisms. The freshwater crustacean Daphnia magna, a commonly used model organism in aquatic toxicity, was exposed to four phthalate pollutants: dimethyl phthalate (DMP), diethyl phthalate (DEP), monomethyl phthalate (MMP), and monoethyl phthalate (MEP). Liquid chromatography-tandem mass spectrometry (LC-MS/MS) was employed in a targeted metabolomic approach to quantify polar metabolites extracted from a single Daphnia body. Individual metabolite percent changes and hierarchical clustering heatmap analysis showed unique metabolic profiles for each phthalate pollutant. Metabolite percent changes were mostly downregulated or presented opposing responses for the low and high concentrations tested. Meanwhile, pathway analyses suggest the disruption of related and unique pathways, mostly connected with amino acid and energy metabolism. The pathways aminoacyl-tRNA biosynthesis, arginine biosynthesis, and glutathione metabolism were disrupted by most selected PAEs. Overall, this study indicates that although phthalate pollutants can elicit distinct metabolic perturbations to each PAE, they still impacted related biochemical pathways. These chemical-class based responses could be associated with a common toxic mechanism of action. The reported findings show how targeted metabolomic approaches can lead to a better understanding of sub-lethal exposure to pollutants, revealing metabolomic endpoints do not hold a close relationship with traditional acute toxicity endpoints.


Assuntos
Poluentes Ambientais , Ácidos Ftálicos , Poluentes Químicos da Água , Animais , Daphnia/metabolismo , Aminoácidos/metabolismo , Cromatografia Líquida , Poluentes Químicos da Água/toxicidade , Espectrometria de Massas em Tandem , Ácidos Ftálicos/toxicidade , Metabolismo Energético , Ésteres , Dibutilftalato
16.
Environ Int ; 171: 107634, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36459821

RESUMO

Concerns regarding the persistence, bioaccumulation behaviour, and toxicity of perfluorooctanoic acid and perfluorooctane sulfonic acid have resulted in the creation of thousands of replacement perfluoroalkyl substances (PFAS). This study reports on the discovery of fluorotelomer ethoxylates (FTEO) in indoor dust (9/15 samples), and industrial effluents (14/37 samples) using gas chromatographic cyclic ion mobility mass spectrometry (GC-cIMS). By filtering the detected unknowns by mass and collision-cross section, a series of FTEO homologues were revealed with the formula F-(CF2)n(C2H4O)xH, where n = 6,8,10, and x = 4-12. The highest concentrations were observed in samples collected from healthcare facilities, consistent with the potential use of these compounds in anti-fog products, sprays used to prevent condensation on eyeglasses. FTEOs were also detected in c. 40 % of industrial effluent samples, with the highest concentrations in electroplating facilities, manufacturers of cosmetics and personal care products, and linen cleaning services for healthcare and work uniforms. These results suggest that FTEOs may well be widespread pollutants that are more persistent than previously thought, underlining the need for further study of their occurrence and potential impact to human health and the environment.


Assuntos
Poluentes Ambientais , Fluorocarbonos , Humanos , Águas Residuárias , Poeira/análise , Fluorocarbonos/análise , Poluentes Ambientais/análise , Cromatografia Gasosa-Espectrometria de Massas
17.
Environ Toxicol Chem ; 42(1): 242-256, 2023 01.
Artigo em Inglês | MEDLINE | ID: mdl-36345965

RESUMO

Per- and polyfluoroalkyl substances (PFAS) are a class of persistent organic pollutants used in industrial applications because of their physicochemical properties, which results in their ubiquitous presence across environmental matrices. To date, legacy PFAS have been well studied; however, the concentration of alternative PFAS may exceed the concentration of legacy pollutants, and more information is needed regarding the sublethal toxicity at the molecular level of aquatic model organisms, such as Daphnia magna. Perfluorobutanoic acid (PFBA), perfluorohexanoic acid (PFHxA), perfluorohexanesulfonic acid (PFHxS), and perfluorononanoic acid (PFNA) are four widely detected PFAS alternatives of varying chain length and polar functionality that are quantified in aquatic environments. The present study examines the metabolic perturbations of PFAS with varying chemistries to D. magna using targeted mass spectrometry-based metabolomics. Daphnia were acutely exposed to sublethal concentrations of PFBA, PFHxA, PFHxS, and PFNA before the polar metabolite profile was extracted from single organisms. Multivariate analysis demonstrated significant separation between the sublethal concentrations of PFHxA, PFHxS, and PFNA relative to the controls; in sum, longer chain lengths demonstrated greater overall perturbations to the extracted metabolic profiles. Univariate statistics revealed significant perturbations in the concentrations of several amino acids, nucleotides/nucleosides, and neurotransmitters with exposure to PFAS. These metabolic perturbations are consistent with disruptions in energy metabolism (pantothenate and coenzyme A metabolism, histidine metabolism) and protein synthesis (aminoacyl-transfer RNA biosynthesis and amino acid metabolism), which were identified through biochemical pathway analysis. These results provide evidence that although PFAS chemistry (chain length and polar functional group) invokes unique metabolic responses, there is also an underlying toxic mode of action that is common with select PFAS exposure. Overall, the present study highlights the capabilities of environmental metabolomics to elucidate the molecular-level perturbations of pollutants within the same chemical class to model aquatic organisms, which can be used to prioritize risk assessment of substituted PFAS alternatives. Environ Toxicol Chem 2023;42:242-256. © 2022 SETAC.


