Element concentrations, histology and serum biochemistry of arctic char (Salvelinus alpinus) and shorthorn sculpins (Myoxocephalus scorpius) in northwest Greenland.

The increasing exploratory efforts in the Greenland mineral industry, and in particular, the proposed rare earth element (REE) mining projects, requires an urgent need to generate data on baseline REE concentrations and their potential environmental impacts. Herein, we have investigated REE concentrations in anadromous Arctic char (Salvelinus alpinus) and shorthorn sculpins (Myoxocephalus scorpius) from uncontaminated sites in Northwest Greenland, along with the relationships between the element concentrations in gills and liver, and gill histology and serum biochemical parameters. Concentrations of arsenic, silver, cadmium, cerium, chromium, copper, dysprosium, mercury, lanthanum, neodymium, lead, selenium, yttrium, and zinc in gills, liver and muscle are presented. No significant statistical correlations were observed between element concentrations in different organs and gill histology or serum biochemical parameters. However, we observed positive relationships between age and histopathology, emphasizing the importance of including age as a co-variable in histological studies of fish. Despite no element-induced effects were observed, this study is considered an important baseline study, which can be used as a reference for the assessment of impacts of potential future REE mine sites in Greenland.

Fluorinated Precursor Compounds in Sediments as a Source of Perfluorinated Alkyl Acids (PFAA) to Biota.

The environmental behavior of perfluorinated alkyl acids (PFAA) and their precursors was investigated in lake Tyrifjorden, downstream a factory producing paper products coated with per- and polyfluorinated alkyl substances (PFAS). Low water concentrations (max 0.18 ng L-1 linear perfluorooctanesulfonic acid, L-PFOS) compared to biota (mean 149 µg kg-1 L-PFOS in perch livers) resulted in high bioaccumulation factors (L-PFOS BAFPerch liver: 8.05 × 105-5.14 × 106). Sediment concentrations were high, particularly for the PFOS precursor SAmPAP diester (max 1 872 µg kg-1). Biota-sediment accumulation factors (L-PFOS BSAFPerch liver: 22-559) were comparable to elsewhere, and concentrations of PFAA precursors and long chained PFAA in biota were positively correlated to the ratio of carbon isotopes (13C/12C), indicating positive correlations to dietary intake of benthic organisms. The sum fluorine from targeted analyses accounted for 54% of the extractable organic fluorine in sediment, and 9-108% in biota. This, and high trophic magnification factors (TMF, 3.7-9.3 for L-PFOS), suggests that hydrophobic precursors in sediments undergo transformation and are a main source of PFAA accumulation in top predator fish. Due to the combination of water exchange and dilution, transformation of larger hydrophobic precursors in sediments can be a source to PFAA, some of which are normally associated with uptake from water.

Bioaccumulation of Fluorotelomer Sulfonates and Perfluoroalkyl Acids in Marine Organisms Living in Aqueous Film-Forming Foam Impacted Waters.

The use of aqueous film-forming foams (AFFFs) has resulted in hot spots polluted with poly- and perfluorinated alkyl substances (PFASs). The phase out of long-chained perfluoroalkyl acids (PFAAs) from AFFFs resulted in the necessity for alternatives, and short-chained PFAAs and fluorotelomer-based surfactants have been used. Here, the distribution of PFAS contamination in the marine environment surrounding a military site in Norway was investigated. Up to 30 PFASs were analyzed in storm, leachate, and fjord water; marine sediments; marine invertebrates (snails, green shore crab, great spider crab, and edible crab); and teleost fish (Atlantic cod, European place, and Lemon sole). Perfluorooctanesulfonic acid (PFOS) was the most abundantly detected PFAS. Differences in PFAS accumulation levels were observed among species, likely reflecting different exposure routes among trophic levels and different capabilities for depuration and/or enzymatic degradation. In agreement with previous literature, almost no 6:2 fluorotelomer sulfonate (6:2 FTS) was detected in teleost fish. However, this study is one of the first to report considerable concentrations of 6:2 FTS in marine invertebrates, suggesting bioaccumulation. Biota monitoring and risk assessments of sites contaminated with fluorotelomer sulfonates (FTSs) and related compounds should not be limited to fish, but should also include invertebrates.

