Long-Term Influence of PCB- and PBDE-Spiked Microplastic Spheres Fed through Rotifers to Atlantic Cod (Gadus morhua) Larvae.

Omnipresent microplastics (MPs) in marine ecosystems are ingested at all trophic levels and may be a vector for the transfer of persistent organic pollutants (POPs) through the food web. We fed rotifers polyethylene MPs (1-4 µm) spiked with seven congeners of polychlorinated biphenyls (PCBs) and two congeners of polybrominated diphenyl ethers (PBDEs). In turn, these rotifers were fed to cod larvae from 2-30 days post-hatching (dph), while the control groups were fed rotifers without MPs. After 30 dph, all the groups were fed the same feed without MPs. Whole-body larvae were sampled at 30 and 60 dph, and four months later the skin of 10 g juveniles was sampled. The PCBs and PBDEs concentrations were significantly higher in MP larvae compared to the control larvae at 30 dph, but the significance dissipated at 60 dph. Expression of stress-related genes in cod larvae at 30 and 60 dph showed inconclusive minor random effects. The skin of MP juveniles showed disrupted epithelial integrity, fewer club cells and downregulation of a suite of genes involved in immunity, metabolism and the development of skin. Our study showed that POPs were transferred through the food web and accumulated in the larvae, but that the level of pollutants decreased once the exposure was ceased, possibly related to growth dilution. Considering the transcriptomic and histological findings, POPs spiked to MPs and/or MPs themselves may have long-term effects in the skin barrier defense system, immune response and epithelium integrity, which may potentially reduce the robustness and overall fitness of the fish.

Mercury contamination of two e-waste recycling sites in Ghana: an investigation into mercury pollution at Dagomba Line (Kumasi) and Agbogbloshie (Accra).

This study investigated mercury pollution at two e-waste recycling sites in Ghana-Dagomba Line in Kumasi and Agbogbloshie in Accra. A total of 129 soil samples taken at 100 m and 50 m resolutions, respectively, for Dagomba Line and Agbogbloshie, were analysed for mercury using a Zeeman atomic absorption spectrometry. Mercury concentrations from the recycling sites (ranging from 0.11 to 7.57 mg/kg Dagomba Line, and 0.01-4.36 mg/kg at Agbogbloshie) were significantly higher than that of the surrounding areas (0.01-0.17 mg/kg in Kumasi and 0.01-2.18 mg/kg in Accra) and unpolluted control sites (0.05 mg/kg in Kumasi and 0.02 mg/kg in Accra). The dismantling sites at both locations had the highest mercury concentrations. Furthermore, the concentrations were significantly higher at the Dagomba Line site in Kumasi than at Agbogbloshie, even though the Dagomba Line site is relatively recent. The mercury concentrations at both sites exceeded the pollution prevention and abatement level of 0.1 mg/kg. However, the estimated human health risk showed no potential human health effects. Moreover, the mercury concentrations in water and sediment (0.12-7.69 ng/L and 0.02-0.28 ng/L for Dagomba Line and Agbogbloshie, respectively) were below the US EPA standards. Findings from this study show that e-waste recycling can contaminate the topsoil with mercury, irrespective of the scale of the activity.

European interlaboratory comparison investigations (ICI) and external quality assurance schemes (EQUAS) for the analysis of bisphenol A, S and F in human urine: Results from the HBM4EU project.

The Human Biomonitoring for Europe initiative (HBM4EU) aims to study the exposure of citizens to chemicals and potentially associated health effects. One objective of this project has been to build a network of laboratories able to answer to the requirements of European human biomonitoring studies. Within the HBM4EU quality assurance and quality control scheme (QA/QC), a number of interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs) were organized to ensure data consistency, comparability and reliability. Bisphenols are among the prioritized substance groups in HBM4EU, including bisphenol A (BPA), bisphenol S (BPS) and bisphenol F (BPF) in human urine. In four rounds of ICI/EQUAS, two target concentration levels were considered, related to around P25 and P95 of the typical exposure distribution observed in the European general population. Special attention was paid to the conjugated phase II metabolites known to be most dominant in samples of environmentally exposed individuals, through the analysis of both native samples and samples fortified with glucuronide forms. For the low level, the average percentage of satisfactory results across the four rounds was 83% for BPA, 71% for BPS and 62% for BPF. For the high level, the percentages of satisfactory results increased to 93% for BPA, 89% for BPS and 86% for BPF. 24 out of 32 participating laboratories (75%) were approved for the analyses of BPA in the HBM4EU project according to the defined criterion of Z-scores for both low and high concentration levels in at least two ICI/EQUAS rounds. For BPS and BPF, the number of qualified laboratories was 18 out of 27 (67%) and 13 out of 28 (46%), respectively. These results demonstrate a strong analytical capability for BPA and BPS in Europe, while improvements may be needed for BPF.

Interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs) for flame retardant analysis in biological matrices: Results from the HBM4EU project.

The European Human Biomonitoring Initiative (HBM4EU) is coordinating and advancing human biomonitoring (HBM). For this purpose, a network of laboratories delivering reliable analytical data on human exposure is fundamental. The analytical comparability and accuracy of laboratories analysing flame retardants (FRs) in serum and urine were investigated by a quality assurance/quality control (QA/QC) scheme comprising interlaboratory comparison investigations (ICIs) and external quality assurance schemes (EQUASs). This paper presents the evaluation process and discusses the results of four ICI/EQUAS rounds performed from 2018 to 2020 for the determination of ten halogenated flame retardants (HFRs) represented by three congeners of polybrominated diphenyl ethers (BDE-47, BDE-153 and BDE-209), two isomers of hexabromocyclododecane (α-HBCD and γ-HBCD), two dechloranes (anti-DP and syn-DP), tetrabromobisphenol A (TBBPA), decabromodiphenylethane (DBDPE), and 2,4,6-tribromophenol (2,4,6-TBP) in serum, and four metabolites of organophosphorus flame retardants (OPFRs) in urine, at two concentration levels. The number of satisfactory results reported by laboratories increased during the four rounds. In the case of HFRs, the scope of the participating laboratories varied substantially (from two to ten) and in most cases did not cover the entire target spectrum of chemicals. The highest participation rate was reached for BDE-47 and BDE-153. The majority of participants achieved more than 70% satisfactory results for these two compounds over all rounds. For other HFRs, the percentage of successful laboratories varied from 44 to 100%. The evaluation of TBBPA, DBDPE, and 2,4,6-TBP was not possible because the number of participating laboratories was too small. Only seven laboratories participated in the ICI/EQUAS scheme for OPFR metabolites and five of them were successful for at least two biomarkers. Nevertheless, the evaluation of laboratory performance using Z-scores in the first three rounds required an alternative approach compared to HFRs because of the small number of participants and the high variability of experts' results. The obtained results within the ICI/EQUAS programme showed a significant core network of comparable European laboratories for HBM of BDE-47, BDE-153, BDE-209, α-HBCD, γ-HBCD, anti-DP, and syn-DP. On the other hand, the data revealed a critically low analytical capacity in Europe for HBM of TBBPA, DBDPE, and 2,4,6-TBP as well as for the OPFR biomarkers.

Accumulation of Short-, Medium-, and Long-Chain Chlorinated Paraffins in Marine and Terrestrial Animals from Scandinavia.

Short-, medium-, and long-chain chlorinated paraffins (SCCPs, MCCPs, and LCCPs) have a wide range of physical-chemical properties, indicating their varying bioaccumulation tendencies in marine and terrestrial ecosystems. However, there are few empirical data to reveal such bioaccumulation tendencies. In this study, we analyzed SCCPs, MCCPs, and LCCPs in samples from 18 species at both low and high trophic levels of marine and terrestrial ecosystems from the Scandinavian region collected during the past decade. These included fish, seabirds, marine mammals, and terrestrial birds and mammals. SCCPs, MCCPs, and LCCPs were present in all the species, with concentrations ranging from 26-1500, 30-1600, 6.0-1200 ng/g lipid, respectively. Although MCCPs and SCCPs predominated in most species, many terrestrial species had generally higher concentrations of LCCPs than marine species. Terrestrial raptors in particular accumulated higher concentrations of LCCPs, including C24/25-which are predominant among very-long-chain components. LCCP concentrations were highest and predominated (55% of total CPs) in peregrine falcons in this study, which is the first report where concentrations of LCCPs surpass those of SCCPs and MCCPs in wildlife. The results also indicate biomagnification of SCCPs, MCCPs, and LCCPs in both marine and terrestrial food chains, but in-depth studies of specific food webs are needed.

