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It is established that organophosphorus pesticide (OPP) toxicity results from modification of amino acids in active sites of target proteins. OPPs can also modify unrelated target proteins such as histones and such covalent histone modifications can alter DNA-binding properties and lead to aberrant gene expression. In the present study, we report on non-enzymatic covalent modifications of calf thymus histones adducted to selected OPPs and organophosphate flame retardants (OPFRs) in vitro using a bottom-up proteomics method approach. Histones were not found to form detectable adducts with the two tested OPFRs but were avidly modified by a few of the seven OPPs that were tested in vitro. Dimethyl phosphate (or diethyl phosphate) adducts were identified on Tyr, Lys and Ser residues. Most of the dialkyl phosphate adducts were identified on Tyr residues. Methyl and ethyl modified histones were also detected. Eleven amino residues in histones showed non-enzymatic covalent methylation by exposure of dichlorvos and malathion. Our bottom-up proteomics approach showing histone-OPP adduct formation warrants future studies on the underlying mechanism of chronic illness from exposure to OPPs.
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Histonas , Compostos Organofosforados , Praguicidas , Histonas/metabolismo , Histonas/química , Compostos Organofosforados/química , Compostos Organofosforados/metabolismo , Compostos Organofosforados/toxicidade , Animais , Praguicidas/química , Praguicidas/metabolismo , Praguicidas/toxicidade , Bovinos , Metilação , Malation/química , Malation/metabolismo , Malation/toxicidade , Proteômica , Retardadores de Chama/toxicidade , Retardadores de Chama/metabolismo , Sequência de Aminoácidos , Diclorvós/química , Diclorvós/toxicidadeRESUMO
Compared to aquatic ecosystem, terrestrial systems have been subjected to fewer investigations on the exposure to halogenated flame retardants (HFRs). Our study utilized peregrine falcon eggs collected from multiple habitats across North America to retrospectively explore both spatial distribution and temporal changes in legacy (e.g., polybrominated diphenyl ethers) and alternative HFRs over a 30 year period (1984-2016). The results reveal intensive HFR exposure in terrestrial ecosystems and chemical-specific spatiotemporal distribution patterns. The correlations between egg levels of the selected HFRs and human population density clearly illustrated a significant urban influence on the exposure of this wildlife species to these HFRs and subsequent maternal transfer to their eggs. Temporal analyses suggest that, unlike aquatic systems, terrestrial ecosystems may undergo continual exposure to consistently high levels of legacy HFRs for a long period of time. Our findings collectively highlight the effectiveness of using peregrine eggs to monitor terrestrial exposure to HFRs and other bioaccumulative chemicals and the need for continuous monitoring of HFRs in terrestrial ecosystems.
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The Yangtze River fishery resources have declined strongly over the past few decades. One suspected reason for the decline in fishery productivity, including silver carp (Hypophthalmichthys molitrix), has been linked to organophosphate esters (OPEs) contaminant exposure. In this study, the adverse effect of OPEs on lipid metabolism in silver carp captured from the Yangtze River was examined, and our results indicated that muscle concentrations of the OPEs were positively associated with serum cholesterol and total lipid levels. In vivo laboratory results revealed that exposure to environmental concentrations of OPEs significantly increased the concentrations of triglyceride, cholesterol, and total lipid levels. Lipidome analysis further confirmed the lipid metabolism dysfunction induced by OPEs, and glycerophospholipids and sphingolipids were the most affected lipids. Hepatic transcriptomic analysis found that OPEs caused significant alterations in the transcription of genes involved in lipid metabolism. Pathways associated with lipid homeostasis, including the peroxisome proliferator-activated receptor (PPAR) signal pathway, cholesterol metabolism, fatty acid biosynthesis, and steroid biosynthesis, were significantly changed. Furthermore, the affinities of OPEs were different, but the 11 OPEs tested could bind with PPARγ, suggesting that OPEs could disrupt lipid metabolism by interacting with PPARγ. Overall, this study highlighted the harmful effects of OPEs on wild fish and provided mechanistic insights into OPE-induced metabolic disorders.
