Development of a supramolecular solvent-based extraction method for application to quantitative analyses of a wide range of organic contaminants in indoor dust.

This study investigates the efficacy of supramolecular solvent (SUPRAS) in extracting a diverse spectrum of organic contaminants from indoor dust. Initially, seven distinct SUPRAS were assessed across nine categories of contaminants to identify the most effective one. A SUPRAS comprising Milli-Q water, tetrahydrofuran, and hexanol in a 70:20:10 ratio, respectively, demonstrated the best extraction performance and was employed for testing a wider array of organic contaminants. Furthermore, we applied the selected SUPRAS for the extraction of organic compounds from the NIST Standard Reference Material (SRM) 2585. In parallel, we performed the extraction of NIST SRM 2585 with conventional extraction methods using hexane:acetone (1:1) for non-polar contaminants and methanol (100%) extraction for polar contaminants. Analysis from two independent laboratories (in Norway and the Czech Republic) demonstrated the viability of SUPRAS for the simultaneous extraction of twelve groups of organic contaminants with a broad range of physico-chemical properties including plastic additives, pesticides, and combustion by-products. However, caution is advised when employing SUPRAS for highly polar contaminants like current-use pesticides or volatile substances like naphthalene.

Dechloranes and chlorinated paraffins in sediments and biota of two subarctic lakes.

Our understanding of the environmental behavior, bioaccumulation and concentrations of chlorinated paraffins (CPs) and Dechloranes (Dec) in the Arctic environment is still limited, particularly in freshwater ecosystems. In this descriptive study, short chain (SCCPs) and medium chain (MCCPs) CPs, Dechlorane Plus (DP) and analogues, and polychlorinated biphenyls (PCBs) were measured in sediments, benthic organisms, three-spined stickleback (Gasterosteus aculeatus), Arctic char (Salvelinus alpinus) and brown trout (Salmo trutta) in two Sub-Arctic lakes in Northern Norway. Takvannet (TA) is a remote lake, with no known local sources for organic contaminants, while Storvannet (ST) is situated in a populated area. SCCPs and MCCPs were detected in all sediment samples from ST with concentration of 42.26-115.29 ng/g dw and 66.18-136.69 ng/g dw for SCCPs and MCCPs, respectively. Only SCCPs were detected in TA sediments (0.4-5.28 ng/g dw). In biota samples, sticklebacks and benthic organisms showed the highest concentrations of CPs, while concentrations were low or below detection limits in both char and trout. The congener group patterns observed in both lakes showed SCCP profiles dominated by higher chlorinated congener groups while the MCCPs showed consistency in their profiles, with C14 being the most prevalent carbon chain length. Anti- and syn-DP isomers were detected in all sediment, benthic and stickleback samples with higher concentrations in ST than in TA. However, they were only present in a few char and trout samples from ST. Dec 601 and 604 were below detection limits in all samples in both lakes. Dec 603 was detected only in ST sediments, sticklebacks and 2 trout samples, while Dec 602 was the only DP analogue found in all samples from both lakes. While there were clear differences in sediment concentrations of DP and Dec 602 between ST and TA, differences between lakes decreased with increasing δ15N. This pattern was similar to the PCB behavior, suggesting the lake characteristics in ST are playing an important role in the lack of biomagnification of pollutants in this lake. Our results suggest that ST receives pollutants from local sources in addition to atmospheric transport.

Can plastic related chemicals be indicators of plastic ingestion in an Arctic seabird?

For decades, the northern fulmar (Fulmarus glacialis) has been found to ingest and accumulate high loads of plastic due to its feeding ecology and digestive tract morphology. Plastic ingestion can lead to both physical and toxicological effects as ingested plastics can be a pathway for hazardous chemicals into seabirds' tissues. Many of these contaminants are ubiquitous in the environment and the contribution of plastic ingestion to the uptake of those contaminants in seabirds' tissues is poorly known. In this study we aimed at quantifying several plastic-related chemicals (PRCs) -PBDE209, several dechloranes and several phthalate metabolites- and assessing their relationship with plastic burdens (both mass and number) to further investigate their potential use as proxies for plastic ingestion. Blood samples from fulmar fledglings and liver samples from both fledgling and non-fledgling fulmars were collected for PRC quantification. PBDE209 and dechloranes were quantified in 39 and 33 livers, respectively while phthalates were quantified in plasma. Plastic ingestion in these birds has been investigated previously and showed a higher prevalence in fledglings. PBDE209 was detected in 28.2 % of the liver samples. Dechlorane 602 was detected in all samples while Dechloranes 601 and 604 were not detected in any sample. Dechlorane 603 was detected in 11 individuals (33%). Phthalates were detected in one third of the analysed blood samples. Overall, no significant positive correlation was found between plastic burdens and PRC concentrations. However, a significant positive relationship between PBDE209 and plastic number was found in fledglings, although likely driven by one outlier. Our study shows the complexity of PRC exposure, the timeline of plastic ingestion and subsequent uptake of PRCs into the tissues in birds, the additional exposure of these chemicals via their prey, even in a species ingesting high loads of plastic.