Human exposure to PFOS and mercury through meat from baltic harbour seals (Phoca vitulina).

The overall aim of the present study was to assess human exposure to environmental contaminants from consumption of harbour seal (Phoca vitulina) meat in the southwestern Baltic Sea. For this purpose, muscle tissue from harbour seals (n = 27) was sampled from Danish locations in the period 2005-2015 and analysed for concentrations of total mercury (Hg), organochlorine contaminants such as polychlorinated biphenyls (PCBs) and organochlorine pesticides as well as perfluoroalkyl substances (PFAS) with particular focus on perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA). Hg, ∑PCB, PFOS and PFOA concentrations in the muscle tissue ranged between 0.27 and 4.76 µg g-1 wet weight (ww; mean: 1.38 µg g-1 ww, n = 27), 12.2-137 ng g-1 ww (mean: 47.5 ng g-1 ww, n = 10), 6.95-33.6 ng g-1 ww (mean: 15.8 ng g-1 ww, n = 10) and 0.16-0.55 ng g-1 ww (mean: 0.28 ng g-1 ww, n = 10), respectively. We compared the concentrations with literature-derived human tolerable weekly intake (TWI) values for mercury (1.3 µg kg-1 week-1), ∑PCB (2.1 µg kg-1 week-1), PFOS (0.013 µg kg-1 week-1) and PFOA (0.006 µg kg-1 week-1). The comparisons showed that the weekly consumption of harbour seal meat by children (weighing 30 kg), women (weighing 60 kg) and men (weighing 80 kg) should not exceed 28, 57 and 76 g (for Hg), 1.3, 2.7 and 3.5 kg (for ∑PCB), 25, 50 and 67 g (for PFOS) and 640, 1290 and 1720 g (for PFOA). In conclusion, Hg and PFOS are the contaminants of most importance in seal meat from this area with respect to existing tolerable intake rates and risks of adverse human health effects.

Regulated and Unregulated Halogenated Flame Retardants in Peregrine Falcon Eggs from Greenland.

Median levels of regulated flame retardants, i.e., polybrominated diphenyl ethers (PBDEs), brominated biphenyl (BB)-153, and hexabromocyclododecane (HBCD), in 33-48 eggs of peregrine falcons (Falco peregrinus) from Greenland were 1909, 359, and 5.98 ng/g lipid weight (lw), respectively, and generally intermediate to levels in North America and Europe. Unregulated flame retardants had lower median concentrations of 1.06 (2-ethylhexyl-2,3,4,5-tetrabromobenzoate, EH-TBB), 2.42 (1,2-bis(2,4,6-tribromophenoxy)-ethane, BTBPE), 0.52 (2,4,6-tribromophenyl 2,3-dibromopropyl ether, DPTE), and 4.78 (dechlorane plus) ng/g lw. Although these compounds are often described as recent replacements for PBDEs, they were also present in eggs from the 1980s. BDE-209 was the only compound with a significant increase (+7.2% annual change) between 1986 and 2014, while BB-153 and DPTE decreased significantly (-8.0% and -2.8% annual change, respectively). Dechlorane plus showed a nonsignificant increase. Individual birds, equipped with light-logging geolocators, confirmed the contaminant exposure over a large geographical area as the birds spent nearly equal time periods in their breeding and wintering grounds in Greenland and Central/South America, respectively, interrupted by 5-6 weeks of migration through North America.

Endosulfan, Short-Chain Chlorinated Paraffins (SCCPs) and Octachlorostyrene in Wildlife from Greenland: Levels, Trends and Methodological Challenges.