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Carpas , Retardadores de Chama , Doenças Metabólicas , Animais , Rios , PPAR gama , Ésteres/análise , Organofosfatos/toxicidade , Organofosfatos/análise , Colesterol/análise , Lipídeos , Retardadores de Chama/análise , China , Monitoramento Ambiental/métodosRESUMO
A comprehensive analytical approach for targeted and non-targeted discovery screening of per- and polyfluoroalkyl substances (PFAS) was developed and applied to model complex environmental biotic samples. Samples were extracted by formic acid-acetonitrile solution and cleaned up and fractionated by SPE (WAX). Target PFAS quantification was performed by ultra-high performance liquid chromatography interfaced with a triple quadrupole mass spectrometer (UPLC-QqQ-MS/MS). Non-targeted analysis (NTA) PFAS screening was performed with UPLC coupled with a quadrupole-Exactive orbitrap high resolution mass spectrometer (UPLC-Q-Exactive-HRMS). An iterative exclusion (IE) approach was applied to data acquisition for NTA suspect screening to increase the potential for unknown PFAS discovery with MS/MS. A complex workflow in Compound Discoverer was set up to automate data processing of the PFAS suspects search. New mass lists and MS/MS databases, which included a large number of PFAS, were set up and introduced into the search for high-throughput structure identification using HRMS techniques. The integrated targeted-NTA method successfully analyzed for legacy and alternative PFAS in model environmental biota samples, namely polar bear liver and bird egg samples. Targeted analysis provided unequivocal identification of well known/established PFAS (mainly perfluoroalkyl acids) with quantification at very low levels. The NTA suspect screening was able to determine a broader range of PFAS. The data analysis method offered high-confidence annotations for PFAS despite lacking available authentic standards. Overall, the analytical coverage of PFAS was greater and elucidated other PFAS present in these model apex predators.
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Fluorocarbonos , Espectrometria de Massas em Tandem , Espectrometria de Massas em Tandem/métodos , Cromatografia Líquida de Alta Pressão/métodos , Espectrometria de Massa com Cromatografia Líquida , Padrões de Referência , Fluorocarbonos/análiseRESUMO
The movement of per- and polyfluoroalkyl substances (PFAS) through linked aquatic-terrestrial food webs is not well understood. Tree swallows (Tachycineta bicolor) in such systems may be exposed to PFAS from multiple abiotic and/or biotic compartments. We show from fatty acid signatures and carbon stable isotopes that tree swallow nestlings in southwestern Ontario fed on both terrestrial and aquatic macroinvertebrates. The PFAS profiles of air, terrestrial invertebrates, and swallows were dominated by perfluorooctanesulfonic acid (PFOS). Short-chain perfluoroalkyl acids (PFAAs) were largely restricted to air, surface water, and sediment, and long-chain PFAAs were mainly found in aquatic invertebrates and tree swallows. PFOS, multiple long-chain perfluorocarboxylic acids [perfluorononanoic acid (PFNA), perfluorodecanoic acid (PFDA), perfluorotridecanoic acid (PFTrDA)] and perfluorooctane sulfonamide precursors were estimated to bioaccumulate from air to tree swallows. PFOS bioaccumulated from air to terrestrial invertebrates, and PFOS, PFDA, and perfluorooctane sulfonamidoacetic acids (FOSAAs) bioaccumulated from water to aquatic invertebrates. PFOS showed biomagnification from both terrestrial and aquatic invertebrates to tree swallows, and PFDA and FOSAAs were also biomagnified from aquatic invertebrates to tree swallows. The movement of PFAS through aquatic-terrestrial food webs appears congener- and compartment-specific, challenging the understanding of PFAS exposure routes for multiple species involved in these food webs.
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Ácidos Alcanossulfônicos , Fluorocarbonos , Animais , Cadeia Alimentar , Fluorocarbonos/análise , Invertebrados , Água , AvesRESUMO
Lipophilic persistent organic pollutants (POPs) tend to biomagnify in food chains, resulting in higher concentrations in species such as killer whales (Orcinus orca) feeding on marine mammals compared to those consuming fish. Advancements in dietary studies include the use of quantitative fatty acid signature analysis (QFASA) and differentiation of feeding habits within and between populations of North Atlantic (NA) killer whales. This comprehensive study assessed the concentrations of legacy and emerging POPs in 162 killer whales from across the NA. We report significantly higher mean levels of polychlorinated biphenyls (PCBs), organochlorine pesticides, and flame retardants in Western NA killer whales compared to those of Eastern NA conspecifics. Mean ∑PCBs ranged from â¼100 mg/kg lipid weight (lw) in the Western NA (Canadian Arctic, Eastern Canada) to â¼50 mg/kg lw in the mid-NA (Greenland, Iceland) to â¼10 mg/kg lw in the Eastern NA (Norway, Faroe Islands). The observed variations in contaminant levels were strongly correlated with diet composition across locations (inferred from QFASA), emphasizing that diet and not environmental variation in contaminant concentrations among locations is crucial in assessing contaminant-associated health risks in killer whales. These findings highlight the urgency for implementing enhanced measures to safely dispose of POP-contaminated waste, prevent further environmental contamination, and mitigate the release of newer and potentially harmful contaminants.