Phthalate contamination in marine mammals off the Norwegian coast.

Phthalates are used in plastics, found throughout the marine environment and have the potential to cause adverse health effects. In the present study, we quantified blubber concentrations of 11 phthalates in 16 samples from stranded and/or free-living marine mammals from the Norwegian coast: the killer whale (Orcinus orca), sperm whale (Physeter macrocephalus), long-finned pilot whale (Globicephala melas), white-beaked dolphin (Lagenorhynchus albirostris), harbour porpoise (Phocoena phocoena), and harbour seal (Phoca vitulina). Five compounds were detected across all samples: benzyl butyl phthalate (BBP; in 50 % of samples), bis(2-ethylhexyl) phthalate (DEHP; 33 %), diisononyl phthalate (DiNP; 33 %), diisobutyl phthalate (DiBP; 19 %), and dioctyl phthalate (DOP; 13 %). Overall, the most contaminated individual was the white-beaked dolphin, whilst the lowest concentrations were measured in the killer whale, sperm whale and long-finned pilot whale. We found no phthalates in the neonate killer whale. The present study is important for future monitoring and management of these toxic compounds.

Occurrence of emerging brominated flame retardants and organophosphate esters in marine wildlife from the Norwegian Arctic.

To understand the exposure and potential sources of emerging brominated flame retardants (EBFR) and organophosphate esters (OPEs) in marine wildlife from the Norwegian Arctic, we investigated concentrations of EBFRs in 157 tissue samples from nine species of marine vertebrates and OPEs in 34 samples from three whale species. The samples, collected from a wide range of species with contrasting areal use and diets, included blubber of blue whales, fin whales, humpback whales, white whales, killer whales, walruses and ringed seals and adipose tissue and plasma from polar bears, as well as adipose tissue from glaucous gulls. Tris(2-ethylhexyl) phosphate (TEHP) and tris(2-chloroisopropyl) phosphate (TCIPP) ranged from <0.61 to 164 and < 0.8-41 ng/g lipid weight, respectively, in blue whales and fin whales. All other EBRFs and OPEs were below the detection limit or detected only at low concentration. In addition to the baseline information on the occurrence of EBFRs and OPEs in marine wildlife from the Arctic, we provide an in-depth discussion regarding potential sources of the detected compounds. This information is important for future monitoring and management of EBFRs and OPEs.

Ingested plastics in northern fulmars (Fulmarus glacialis): A pathway for polybrominated diphenyl ether (PBDE) exposure?

Although it has been suggested that plastic may act as a vector for pollutants into the tissue of seabirds, the bioaccumulation of harmful contaminants, such as polybrominated diphenyl ethers (PBDEs), released from ingested plastics is poorly understood. Plastic ingestion by the procellariiform species northern fulmar (Fulmarus glacialis) is well documented. In this study, we measured PBDEs levels in liver tissue of northern fulmars without and with (0.13-0.43 g per individual) stomach plastics. PBDE concentrations in the plastic sampled from the same birds were also quantified. Birds were either found dead on beaches in southern Norway or incidentally caught in longline fisheries in northern Norway. PBDEs were detected in all birds but high concentrations were only found in liver samples from beached birds, peaking at 2900 ng/g lipid weight. We found that body condition was a significant factor explaining the elevated concentration levels in livers of beached birds. BDE209 was found in ingested plastic particles and liver tissue of birds with ingested plastics but was absent in the livers of birds without ingested plastics. This strongly suggests a plastic-derived transfer and accumulation of BDE209 to the tissue of fulmars, levels of which might prove useful as a general indicator of plastic ingestion in seabirds.

Concentrations and endocrine disruptive potential of phthalates in marine mammals from the Norwegian Arctic.