In Vitro and in Silico Competitive Binding of Brominated Polyphenyl Ether Contaminants with Human and Gull Thyroid Hormone Transport Proteins.

Tetradecabromo-1,4-diphenoxybenzene (TeDB-DiPhOBz) is a highly brominated additive flame retardant (FR). Debrominated photodegradates of TeDB-DiPhOBz are hydroxylated in vitro in liver microsomal assays based on herring gulls (Larus argentatus), including one metabolite identified as 4″-OH-2,2',2″,4-tetrabromo-DiPhOBz. Chemically related methoxylated tetra- to hexabromo-DiPhOBzs are known contaminants in herring gulls. Collectively, nothing is currently known about biological effects of these polybrominated (PB) DiPhOBz-based compounds. The present study investigated the potential thyroidogenicity of 2,2',2″,4-tetrabromo-(TB)-DiPhOBz along with its para-methoxy (MeO)- and hydroxy-(OH)-analogues, using an in vitro competitive protein binding assay with the human thyroid hormone (TH) transport proteins transthyretin (hTTR) and albumin (hALB). This model para-OH-TB-DiPhOBz was found to be capable of competing with thyroxine (T4) for the binding site on hTTR and hALB. In silico analyses were also conducted using a 3D homology model for gull TTR, to predict whether these TB-DiPhOBz-based compounds may also act as ligands for an avian TH transport protein despite evolutionary differences with hTTR. This analysis found all three TB-DiPhOBz analogues to be potential ligands for gull TTR and have similar binding efficacies to THs. Results indicate structure-related differences in binding affinities of these ligands and suggest there is potential for these contaminants to interact with both mammalian and avian thyroid function.

Steroid hormones and persistent organic pollutants in plasma from North-eastern Atlantic pilot whales.

Persistent organic pollutants (POPs) are known to have endocrine disruptive effects, interfering with endogenous steroid hormones. The present study examined nine steroid hormones and their relationships with the concentrations of selected POPs in pilot whales (Globicephala melas) from the Faroe Islands, NE Atlantic. The different steroids were detected in 15 to all of the 26 individuals. High concentrations of progesterone (83.3-211.7pmol/g) and pregnenolone (PRE; 4.68-5.69pmol/g) were found in three adult females indicating that they were pregnant or ovulating. High androgen concentrations in two of the males reflected that one was adult and that one (possibly) had reached puberty. In males a significant positive and strong correlation between body length and testosterone (TS) levels was identified. Furthermore, positive and significant correlations were found between 4-OH-CB107/4'-OH-CB108 and 17ß-estradiol in males. In adult females significant positive correlations were identified between PRE and CB149 and t-nonachlor, between estrone and CB138, -149, -187 and p,p'-DDE, between androstenedione and CB187, and between TS and CB-99 and -153. Although relationships between the POPs and the steroid hormones reported herein are not evidence of cause-effect relationships, the positive correlations between steroids and POPs, particularly in females, suggest that POPs may have some endocrine disrupting effects on the steroid homeostasis in this species.

Japanese quail (Coturnix japonica) liver and thyroid gland histopathology as a result of in ovo exposure to the flame retardants tris(1,3-dichloro-2-propyl) phosphate and Dechlorane Plus.

Japanese quails (Coturnix japonica) were exposed in ovo to tris(1,3-dichloro-2-propyl) phosphate (TDCIPP; 500 ng/µl), Dechlorane Plus (DP; 500 ng/µl), or a 1:1 mixture of these two to investigate the effects on liver and thyroid gland morphology. Histological examination of 14-day-old quails showed that exposure to TDCIPP or the mixture induced hepatic sinusoidal dilatation. No marked effects were seen for DP alone. In addition, the mixture produced divergence of thyroid gland follicles and proliferation of follicular cells. Our study is the first demonstrating histopathological alterations as a result of exposure during early development to the flame retardants TDCIPP or a TDCIPP-DP mixture suggesting the need for further research efforts to investigate potential adverse health effects associated with exposure to these environmental chemicals in wild birds.

Carbon Nanotube Properties Influence Adsorption of Phenanthrene and Subsequent Bioavailability and Toxicity to Pseudokirchneriella subcapitata.