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Caniformia , Bifenilos Policlorados , Orca , Animais , Monitoramento Ambiental , Canadá , Bifenilos Policlorados/análise , DietaRESUMO
We investigated the trophic magnification potential of perfluoroalkyl substances (PFAS) in a terrestrial food web by using a chemical activity-based approach, which involved normalizing concentrations of PFAS in biota to their relative biochemical composition in order to provide a thermodynamically accurate basis for comparing concentrations of PFAS in biota. Samples of hawk eggs, songbird tissues, and invertebrates were collected and analyzed for concentrations of 18 perfluoroalkyl acids (PFAAs) and for polar lipid, neutral lipid, total protein, albumin, and water content. Estimated mass fractions of PFCA C8-C11 and PFSA C4-C8 predominantly occurred in albumin within biota samples from the food web with smaller estimated fractions in polar lipids > structural proteins > neutral lipids and insignificant amounts in water. Estimated mass fractions of longer-chained PFAS (i.e., C12-C16) mainly occurred in polar lipids with smaller estimated fractions in albumin > structural proteins > neutral lipids > and water. Chemical activity-based TMFs indicated that PFNA, PFDA, PFUdA, PFDoA, PFTrDA, PFTeDA, PFOS, and PFDS biomagnified in the food web; PFOA, PFHxDA, and PFHxS did not appear to biomagnify; and PFBS biodiluted. Chemical activity-based TMFs for PFCA C8-C11 and PFSA C4-C8 were in good agreement with corresponding TMFs derived with concentrations normalized to only total protein in biota, suggesting that concentrations normalized to total protein may be appropriate proxies of chemical activity-based TMFs for PFAS, which predominantly partition to albumin. Similarly, TMFs derived with concentrations normalized to albumin may be suitable proxies of chemical activity-based TMFs for longer-chained PFAS, which predominantly partition to polar lipids.
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Fluorocarbonos , Cadeia Alimentar , Animais , Aves , Albuminas , Água , LipídeosRESUMO
The list of organophosphate esters (OPEs) reported in the environment continues to expand as evidenced by the increasing number of OPE studies in the literature. However, there remains a general dearth of information on more recently produced and used OPEs that are proving to be emerging environmental contaminants. The present review summarizes the available studies in a systematic framework of the current state of knowledge on the analysis, environmental fate, and behavior of emerging OPEs. This review also details future directions to better understand emerging OPEs in the environment. Firstly, we make recommendations that the current structural/practical abbreviations and naming of OPEs be revised and updated. A chemical database (CDB) containing 114 OPEs is presently established based on the suspect list from the current scientific literature. There are 12 established OPEs and a total of 83 emerging OPEs that have been reported in human and/or biota samples. Of the emerging OPEs more than 80% have nearly 100% detection frequencies in samples of certain environmental media including indoor air, wastewater treatment plants, sediment, and fish. In contrast to OPEs considered established contaminants, most emerging OPEs have been identified more recently due to the more pervasive use of high-resolution mass spectrometry (HRMS) based approaches and especially gas or liquid chromatography coupled with HRMS-based non-target analysis (NTA) of environmental sample fractions. Intentional/unintentional industrial use and non-industrial formation are sources of emerging OPEs in the environment. Predicted physical-chemical properties in silico of newer, molecularly larger and more oligomeric OPEs strongly suggest that some compounds such as bisphenol A diphenyl phosphate (BPA-DPP) are highly persistent, bioaccumulative and/or toxic. Limited information on laboratory-based toxicity data has shown that some emerging OPEs elicit harmful effects such as cytotoxicity, development toxicity, hepatotoxicity, and endocrine disruption in exposed humans and mammals. Established, and to a much lesser degree emerging OPEs, have also been shown to transform and degrade in biota and possibly alter their toxicological effects. Research on emerging OPE contaminants is presently limited and more study is warranted on sample analysis methods, source apportionment, transformation processes, environmental behavior, biomarkers of exposure and toxicity.