Besides globally banned "legacy" persistent organic pollutants, other compounds might be present in Arctic wildlife, for which regulation was introduced recently (the insecticide endosulfan), is considered (short-chain chlorinated paraffins, SCCPs) or does not exist (octachlorostyrene, OCS, a byproduct of manufacturing and combustion processes involving chlorine). The purpose of this study was to analyze the time trend of endosulfan (1986-2012) in ringed seals and to address the levels of SCCPs and OCS in wildlife species from Greenland (black guillemot, glaucous gull, ringed seal, polar bear), while taking a critical standpoint to analytical methods typically applied. The metabolite endosulfan sulfate was the only endosulfan compound consistently above detection limits, with a median concentration of 0.23 ng/g lipid weight (lw) and a significant annual decrease of -5.6%. The low-resolution mass spectrometry (LRMS) method appeared accurate and sufficiently precise; however, the gel permeation chromatography had to balance lipid removal and analyte loss. SCCPs and OCS were present in all samples. OCS median concentrations were between 2.8 (ringed seal blubber) and 29 (glaucous gull liver) ng/g lw, determined by a straightforward dual column electron capture detection method. SCCPs were analyzed by LRMS, following removal of potential interferences, and had median concentrations of several 100 ng/g wet weight. While the method showed good precision and recovery rates as well as acceptable accuracy in control samples, the Greenland samples had high concentrations in an Arctic context, possibly indicating limited selectivity of the LRMS method.

Passive Sampling in Regulatory Chemical Monitoring of Nonpolar Organic Compounds in the Aquatic Environment.

We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths and shortcomings of passive sampling are assessed for water, sediments, and biota. Passive water sampling is a suitable technique for measuring concentrations of freely dissolved compounds. This method yields results that are incompatible with the EU's quality standard definition in terms of total concentrations in water, but this definition has little scientific basis. Insufficient quality control is a present weakness of passive sampling in water. Laboratory performance studies and the development of standardized methods are needed to improve data quality and to encourage the use of passive sampling by commercial laboratories and monitoring agencies. Successful prediction of bioaccumulation based on passive sampling is well documented for organisms at the lower trophic levels, but requires more research for higher levels. Despite the existence of several knowledge gaps, passive sampling presently is the best available technology for chemical monitoring of nonpolar organic compounds. Key issues to be addressed by scientists and environmental managers are outlined.

Modeling Population-Level Consequences of Polychlorinated Biphenyl Exposure in East Greenland Polar Bears.

Polychlorinated biphenyls (PCBs) can cause endocrine disruption, cancer, immunosuppression, or reproductive failure in animals. We used an individual-based model to explore whether and how PCB-associated reproductive failure could affect the dynamics of a hypothetical polar bear (Ursus maritimus) population exposed to PCBs to the same degree as the East Greenland subpopulation. Dose-response data from experimental studies on a surrogate species, the mink (Mustela vision), were used in the absence of similar data for polar bears. Two alternative types of reproductive failure in relation to maternal sum-PCB concentrations were considered: increased abortion rate and increased cub mortality. We found that the quantitative impact of PCB-induced reproductive failure on population growth rate depended largely on the actual type of reproductive failure involved. Critical potencies of the dose-response relationship for decreasing the population growth rate were established for both modeled types of reproductive failure. Comparing the model predictions of the age-dependent trend of sum-PCBs concentrations in females with actual field measurements from East Greenland indicated that it was unlikely that PCB exposure caused a high incidence of abortions in the subpopulation. However, on the basis of this analysis, it could not be excluded that PCB exposure contributes to higher cub mortality. Our results highlight the necessity for further research on the possible influence of PCBs on polar bear reproduction regarding their physiological pathway. This includes determining the exact cause of reproductive failure, i.e., in utero exposure versus lactational exposure of offspring; the timing of offspring death; and establishing the most relevant reference metrics for the dose-response relationship.

Polybrominated diphenyl ethers and perfluoroalkyl substances in serum of pregnant women: levels, correlations, and potential health implications.

Polybrominated diphenyl ethers (PBDEs), a group of flame retardants, and perfluoroalkyl substances (PFASs) were analysed in serum samples of pregnant women from Denmark to provide information about their exposure and to study indications of common exposure pathways. The main BDE congener was the fully brominated BDE-209 with a median value of 7.5 ng/g lipid (46 pg/mL; 9.8 pmol/g lipid). Other BDE congeners decreased in the order BDE-47 > BDE-99 > BDE-153. The summed concentration of tri- to hepta-BDEs was 7.7 ng/g lipid, i.e. in the higher end of previously reported concentrations from Europe, including plasma samples of pregnant Danish women. Total lipid contents were relatively low, on average 5.9 g/L (9.0 mmol/L). The main PFAS compound was perfluorooctane sulfonate with a median concentration of 8.4 ng/mL. Other PFASs decreased in the order perfluorooctanoic acid > perfluorononanoic acid > perfluorodecanoic acid > perfluorohexane sulfonate and resulted in a ΣPFAS of 12 ng/mL. Within each group, compounds were highly intercorrelated with the exception of BDE-209, which was not correlated with any of the other compounds. No correlations were found either between PFASs and PBDEs suggesting different sources of exposure and/or pharmacokinetic and metabolisation processes. PBDE and PFAS concentrations were in the range associated with adverse effects in some epidemiological studies.