The bioavailability of organic contaminants adsorbed to carbon nanotubes (CNTs) remains unclear, especially in complex natural freshwaters containing natural organic matter (NOM). Here, we report on the adsorption capacity (Q(0)) of five CNTs exhibiting different physicochemical properties, including a single-walled CNT (SWCNTs), multiwalled CNTs (MWCNT-15 and MWCNT-30), and functionalized MWCNTs (hydroxyl, -OH, and carboxyl, -COOH), for the model polycyclic aromatic hydrocarbon phenanthrene (3.1-800 µg/L). The influence of phenanthrene adsorption by the CNTs on bioavailability and toxicity was investigated using the freshwater algae Pseudokirchneriella subcapitata. CNTs were dispersed in algal growth media containing NOM (DOC, 8.77 mg/L; dispersed concentrations: 0.5, 1.3, 1.3, 3.3, and 6.1 mg/L for SWCNT, MWCNT-15, MWCNT-30, MWCNT-OH, and MWCNT-COOH, respectively). Adsorption isotherms of phenanthrene to the dispersed CNTs were fitted with the Dubinin-Ashtakhov model. Q(0) differed among the CNTs, increasing with increasing surface area and decreasing with surface functionalization. SWCNT and MWCNT-COOH exhibited the highest and lowest log Q(0) (8.891 and 7.636 µg/kg, respectively). The presence of SWCNTs reduced phenanthrene toxicity to algae (EC50; 528.4) compared to phenanthrene-only (EC50; 438.3), and the presence of MWCNTs had no significant effect on phenanthrene toxicity. However, phenanthrene adsorbed to NOM-dispersed CNTs proved to be bioavailable and contribute to exert toxicity to P. subcapitata.

Phenanthrene Bioavailability and Toxicity to Daphnia magna in the Presence of Carbon Nanotubes with Different Physicochemical Properties.

Studies investigating the effect of carbon nanotubes (CNTs) on the bioavailability and toxicity of hydrophobic organic compounds in aquatic environments have generated contradictory results, and the influence of different CNT properties remains unknown. Here, the adsorption of the polycyclic aromatic hydrocarbon phenanthrene (70-735 µg/L) to five types of CNTs exhibiting different physical and chemical properties was studied. The CNTs were dispersed in the presence of natural organic matter (nominally 20 mg/L) in order to increase the environmental relevance of the study. Furthermore, the bioavailability and toxicity of phenanthrene to Daphnia magna in the absence and presence of dispersed CNTs was investigated. Both CNT dispersion and adsorption of phenanthrene appeared to be influenced by CNT physical properties (diameter and specific surface area). However, dispersion and phenanthrene adsorption was not influenced by CNT surface chemical properties (surface oxygen content), under the conditions tested. Based on nominal phenanthrene concentrations, a reduction in toxicity to D. magna was observed during coexposure to phenanthrene and two types of CNTs, while for the others, no influence on phenanthrene toxicity was observed. Based on freely dissolved concentrations, however, an increased toxicity was observed in the presence of all CNTs, indicating bioavailability of CNT-adsorbed phenanthrene to D. magna.

Antioxidant Responses in Relation to Persistent Organic Pollutants and Metals in a Low- and a High-Exposure Population of Seabirds.

Oxidative stress occurs when there is an imbalance between the production of reactive oxygen species (ROS) and antioxidant defense. Exposure to pollutants may increase ROS and affect antioxidant levels, and the resulting oxidative stress may negatively affect both reproduction and survival. We measured concentrations of 18 persistent organic pollutants (POPs) and 9 toxic elements in blood, as well as total antioxidant capacity (TAC), total glutathione (tGSH), and carotenoids in plasma of Baltic and Arctic female common eiders (Somateria mollissima) (N = 54) at the end of their incubation-related fasting. The more polluted Baltic population had higher TAC and tGSH concentrations compared to the Arctic population. Carotenoid levels did not differ between populations. The effect of mixtures of pollutants on the antioxidants was assessed, and the summed molar blood concentrations of 14 POPs were positively related to TAC. There was no significant relationship between the analyzed pollutants and tGSH concentrations. The adaptive improvement of the antioxidant defense system in the Baltic population may be a consequence of increased oxidative stress. However, both increased oxidative stress and energy allocation toward antioxidant defense may have adverse consequences for Baltic eiders at the incubation stage, when energy resources reach an annual minimum due to incubation-related fasting.