Assuntos
Ácidos Alcanossulfônicos , Poluentes Ambientais , Fluorocarbonos , Animais , Daphnia/metabolismo , Ácidos Sulfônicos/metabolismo , Poluentes Ambientais/metabolismo , Fluorocarbonos/análise , Ácidos Alcanossulfônicos/toxicidade
18.
Metabolomics ; 19(1): 1, 2022 12 20.
Artigo em Inglês | MEDLINE | ID: mdl-36538272

RESUMO

INTRODUCTION: The rapid growth in the worldwide use of plastics has resulted in a vast accumulation of microplastics in the air, soil and water. The impact of these microplastics on pregnancy and fetal development remains largely unknown. In pregnant mice, we recently demonstrated that exposure to micro- and nanoplastics throughout gestation resulted in significant fetal growth restriction. One possible explanation for reduced fetal growth is abnormal placental metabolism. OBJECTIVES: To evaluate the effect of maternal exposure to microplastics on placental metabolism. METHODS: In the present study, CD-1 pregnant mice were exposed to 5 µm polystyrene microplastics in filtered drinking water at one of four concentrations (0 ng/L (controls), 102 ng/L, 104 ng/L, 106 ng/L) throughout gestation (n = 7-11/group). At embryonic day 17.5, placental tissue samples were collected (n = 28-44/group). Metabolite profiles were determined using 1 H high-resolution magic angle spinning magnetic resonance spectroscopy. RESULTS: The relative concentration of lysine (p = 0.003) and glucose (p < 0.0001) in the placenta were found to decrease with increasing microplastic concentrations, with a significant reduction at the highest exposure concentration. Multivariate analysis identified shifts in the metabolic profile with MP exposure and pathway analysis identified perturbations in the biotin metabolism, lysine degradation, and glycolysis/gluconeogenesis pathways. CONCLUSION: Maternal exposure to microplastics resulted in significant alterations in placental metabolism. This study highlights the potential impact of microplastic exposure on pregnancy outcomes and that efforts should be made to minimize exposure to plastics, particularly during pregnancy.


Assuntos
Microplásticos , Placenta , Humanos , Gravidez , Feminino , Animais , Camundongos , Placenta/metabolismo , Microplásticos/metabolismo , Poliestirenos/metabolismo , Plásticos/metabolismo , Exposição Materna/efeitos adversos , Lisina/metabolismo , Metabolômica
19.
Anal Chem ; 94(31): 11096-11103, 2022 08 09.
Artigo em Inglês | MEDLINE | ID: mdl-35912800

RESUMO

Per- and polyfluoroalkyl substances (PFASs) have been widely used since the 1940s in industry and everyday household products. They also persist in the environment and bioaccumulate in humans and wildlife. Despite these concerns, the identities of most PFASs in environmental and biological samples are unknown. Herein, we describe a novel cyclic ion mobility mass spectrometer (cIMS), hyphenated with gas chromatography (GC) atmospheric pressure chemical ionization, that can reveal the presence of unknown PFASs on the basis of the ratio of their mass and collision cross section (CCS). Prediction of the CCS of ca. 20,000 chemicals used in industry and commerce indicates that most compounds characterized by CCS values that are less than the sum of 100 Å2 and one-fifth of their mass are either PFASs or polybrominated flame retardants. When this filter is applied to GC-cIMS data collected from a set of 20 indoor dust samples, PFAS compounds are revealed without prior knowledge of their occurrence. Validation of this approach was performed using SRM 2585, a standard reference material of household dust, by comparing the PFASs detected with those (tentatively) identified in previous studies. Chlorofluoro phthalimides tentatively identified previously were confirmed with a synthesized standard. The method also reveals the presence of chlorofluoro n-alkanes as an emerging class of "forever chemicals" that contaminate the indoor environment.


Assuntos
Fluorocarbonos , Cromatografia Líquida , Poeira/análise , Fluorocarbonos/análise , Cromatografia Gasosa-Espectrometria de Massas , Humanos , Espectrometria de Massas
20.
Anal Chem ; 94(32): 11113-11117, 2022 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-35913896

RESUMO

Gas chromatography multiplexed with cyclic ion mobility mass spectrometry is a comprehensive two-dimensional separation technique that can resolve compounds that would otherwise coelute in a single-dimension separation. The cyclic geometry of the ion mobility cell enables ions to travel multiple passes, increasing their drift times to the detector and relative separation. However, the quality of the separation may be obfuscated when "wrap-around" occurs, during which speedier ions catch up with slower ion populations when allowed to travel through more than one pass. Consequently, cyclic ion mobility is incorrectly perceived as a targeted approach that requires preselection of ions prior to separation. The present study demonstrates that "wrap-around" can be mitigated by comparing drift times measured during single- and multipass experiments and extrapolating the number of passes experienced by each ion. This straightforward calculation results in the "unwrapping" of cyclic ion mobility data so that the experiments can be interpreted in a nontargeted way while reaping the benefit of peak capacities that rival those achieved using other comprehensive two-dimensional separations.


Assuntos
Espectrometria de Mobilidade Iônica , Cromatografia Líquida , Cromatografia Gasosa-Espectrometria de Massas , Íons/química , Espectrometria de Massas/métodos
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