A Review of the Occurrence of Metals and Xenobiotics in European Hedgehogs (Erinaceus europaeus).

Monitoring data from several European countries indicate that European hedgehog (Erinaceus europaeus) populations are declining, and research exploring the causes of the decline, including exposure to potentially harmful xenobiotics and metals, may inform conservation initiatives to protect this species in the wild. Hedgehogs are ground-dwelling mammals, feeding on a range of insects, slugs, snails, and earthworms, as well as eggs, live vertebrates, and carrion, including carcasses of apex predator species representing higher levels of the food chain. Consequently, hedgehogs come into close contact with contaminants present in their habitats and prey. This review investigated the studies available on the subject of the occurrence of metals and organic xenobiotics in hedgehogs. This study found that a vast range of different pesticides; persistent organic pollutants (POPs), including organochlorine compounds and brominated flame retardants (BFRs); as well as toxic heavy metals could be detected. Some compounds occurred in lethal concentrations, and some were associated with a potential adverse effect on hedgehog health and survival. Due to their ecology, combined with the opportunity to apply non-invasive sampling techniques using spines as sampling material, we suggest that the European hedgehog is a relevant bioindicator species for monitoring the exposure of terrestrial wildlife to potential toxicants in urban and rural environments.

Pesticides in the population of European hedgehogs (Erinaceus europaeus) in Denmark.

European hedgehogs (Erinaceus europaeus) inhabit most of Denmark, except for a few smaller islands. Research from other European countries has shown that the hedgehog populations are in decline. The exposure to chemicals might contribute to this development, although their role is currently unknown. Our research studied the occurrence of 19 selected pesticides in the Danish hedgehog population as well as factors potentially explaining the levels of chemicals detected. We analysed 115 liver samples obtained from dead hedgehogs in 2016 for seven rodenticides, four insecticides and eight herbicides commonly used in Denmark at the time of sampling, applying a high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method. Detection frequencies varied between 0.9% for fluroxypyr and trans-permethrin and 79% for bromadiolone. Rodenticides, insecticides and herbicides were detected in 84, 43, and 50% of the samples, respectively. The compounds most frequently detected included the insecticide imidacloprid (35%), the herbicide metamitron (29%) and the rodenticide bromadiolone (79%). Individual concentrations varied between non-detected to >2 µg/g. A total of 79% of the 115 hedgehogs contained more than one detectable pesticide, with up to nine of the 19 compounds detected in one individual. The detection frequencies were found to differ significantly between the Eastern and Western part of Denmark for difenacoum, difethialone and imidacloprid. However, no associations were found with sex, age, habitat type or the prevalence of mecC-MRSA and endoparasites in the hedgehogs tested. Whether or not the pesticide levels detected carry a health risk for the hedgehogs remains unknown as no adverse effect levels have yet been established for European hedgehogs for single compounds or pesticide mixtures.

Chemical threats for the sentinel Pygoscelis adeliae from the Ross Sea (Antarctica): Occurrence and levels of persistent organic pollutants (POPs), perfluoroalkyl substances (PFAS) and mercury within the largest marine protected area worldwide.