Relationships between concentrations of selected organohalogen contaminants and thyroid hormones and vitamins A, E and D in Faroese pilot whales.

Pilot whales (Globicephala melas) from the Faroe Islands, North-East Atlantic, have high body concentrations of organohalogenated compounds (OHCs), such as polychlorinated biphenyls (PCBs), organochlorinated pesticides (OCPs) and brominated flame retardants (BFRs). The aim of the present study was to examine if and to what extent blood plasma and liver concentrations of several groups of these OHCs are related to concentrations of relevant nutritional and hormonal biomarkers in pilot whales. Thyroid hormones (THs: total and free thyroxine and total and free triiodothyronine) and vitamin A (retinol), D (25-hydroxyvitamin D3) and E (α-tocopherol) were analysed in plasma (n=27) and vitamin A (total vitamin A, retinol and retinyl palmitate) and E (α- and γ-tocopherol) were analysed in liver (n=37) of Faroe Island pilot whales. Correlative relationships between the biomarkers and OHC concentrations previously analysed in the same tissues in these individuals were studied. The TH concentrations in plasma were significantly higher in juveniles than in adults. Vitamin D concentrations in plasma and α- and γ-tocopherol in liver were higher in adults than in juveniles. Multivariate statistical modelling showed that the age and sex influenced the relationship between biomarkers and OHCs. Some significant positive relationships were found between OHCs and thyroid hormone concentrations in the youngest juveniles (p<0.05). In plasma of juvenile whales α-tocopherol was also positively correlated with all the OHCs (p<0.05). Only few significant correlations were found between single OHCs and retinol and vitamin D in plasma within the age groups. There were significant negative relationships between hepatic PBDE concentrations and retinol (BDE-47) and γ-tocopherol (BDE-49, -47, -100, -99, -153) in liver. The relationships between OHCs and THs or vitamins suggest that in pilot whales OHCs seem to have minor effects on TH and vitamin concentrations.

DNA double-strand breaks in incubating female common eiders (Somateria mollissima): Comparison between a low and a high polluted area.

Alterations in the genetic material may have severe consequences for individuals and populations. Hence, genotoxic effects of environmental exposure to pollutants are of great concern. We assessed the impact of blood concentrations of persistent organic pollutants (POPs) and mercury (Hg) on DNA double-strand break (DSB) frequency, in blood cells of a high-exposed Baltic, and lower exposed Arctic population of common eiders (Somateria mollissima). Furthermore, we examined whether the genotoxic response was influenced by antioxidant concentration (plasma total glutathione (tGSH) and total antioxidant capacity) and female body mass. The DNA DSB frequency did not differ between the two populations. We found significant positive relationships between Hg and DNA DSB frequency in Baltic, but not in Arctic eiders. Although both p,p'-DDE and PCB 118 had a lesser effect than Hg, they exhibited a positive association with DNA DSB frequency in Baltic eiders. Antioxidant levels were not important for the genotoxic effect, suggesting alternative mechanisms other than GSH depletion for the relationship between Hg and DNA DSBs. Hence, the Baltic population, which is considered to be endangered and is under the influence of several environmental stressors, may be more susceptible to genotoxic effects of environmental exposure to Hg than the Arctic population.

Hydroxylated polychlorinated biphenyls decrease circulating steroids in female polar bears (Ursus maritimus).