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Ésteres , Retardadores de Chama , Animais , Humanos , Ésteres/toxicidade , Ésteres/análise , Retardadores de Chama/toxicidade , Retardadores de Chama/análise , Organofosfatos/análise , Monitoramento Ambiental/métodos , Fosfatos/análise , China , MamíferosRESUMO
Per- and polyfluoroalkyl substances (PFAS) are a diverse group of surface treatment chemicals falling under non-polymeric and polymeric categories. Polymeric PFAS are comprised of fluoropolymers, perfluoropolyethers and side-chain fluorinated polymers (SCFPs). Fluorinated polymers and polymeric substances have gained a significant market due to their chemical stability. To date, research and regulatory concern has primarily focused on the environmental occurrence and health effects of non-polymeric PFAS, particularly perfluoroalkyl acids and precursors. Industries consider most fluoropolymers as being "polymers of low concern", although there is already a considerable environmental burden and widespread contamination resulting from their production, manufacturing and use. For example, SCFPs are widely used, and known to release their perfluorinated side chains. Concerted action is needed to address the dearth of environment-associated information and understanding on polymeric PFAS.
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Legacy persistent organic pollutants (POPs) such as polychlorinated biphenyls (PCBs) are chemicals that undergo long-range transport to the Arctic. These chemicals possess endocrine disruptive properties raising concerns for development and reproduction. Here, we report the relationship between concentrations of testosterone (T) and persistent organic pollutant (POPs) in 40 East Greenland male polar bears (Ursus maritimus) sampled during January to September 1999-2001. The mean ± standard concentrations of blood T were 0.31 ± 0.49 (mean ± SD) ng/mL in juveniles/subadults (n = 22) and 3.58 ± 7.45 ng/mL in adults (n = 18). The ∑POP concentrations (mean ± SD) in adipose tissue were 8139 ± 2990 ng/g lipid weight (lw) in juveniles/subadults and 11,037 ± 3950 ng/g lw in adult males, respectively, of which Σpolychlorinated biphenyls (ΣPCBs) were found in highest concentrations. The variation in T concentrations explained by sampling date (season), biometrics and adipose tissue POP concentrations was explored using redundancy analysis (RDA). The results showed that age, body length, and adipose lipid content in adult males contributed (p = 0.02) to the variation in POP concentrations. However, although some significant relationships between individual organochlorine contaminants and T concentrations in both juveniles/subadults and adult polar bears were identified, no significant relationships (p = 0.32) between T and POP concentrations were identified by the RDAs. Our results suggest that confounders such as biometrics and reproductive status may mask the endocrine disruptive effects that POPs have on blood T levels in male polar bears, demonstrating why it can be difficult to detect effects on wildlife populations.
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Histones are the major proteinaceous components of chromatin in eukaryotic cells and an important part of the epigenome. The broad-spectrum herbicide atrazine (2-chloro-4-[ethylamino]-6-[isopropylamino]-1, 3, 5-triazine) and its metabolites are known to form protein adducts, but the formation of atrazine-histone adducts has not been studied. In this study, a bottom-up proteomics analysis method was optimized and applied to identify histone adduction by atrazine in vitro. Whole histones of calf thymus or human histone H3.3 were incubated with atrazine. After solvent-based protein precipitation, the protein was digested by trypsin/Glu-C and the resulting peptides were analyzed by high-resolution mass spectrometry using an ultra-high-performance liquid chromatograph interfaced with a quadrupole Exactive-Orbitrap mass spectrometer. The resulting tryptic/Glu-C peptide of DTNLCAIHAK from calf thymus histone H3.1 or human histone H3.3 was identified with an accurate mass shift of +179.117 Da in atrazine incubated samples. It is deduced that a chemical group with an elemental composition of C8H13N5 (179.1171 Da) from atrazine adducted with calf thymus histone H3.1 or human histone H3.3. It was confirmed by MS/MS analysis that the adduction position was at its cysteine 110 residue. Time- and concentration-dependent assays also confirmed the non-enzymatic covalent modification of histone H3.3 by atrazine in vitro. Thus, the potential exists that atrazine adduction may lead to the alteration of histones that subsequently disturbs their normal function.