The Ross Sea Marine Protected Area (RS-MPA) hosts endemic species that have to cope with multiple threats, including chemical contamination. Adèlie penguin is considered a good sentinel species for monitoring pollutants. Here, 23 unhatched eggs, collected from three colonies along the Ross Sea coasts, were analysed to provide updated results on legacy pollutants and establish a baseline for newer ones. Average sum of polychlorinated biphenyls (∑PCBs) at the three colonies ranged 20.9-24.3 ng/g lipid weight (lw) and included PCBs IUPAC nos. 28, 118, 153, 138, 180. PCBs were dominated by hexachlorinated congeners as previously reported. Hexachlorobenzene (HCB) and p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) ranged between 134 and 166 and 181-228 ng/g lw, respectively. Overall, ∑PCBs was exceeded by pesticides, contrary to previous studies from the Ross Sea. Sum of polybrominated diphenyl ethers (∑PBDEs) ranged between 0.90 and 1.18 ng/g lw and consisted of BDE-47 (that prevailed as expected, representing 60-80 % of the ∑PBDEs) and BDE-85. Sum of perfluoroalkyl substances (∑PFAS) ranged from 1.04 to 1.53 ng/g wet weight and comprised five long-chain perfluorinated carboxylic acids (PFCAs), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS) and perfluorooctanoic acid (PFOA); perfluorooctane sulfonamide (PFOSA) was also detected. The PFAS profile was dominated by PFCAs as already observed in Arctic seabirds. Mercury ranged from 0.07 to 0.15 mg/kg dry weight similarly to previous studies. Legacy pollutants confirmed their ongoing presence in Antarctic biota and their levels seemed mostly in line with the past, but with minor variations in some cases, likely due to continued input or release from past reservoirs. PFAS were reported for the first time in penguins from the Ross Sea, highlighting their ubiquity. Although further studies would be useful to increase the sample size and accordingly improve our knowledge on spatial and temporal trends, this study provides interesting data for future monitoring programs within the RS-MPA that will be crucial to test its effectiveness against human impacts.

Suspect and non-target screening of chemicals of emerging Arctic concern in biota, air and human serum.

Contaminants of emerging concern receive increasing attention in the Arctic environment. The aim of this study was to screen for chemicals of emerging Arctic concern (CEACs) in different types of Arctic samples including biota, air and human serum. We used a combination of gas chromatography (GC) and liquid chromatography (LC) with high resolution mass spectrometry (HRMS) for suspect and non-target screening (NTS). Suspect screening of 25 CEACs was based on published in-silico approaches for the identification of CEACs and revealed tetrabromophthalic anhydride (TBPA) in pilot whale and air, albeit with low detection frequencies (17 and 33%, respectively). An NTS workflow detected 49, 42, 31 and 30 compounds in pilot whale, ringed seal, air, and human serum, respectively, at confidence level 2 and 3. Although legacy POPs still dominated the samples, 64 CEACs were tentatively identified and further assessed for persistence (P), bioaccumulation (B), mobility (M), toxicity (T), and long-range transport potential (LRTP). While four PBT compounds were identified, 37 PMT substances dominated among these 64 compounds. Our study indicated that many chemicals of potential risk might be present in Arctic samples and would benefit from confirmation and further studies of their transport to and accumulation in the Arctic environment.

Computational Tools to Facilitate Early Warning of New Emerging Risk Chemicals.

Innovative tools suitable for chemical risk assessment are being developed in numerous domains, such as non-target chemical analysis, omics, and computational approaches. These methods will also be critical components in an efficient early warning system (EWS) for the identification of potentially hazardous chemicals. Much knowledge is missing for current use chemicals and thus computational methodologies complemented with fast screening techniques will be critical. This paper reviews current computational tools, emphasizing those that are accessible and suitable for the screening of new and emerging risk chemicals (NERCs). The initial step in a computational EWS is an automatic and systematic search for NERCs in literature and database sources including grey literature, patents, experimental data, and various inventories. This step aims at reaching curated molecular structure data along with existing exposure and hazard data. Next, a parallel assessment of exposure and effects will be performed, which will input information into the weighting of an overall hazard score and, finally, the identification of a potential NERC. Several challenges are identified and discussed, such as the integration and scoring of several types of hazard data, ranging from chemical fate and distribution to subtle impacts in specific species and tissues. To conclude, there are many computational systems, and these can be used as a basis for an integrated computational EWS workflow that identifies NERCs automatically.

Cross-cutting studies of per- and polyfluorinated alkyl substances (PFAS) in Arctic wildlife and humans.