As a top predator in the Arctic food chain, polar bears (Ursus maritimus) are exposed to high levels of persistent organic pollutants (POPs). Because several of these compounds have been reported to alter endocrine pathways, such as the steroidogenesis, potential disruption of the sex steroid synthesis by POPs may cause implications for reproduction by interfering with ovulation, implantation and fertility. Blood samples were collected from 15 female polar bears in Svalbard (Norway) in April 2008. The concentrations of nine circulating steroid hormones; dehydroepiandrosterone (DHEA), androstenedione (AN), testosterone (TS), dihydrotestosterone (DHT), estrone (E1), 17α-estradiol (αE2), 17ß-estradiol (ßE2), pregnenolone (PRE) and progesterone (PRO) were determined. The aim of the study was to investigate associations among circulating levels of specific POP compounds and POP-metabolites (hydroxylated PCBs [OH-PCBs] and hydroxylated PBDEs [OH-PBDEs]), steroid hormones, biological and capture variables in female polar bears. Inverse correlations were found between circulating levels of PRE and AN, and circulating levels of OH-PCBs. There were no significant relationships between the steroid concentrations and other analyzed POPs or the variables capture date and capture location (latitude and longitude), lipid content, condition and body mass. Although statistical associations do not necessarily represent direct cause-effect relationships, the present study indicate that OH-PCBs may affect the circulating levels of AN and PRE in female polar bears and that OH-PCBs thus may interfere with the steroid homeostasis. Increase in PRO and a decrease in AN concentrations suggest that the enzyme CYP17 may be a potential target for OH-PCBs. In combination with natural stressors, ongoing climate change and contaminant exposure, it is possible that OH-PCBs may disturb the reproductive potential of polar bears.

DNA double-strand breaks in relation to persistent organic pollutants in a fasting seabird.

Lipophilic persistent organic pollutants (POPs) are released from fat reserves during fasting, causing increased blood concentrations. Thus, POPs represent a potential anthropogenic stressor during fasting periods. We analysed the blood of female common eiders (Somateria mollissima) by using agarose gel electrophoresis and image data analysis to quantify the DNA-fraction, of total DNA, that migrated into the gel (DNA-FTM) as a relative measure of DNA double strand-breaks (DSBs) during the fasting incubation period in the high arctic. In 2008 and in 2009 blood samples were obtained for analysis of 9 POPs and DNA-FTM at day 5 of the incubation period, and then in the same individuals at day 20. This unique study design gave us the opportunity to analyse the same individuals throughout two points in time, with low and high stress burdens. During the incubation period the body mass (BM) decreased by 21-24%, whereas the POP levels increased by 148-639%. The DNA-FTM increased by 61-67% (being proportional to the increase in DSBs). At day 5, but not day 20, DNA-FTM was positively correlated with most analysed POPs. The increase in DNA-FTM was positively correlated with the decrease in BM (g) during incubation. Thus, we suggest that fasting stress (BM loss) decreases DNA integrity and that stress caused by fasting on BM loss appeared to override the additional stress caused by concurrent increase in levels of the analysed POPs in the eiders. Blood levels of POPs in the eiders in Svalbard were relatively low, and additive and/or synergistic genotoxic effects of fasting stress and POP exposure may occur in populations with higher POP levels.

Toxicity and biokinetics following pulmonary exposure to aluminium (aluminum): A review.

During the manufacture and use of aluminium (aluminum), inhalation exposure may occur. We reviewed the pulmonary toxicity of this metal including its toxicokinetics. The normal serum/plasma level based on 17 studies was 5.7 ± 7.7 µg Al/L (mean ± SD). The normal urine level based on 15 studies was 7.7 ± 5.3 µg/L. Bodily fluid and tissue levels during occupational exposure are also provided, and the urine level was increased in aluminium welders (43 ± 33 µg/L) based on 7 studies. Some studies demonstrated that aluminium from occupational exposure can remain in the body for years. Excretion pathways include urine and faeces. Toxicity studies were mostly on aluminium flakes, aluminium oxide and aluminium chlorohydrate as well as on mixed exposure, e.g. in aluminium smelters. Endpoints affected by pulmonary aluminium exposure include body weight, lung function, lung fibrosis, pulmonary inflammation and neurotoxicity. In men exposed to aluminium oxide particles (3.2 µm) for two hours, lowest observed adverse effect concentration (LOAEC) was 4 mg Al2O3/m3 (= 2.1 mg Al/m3), based on increased neutrophils in sputum. With the note that a similar but not statistically significant increase was seen during control exposure. In animal studies LOAECs start at 0.3 mg Al/m3. In intratracheal instillation studies, all done with aluminium oxide and mainly nanomaterials, lowest observed adverse effect levels (LOAELs) started at 1.3 mg Al/kg body weight (bw) (except one study with a LOAEL of ∼0.1 mg Al/kg bw). The collected data provide information regarding hazard identification and characterisation of pulmonary exposure to aluminium.