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Atrazina , Herbicidas , Humanos , Histonas/química , Herbicidas/análise , Espectrometria de Massas em Tandem/métodos , Proteômica/métodosRESUMO
Perfluoroalkyl acids (PFAAs) include perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), perfluorohexane sulfonic acid (PFHxS), and perfluorodecane sulfonic acid (PFDS), as well as increasingly used alternative short-chain perfluorosulfonic acids (PFSAs) and short- and long-chain (≥C9) perfluorocarboxylic acids (PFCAs). In the present study, tissues of tree swallows (Tachycineta bicolor) from two sites in southern Ontario, Canada, were analyzed for 17 individual PFAAs and showed egg and nestling tissue (liver, carcass) profiles dominated by PFOS (57-66%). The remaining PFAAs contributed ≤7% each, although collectively the long-chain PFCAs comprised 21-29% of the PFAAs. The short-chain PFSAs and PFCAs were among the lowest concentrations, suggesting that despite increased production and use of these alternative PFAAs, they are not accumulated to the same extent as the long-chain PFSAs and PFCAs. PFOS, PFDS, and some long-chain PFCAs were significantly higher in eggs than in livers and carcasses, whereas PFOA and the two short-chain PFCAs were significantly higher in nestling tissues than in eggs. For the two short-chain PFSAs, concentrations were similar among tissues. Tree swallow tissues at the site near a wastewater treatment plant (WWTP) outfall showed higher concentrations of PFOS, PFDS, PFHxS, and some long-chain PFCAs than tree swallows sampled at the nearby reference site; however, the influence of the WWTP was more equivocal for PFOA, other long-chain PFCAs, and short-chain PFSAs and PFCAs. Carbon stable isotopes (δ13C) and fatty acid signatures indicated that the diets of the WWTP swallows were more terrestrial than the reference swallows. Nonetheless, models considering environmental and ecological variables indicated that site was often the primary driver of PFAA variation among the swallows, with less or no influence of dietary patterns, or sex or body condition, revealing that of WWTP effluent can be an important environmental source of the major PFAAs in tree swallows.
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Ácidos Alcanossulfônicos , Fluorocarbonos , Andorinhas , Animais , Monitoramento Ambiental , Fluorocarbonos/análise , Ácidos Alcanossulfônicos/análise , OntárioRESUMO
Recently, we found that Ustiloxin A (UA, a mycotoxin) was widely detected in paddy environment and rice samples from several countries, and was also detected in human urine samples from China. However, the current knowledge about the health risks of UA are limited. In this research, the cytotoxicity of UA in mice renal tubular epithelial cells (mRTECs) was evaluated, and the results indicated that UA arrested cell cycle in G2/M phase via altering cellular morphology and microtubule, and inhibited the proliferation and division of mRTECs. Furthermore, UA could inhibit mitochondrial respiration via binding to the CoQ-binding site in dihydro-orotate dehydrogenase (DHODH) protein, and resulted in mitochondrial damage. These adverse effects of UA on mitochondria might be responsible for the cytotoxicity observed in vitro. In vivo, UA at concentrations that were comparable to the realistic concentrations of human exposure induced renal insufficiency in mice, and this might be associated with the renal mitochondrial damage in mice. However, exposure to UA at those realistic concentrations did not promote the progression from renal insufficiency to renal fibrosis and chronic kidney disease was not observed in mice.