This cross-cutting review focuses on the presence and impacts of per- and polyfluoroalkyl substances (PFAS) in the Arctic. Several PFAS undergo long-range transport via atmospheric (volatile polyfluorinated compounds) and oceanic pathways (perfluorinated alkyl acids, PFAAs), causing widespread contamination of the Arctic. Beyond targeting a few well-known PFAS, applying sum parameters, suspect and non-targeted screening are promising approaches to elucidate predominant sources, transport, and pathways of PFAS in the Arctic environment, wildlife, and humans, and establish their time-trends. Across wildlife species, concentrations were dominated by perfluorooctane sulfonic acid (PFOS), followed by perfluorononanoic acid (PFNA); highest concentrations were present in mammalian livers and bird eggs. Time trends were similar for East Greenland ringed seals (Pusa hispida) and polar bears (Ursus maritimus). In polar bears, PFOS concentrations increased from the 1980s to 2006, with a secondary peak in 2014-2021, while PFNA increased regularly in the Canadian and Greenlandic ringed seals and polar bear livers. Human time trends vary regionally (though lacking for the Russian Arctic), and to the extent local Arctic human populations rely on traditional wildlife diets, such as marine mammals. Arctic human cohort studies implied that several PFAAs are immunotoxic, carcinogenic or contribute to carcinogenicity, and affect the reproductive, endocrine and cardiometabolic systems. Physiological, endocrine, and reproductive effects linked to PFAS exposure were largely similar among humans, polar bears, and Arctic seabirds. For most polar bear subpopulations across the Arctic, modeled serum concentrations exceeded PFOS levels in human populations, several of which already exceeded the established immunotoxic thresholds for the most severe risk category. Data is typically limited to the western Arctic region and populations. Monitoring of legacy and novel PFAS across the entire Arctic region, combined with proactive community engagement and international restrictions on PFAS production remain critical to mitigate PFAS exposure and its health impacts in the Arctic.

A two-dimensional HPLC separation for the enantioselective determination of hexabromocyclododecane (HBCD) isomers in biota samples.

A new method for enantioselective analysis of isomers of hexabromocyclododecane (HBCD) is described, using a two-dimensional high-performance liquid chromatography (HPLC) approach to avoid coelution, in particular between (+) α-HBCD, (+) ß-HBCD, or (+) γ-HBCD. After isomer separation on a conventional column, the single isomers are transferred to an enantioselective HPLC column using heart cuts. Two enantioseparations are conducted in two separate partial chromatograms: one for α-HBCD and one for ß- and γ-HBCD. The result is a completely undisturbed enantioselective separation for α-HBCD at a resolution of 4.11. A peak capacity of 107 was achieved. This peak capacity is utilized by the six peaks of the three isomers with two enantiomers each by 6%. This method was applied to samples of sand eel oil, glaucous gull, and ringed seal. The calibration was performed by treating each enantiomer as a single analyte using a multilevel internal standard calibration. Enantiomeric fractions of 0.495-0.501 with standard deviations (SDs) of 0.056-0.071 were determined for racemic standards of α-HBCD, while the values for fish oil were 0.548-0.562 with SD of 0.018-0.041, depending on the respective mass spectrometric transition.

Endocrine disrupting chemicals in indoor dust: A review of temporal and spatial trends, and human exposure.

Several chemicals with widespread consumer uses have been identified as endocrine-disrupting chemicals (EDCs), with a potential risk to humans. The occurrence in indoor dust and resulting human exposure have been reviewed for six groups of known and suspected EDCs, including phthalates and non-phthalate plasticizers, flame retardants, bisphenols, per- and polyfluoroalkyl substances (PFAS), biocides and personal care product additives (PCPs). Some banned or restricted EDCs, such as polybrominated diphenyl ethers (PBDEs), di-(2-ethylhexyl) phthalate (DEHP), bisphenol A (BPA), perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), are still widely detected in indoor dust in most countries, even as the predominating compounds of their group, but generally with decreasing trends. Meanwhile, alternatives that are also potential EDCs, such as bisphenol S (BPS), bisphenol F (BPF), decabromodiphenyl ethane (DBDPE) and organophosphate flame retardants (OPFRs), and PFAS precursors, such as fluorotelomer alcohols, have been detected in indoor dust with increasing frequencies and concentrations. Associations between some known and suspected EDCs, such as phthalate and non-phthalate plasticizers, FRs and BPs, in indoor dust and paired human samples indicate indoor dust as an important human exposure pathway. Although the estimated daily intake (EDI) of most of the investigated compounds was mostly below reference values, the co-exposure to a multitude of known or suspected EDCs requires a better understanding of mixture effects.