Effect-Directed Analysis Based on Transthyretin Binding Activity of Per- and Polyfluoroalkyl Substances in a Contaminated Sediment Extract.

Only a fraction of the total number of per- and polyfluoroalkyl substances (PFAS) are monitored on a routine basis using targeted chemical analyses. We report on an approach toward identifying bioactive substances in environmental samples using effect-directed analysis by combining toxicity testing, targeted chemical analyses, and suspect screening. PFAS compete with the thyroid hormone thyroxin (T4 ) for binding to its distributor protein transthyretin (TTR). Therefore, a TTR-binding bioassay was used to prioritize unknown features for chemical identification in a PFAS-contaminated sediment sample collected downstream of a factory producing PFAS-coated paper. First, the TTR-binding potencies of 31 analytical PFAS standards were determined. Potencies varied between PFAS depending on carbon chain length, functional group, and, for precursors to perfluoroalkyl sulfonic acids (PFSA), the size or number of atoms in the group(s) attached to the nitrogen. The most potent PFAS were the seven- and eight-carbon PFSA, perfluoroheptane sulfonic acid (PFHpS) and perfluorooctane sulfonic acid (PFOS), and the eight-carbon perfluoroalkyl carboxylic acid (PFCA), perfluorooctanoic acid (PFOA), which showed approximately four- and five-times weaker potencies, respectively, compared with the native ligand T4 . For some of the other PFAS tested, TTR-binding potencies were weak or not observed at all. For the environmental sediment sample, not all of the bioactivity observed in the TTR-binding assay could be assigned to the PFAS quantified using targeted chemical analyses. Therefore, suspect screening was applied to the retention times corresponding to observed TTR binding, and five candidates were identified. Targeted analyses showed that the sediment was dominated by the di-substituted phosphate ester of N-ethyl perfluorooctane sulfonamido ethanol (SAmPAP diester), whereas it was not bioactive in the assay. SAmPAP diester has the potential for (bio)transformation into smaller PFAS, including PFOS. Therefore, when it comes to TTR binding, the hazard associated with this substance is likely through (bio)transformation into more potent transformation products. Environ Toxicol Chem 2024;43:245-258. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Human exposure to per- and polyfluoroalkyl substances (PFAS) via the consumption of fish leads to exceedance of safety thresholds.

Per- and polyfluoroalkyl substances (PFAS) receive global attention due to their adverse effects on human health and the environment. Fish consumption is a major source of human PFAS exposure. The aim of this work was to address the lack of harmonization within legislations (in the EU and the USA) and highlight the level of PFAS in fish exposed to pollution from diffuse sources in the context of current safety thresholds. A non-exhaustive literature review was carried out to obtain PFAS concentrations in wild fish from the Norwegian mainland, Svalbard, the Netherlands, the USA, as well as sea regions (North Sea, English Channel, Atlantic Ocean), and farmed fish on the Dutch market. Median sum wet weight concentrations of PFOA, PFNA, PFHxS, and PFOS ranged between 0.1 µg kg-1 (farmed fish) and 22 µg kg-1 (Netherlands eel). Most concentrations fell below the EU environmental quality standard (EQSbiota) for PFOS (9.1 µg kg-1) and would not be defined as polluted in the EU. However, using recent tolerable intake or reference dose values in the EU and the USA revealed that even limited fish consumption would lead to exceedance of these thresholds - possibly posing a challenge for risk communication.

Transthyretin-binding activity of contaminants in blood from polar bear (Ursus maritimus) cubs.