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Rim , Insuficiência Renal Crônica , Camundongos , Humanos , Animais , Rim/metabolismo , Células Epiteliais/metabolismo , Respiração , Mitocôndrias/metabolismo , Proliferação de CélulasRESUMO
Increased production and usage of organophosphate esters (OPEs) as flame retardants and plasticizers has trended towards larger and 'novel' (oligomeric) OPEs, although there is a dearth of understanding of the environmental fate, stability, toxicokinetics, biotransformation and bioaccumulation of novel OPEs in exposed biota. The present study characterized in vitro biotransformation of the novel OPE bisphenol-A bis(diphenyl phosphate) (BPADP) using Wistar-Han rat and herring gull liver based microsomal assays. Hypothesized target metabolites bisphenol-A (BPA) and diphenyl phosphate (DPHP) and other metabolites were investigated by applying a lines of evidence approach. In silico modelling predicted both BPA and DPHP as rat metabolites of BPADP, these metabolites were quantified via UHPLC-QQQ-MS/MS. Additional non-target metabolites were determined by UHPLC-Q-Exactive-Orbitrap-HRMS/MS and identified by Compound Discoverer software. Mean BPADP depletion of 44 ± 10% was quantified with 3.9% and 2.6% conversion to BPA and DPHP, respectively, in the rat assay. BPADP metabolism was much slower when compared to the well-studied OPE, triphenyl phosphate (TPHP). BPADP depletion in gull liver assays was far slower relative to the rat. Additional non-target metabolites identified included two Phase I, O-dealkylation products, five Phase I oxidation products and one Phase II glutathione adduct, demonstrating agreement between lines of in vitro and in silico evidence. Lines of evidence suggest that BPADP is biologically persistent in exposed mammals or birds. These findings add to the understanding of BPADP stability and biotransformation, and perhaps of other novel OPEs, which are factors highly applicable to hazard assessments of exposure, persistence and bioaccumulation in biota.
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Retardadores de Chama , Fosfatos , Ratos , Animais , Fosfatos/metabolismo , Espectrometria de Massas em Tandem , Ratos Wistar , Organofosfatos/análise , Retardadores de Chama/análise , Biotransformação , Aves/metabolismo , Fígado/metabolismo , Ésteres/análise , Mamíferos/metabolismoRESUMO
Time series of contaminants in the Arctic are an important instrument to detect emerging issues and to monitor the effectiveness of chemicals regulation, based on the assumption of a direct reflection of changes in primary emissions. Climate change has the potential to influence these time trends, through direct physical and chemical processes and/or changes in ecosystems. This study was part of an assessment of the Arctic Monitoring and Assessment Programme (AMAP), analysing potential links between changes in climate-related physical and biological variables and time trends of persistent organic pollutants (POPs) in Arctic biota, with some additional information from the Antarctic. Several correlative relationships were identified between POP temporal trends in freshwater and marine biota and physical climate parameters such as oscillation indices, sea-ice coverage, temperature and precipitation, although the mechanisms behind these observations remain poorly understood. Biological data indicate changes in the diet and trophic level of some species, especially seabirds and polar bears, with consequences for their POP exposure. Studies from the Antarctic highlight increased POP availability after iceberg calving. Including physical and/or biological parameters in the POP time trend analysis has led to small deviations in some declining trends, but did generally not change the overall direction of the trend. In addition, regional and temporary perturbations occurred. Effects on POP time trends appear to have been more pronounced in recent years and to show time lags, suggesting that climate-related effects on the long time series might be gaining importance.
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Poluentes Ambientais , Poluentes Orgânicos Persistentes , Monitoramento Ambiental , Mudança Climática , Fatores de Tempo , Ecossistema , Regiões Antárticas , Regiões Árticas , Poluentes Ambientais/análise , BiotaRESUMO
A number of brominated flame retardants (BFRs) have been reported to interfere with the thyroid signaling pathway and cause oxidative stress in birds, yet the underlying shifts in gene expression associated with these effects remain poorly understood. In this study, we measured hepatic transcriptional responses of 31 genes in American kestrel (Falco sparverius) hatchlings following in ovo exposure to one of three high-volume alternative BFRs: 1,2-bis(2,4,6-tribromophenoxy) ethane (BTPBE), bis(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH), or 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB). Hatchling kestrels exhibited shifts in the expression of genes related to oxidative stress (CYP, GSTA, SOD, and GPX1), thyroid hormone metabolism and transport (DIO1, DIO2, and TTR), lipid and protein metabolism (PPAR, HMGCR, FAB1, and LPL), and cytokine-mediated inflammation (TLR3, IL18, IRF7, STAT3, RACK1, and CEBPB). Male and female hatchlings differed in which genes were differentially expressed, as well as the direction of the effect (up- vs. downregulation). These results build upon our previous findings of increased oxidative stress and disrupted thyroid signaling pathway in the same hatchlings. Furthermore, our results indicate that inflammatory responses appear to occur in female hatchlings exposed to BTBPE and EHTBB in ovo. Gene expression analysis revealed multiple affected pathways, adding to the growing evidence that sublethal physiological effects are complex and are a concern for birds exposed to BTBPE, EHTBB, or TBPH in ovo.
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Through ingestion and subsequent egestion, Arctic seabirds can bioaccumulate microplastics at and around their colony breeding sites. While microplastics in Arctic seabirds have been well documented, it is not yet understood to what extent these particles can act as transport vehicles for plastic-associated contaminants, including legacy persistent organic pollutants (POPs), trace metals, and organic additives. We investigated the occurrence and pattern of organic and inorganic co-contaminants of microplastics in two seabird species from the Canadian Arctic - northern fulmar (Fulmarus glacialis) and black-legged kittiwake (Rissa tridactyla). We found that fulmars had higher levels of plastic contamination and emerging organic compounds (known to be plastic additives) than kittiwakes, whereas higher concentrations of legacy POPs were found in kittiwakes than the fulmars. Furthermore, fulmars, the species with the much larger foraging range (â¼200 km), had higher plastic pollution and overall contaminant burdens, indicating that birds may be acting as long-range transport vectors for plastic-associated pollution. Our results suggest a potential connection between plastic additive contamination and plastic pollution burdens in the bird stomachs, highlighting the importance of treating plastic particles and plastic-associated organic additives as co-contaminants rather than separate pollution issues.
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The contamination of pesticides has been recognized as a major stressor in fresh water ecosystems in terms of the losses of services and population declines and extinctions. However, information on the adverse effects of pesticides on zooplankton communities under natural field conditions are still lacking, although zooplankton is quite sensitive to most of pesticides in laboratory studies. In this study, a natural lake ecosystem (Liangzi Lake) was used to determine the relationship between pesticide contamination and abundance decline of metazoan zooplankton. In August 2020, the comprehensive trophic level indexes and the abundance of phytoplankton in the 14 sampling sites of Liangzi Lake were comparable, but the abundance of metazoan zooplankton showed significant variations across two orders of magnitude. These results suggested that other factors, such as pesticide contamination, might be responsible for the variations of metazoan zooplankton community. Furthermore, the responsible pesticides were screened, and totally 29 pesticides were obtained. Finally, five pesticides were identified to provide more than 99.4% toxic contributions and chlorpyrifos and cypermethrin were two main causal agents. These results were further supported by laboratory exposure experiments using D. magna and field study in November 2020, where the concentrations of the 29 pesticides were strongly decreased and the abundance of metazoan zooplankton was comparable across the 14 sites of Liangzi Lake. Taken together, this work provided an evidence that the contamination of pesticides might be responsible for the abundance decline of metazoan zooplankton in a natural freshwater ecosystem.
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Clorpirifos , Praguicidas , Animais , Ecossistema , Lagos , Praguicidas/toxicidade , Fitoplâncton , ZooplânctonRESUMO
Since the last Arctic Monitoring and Assessment Programme (AMAP) effort to review biological effects of mercury (Hg) on Arctic biota in 2011 and 2018, there has been a considerable number of new Arctic bird studies. This review article provides contemporary Hg exposure and potential health risk for 36 Arctic seabird and shorebird species, representing a larger portion of the Arctic than during previous AMAP assessments now also including parts of the Russian Arctic. To assess risk to birds, we used Hg toxicity benchmarks established for blood and converted to egg, liver, and feather tissues. Several Arctic seabird populations showed Hg concentrations that exceeded toxicity benchmarks, with 50 % of individual birds exceeding the "no adverse health effect" level. In particular, 5 % of all studied birds were considered to be at moderate or higher risk to Hg toxicity. However, most seabirds (95 %) were generally at lower risk to Hg toxicity. The highest Hg contamination was observed in seabirds breeding in the western Atlantic and Pacific Oceans. Most Arctic shorebirds exhibited low Hg concentrations, with approximately 45 % of individuals categorized at no risk, 2.5 % at high risk category, and no individual at severe risk. Although the majority Arctic-breeding seabirds and shorebirds appeared at lower risk to Hg toxicity, recent studies have reported deleterious effects of Hg on some pituitary hormones, genotoxicity, and reproductive performance. Adult survival appeared unaffected by Hg exposure, although long-term banding studies incorporating Hg are still limited. Although Hg contamination across the Arctic is considered low for most bird species, Hg in combination with other stressors, including other contaminants, diseases, parasites, and climate change, may still cause adverse effects. Future investigations on the global impact of Hg on Arctic birds should be conducted within a multi-stressor framework. This information helps to address Article 22 (Effectiveness Evaluation) of the Minamata Convention on Mercury as a global pollutant.