We determined the transthyretin (TTR)-binding activity of blood-accumulating contaminants in blood plasma samples of approximately 4-months-old polar bear (Ursus maritimus) cubs from Svalbard sampled in 1998 and 2008. The TTR-binding activity was measured as thyroxine (T4)-like equivalents (T4-EQMeas). Our findings show that the TTR-binding activity related to contaminant levels was significantly lower (45%) in 2008 than in 1998 (mean ± standard error of mean: 1998, 2265 ± 231 nM; 2008, 1258 ± 170 nM). Although we cannot exclude a potential influence of between-year differences in capture location and cub body mass, our findings most likely reflect reductions of TTR-binding contaminants or their precursors in the arctic environment (e.g., polychlorinated biphenyls [PCBs]). The measured TTR-binding activity correlated positively with the cubs' plasma levels of hydroxylated PCBs (OH-PCBs). No such association was found between TTR-binding activity and the plasma levels of perfluoroalkyl substances (PFASs). The OH-PCBs explained 60 ± 7% and 54 ± 4% of the TTR-binding activity in 1998 and 2008, respectively, and PFASs explained ≤1.2% both years. Still, almost half the TTR-binding activity could not be explained by the contaminants we examined. The considerable levels of TTR-binding contaminants warrant further effect directed analysis (EDA) to identify the contaminants responsible for the unexplained part of the observed TTR-binding activity.

Effect-directed analysis to explore the polar bear exposome: identification of thyroid hormone disrupting compounds in plasma.

Compounds with transthyretin (TTR)-binding potency in the blood plasma of polar bear cubs were identified with effect-directed analysis (EDA). This approach contributes to the understanding of the thyroid disrupting exposome of polar bears. The selection of these samples for in-depth EDA was based on the difference between the observed TTR-binding potency on the one hand and the calculated potency (based on known concentrations of TTR-binding compounds and their relative potencies) on the other. A library-based identification was applied to the liquid chromatography-time-of-flight-mass spectrometry (LC-ToF-MS) data by screening for matches between compound lists and the LC-ToF-MS data regarding accurate mass and isotope pattern. Then, isotope cluster analysis (ICA) was applied to the LC-ToF-MS data allowing specific screening for halogen isotope patterns. The presence of linear and branched nonylphenol (NP) was observed for the first time in polar bears. Furthermore, the presence of one di- and two monohydroxylated octachlorinated biphenyls (octaCBs) was revealed in the extracts. Linear and branched NP, 4'-OH-CB201 and 4,4'-OH-CB202 could be successfully confirmed with respect to their retention time in the analytical system. In addition, branched NP, mono- and dihydroxylated-octaCBs showed TTR-binding potencies and could explain another 32 ± 2% of the total measured activities in the extracts.

EU need to protect its environment from toxic per- and polyfluoroalkyl substances.

The Environmental Protection Agencies (EPAs) of Denmark, Sweden, Norway, Germany and the Netherlands submitted a proposal to the European Chemical Agency (ECHA) in February 2023 calling for a ban in the use of toxic industrial chemicals per- and polyfluoroalkyl substances (PFAS). These chemicals are highly toxic causing elevated cholesterol, immune suppression, reproductive failure, cancer and neuro-endocrine disruption in humans and wildlife being a significant threat to biodiversity and human health. The main reason for the submitted proposal is recent findings of significant flaws in the transition to PFAS replacements that is leading to a widespread pollution. Denmark was the first country banning PFAS, and now other EU countries support the restrictions of these carcinogenic, endocrine disruptive and immunotoxic chemicals. The proposed plan is among the most extensive received by the ECHA for 50 years. Denmark is now the first EU country to initiate the establishment of groundwater parks to try and protect its drinking water. These parks are areas free of agricultural activities and nutritious sewage sludge to secure drinking water free of xenobiotic including PFAS. The PFAS pollution also reflects the lack of comprehensive spatial and temporal environmental monitoring programs in the EU. Such monitoring programs should include key indicator species across ecosystems of livestock, fish and wildlife, to facilitate detection of early ecological warning signals and sustain public health. Simultaneously with inferring a total PFAS ban, the EU should also push for more persistent, bioaccumulative and toxic (PBT) PFAS substances to be listed on the Stockholm Convention (SC) Annex A such as PFOS (perfluorooctane sulfonic acid) that is currently listed on the SCs Annex B. The combination of these regulative restrictions combined with groundwater parks and pan-European biomonitoring programs, would pave the way forward for a cleaner environment to sustain health across the EU.

Testosterone and persistent organic pollutants in East Greenland male polar bears (Ursus maritimus).

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.