This study investigated concentrations of phthalates (diesters of phthalic acids) in blubber/adipose tissue of blue whales (Balaenoptera musculus), fin whales (Balaenoptera physalus), bowhead whales (Balaena mysticetus) and polar bears (Ursus maritimus) sampled in the Svalbard Archipelago (extending westward in the case of bowhead whales). Additionally, total concentrations (free and conjugated forms) of eight phthalate monoester metabolites were analysed in plasma of polar bears. Bis(2-ethylhexyl) phthalate (DEHP) was the only phthalate quantified among the 12 phthalates investigated. This compound was present in 6/7 fin whale samples, 4/7 blue whale samples, 2/5 bowhead whale samples and 1/12 polar bear samples. DEHP concentrations ranged from <20-398 ng/g wet weight. Phthalate metabolites, mono-n-butyl phthalate and monoisobutyl phthalate, were found in low concentrations (<1.2 ng/mL) in some of the polar bear samples. In vitro reporter gene assays were used to assess transcriptional activity of fin whale peroxisome proliferator-activated receptor gamma (PPARG), glucocorticoid receptor (GR) and the thyroid hormone receptor beta (THRB) by DEHP and diisononyl phthalate (DiNP). Due to the high degree of similarity of the ligand binding domain in the THRB and PPARG among whales, polar bears and humans, the transactivation results also apply for these species. DEHP showed both agonistic and antagonistic effects towards whale THRB at considerably higher concentrations than measured in the study animals; DiNP was a weak agonist of whale THRB. No significant agonistic or antagonistic effects were detected for DEHP or DiNP for whale PPARG, whereas DEHP and DiNP decreased basal luciferase activity mediated by whale GR at several test concentrations. In conclusion, DEHP was detected in the blubber of marine mammals from the Norwegian Arctic and it appears to have potential to modulate the transcriptional activity of whale THRB, but current DEHP concentrations do not modulate the function of the studied nuclear receptors in adipose tissue of blue whales, fin whales, bowhead whales or polar bears sampled from the Norwegian Arctic.

Hepatic Gene Expression Profiling of Atlantic Cod (Gadus morhua) Liver after Exposure to Organophosphate Flame Retardants Revealed Altered Cholesterol Biosynthesis and Lipid Metabolism.

Since the phasing out and eventual ban on the production of organohalogen flame retardants, the use of organophosphate flame retardants (OPFRs) has increased rapidly. This has led to the detection of OPFRs in various environments including the Arctic. Two of the most prevalent OPFRs found in the Arctic are tris(2-chloroisopropyl) phosphate (TCPP), and 2-ethylhexyl diphenyl phosphate (EHDPP). The impacts of exposure to OPFRs on Arctic organisms is poorly understood. The objective of the present study was to determine the effects of exposure to TCPP, EHDPP, and a mixture of OPFRs on gene expression patterns in Atlantic cod, Gadus morhua. Precision-cut liver slices from Atlantic cod in vitro were exposed to either TCPP or EHDPP alone or in a mixture and sampled at 2 different time points to quantify gene expression patterns using RNA sequencing. We exposed the liver slices to 2 concentrations of TCPP and EHDPP, one of which was chosen based on the levels found in the Arctic environment. The RNA sequencing results demonstrated differential expression of hundreds of genes in response to exposure. The genes representing cholesterol biosynthesis and lipid metabolism pathway were significantly enriched in all the treatment groups. Almost all the cholesterol biosynthesis genes were significantly down-regulated in response to OPFR exposure. The effects on these pathways could involve various physiological processes including reproduction, growth, and behavior as well as adaptation to changing temperatures. Membrane fluidity is an important adaptive mechanism among aquatic organisms. Altered cholesterol homeostasis could have long-term consequences by altering the adaptive potential of aquatic organisms to changing water temperatures, particularly those living in polar environments. These results suggest that OPFRs could have unique effects on the organisms living in the Arctic compared with other environments. Further studies are needed to understand the long-term impacts of exposure to environmentally realistic concentrations using laboratory and field-based studies. Environ Toxicol Chem 2021;40:1639-1648. © 2021 SETAC.

Seabird-Transported Contaminants Are Reflected in the Arctic Tundra, But Not in Its Soil-Dwelling Springtails (Collembola).

Arctic-breeding seabirds contain high levels of many anthropogenic contaminants, which they deposit through guano to the tundra near their colonies. Nutrient-rich soil in vicinity to seabird colonies are favorable habitats for soil invertebrates, such as springtails (Collembola), which may result in exposure to seabird-derived contaminants. We quantified a wide range of lipid-soluble and protein-associated environmental contaminants in two springtail species (Megaphorura arctica and Hypogastrura viatica) and their respective habitats (soil/moss) collected underneath seabird cliffs. Although springtails are commonly used in laboratory toxicity tests, this is the first study to measure concentrations of persistent organic pollutants (POPs) and mercury (Hg) in springtails from the field, and to study biotransportation of contaminants by seabirds to soil fauna. We categorized the sites a priori as of low, medium, or high seabird influence, based on the seabird abundance and species composition. This ranking was reflected in increasing δ15N values in soil/moss and springtails with increasing seabird influence. We found clear indications of seabirds impacting the terrestrial soil environments with organic contaminants, and that concentrations were higher in soil and moss close to the bird cliff, compared to farther away. However, we did not find a relationship between contaminant concentration in springtails and the concentrations in soil/moss, or with level of seabird influence. Our study indicates a low uptake of contaminants in the soil fauna, despite seabird-derived contamination of their habitat.

Environmental contaminants modulate the transcriptional activity of polar bear (Ursus maritimus) and human peroxisome proliferator-activated receptor alpha (PPARA).

Peroxisome proliferator-activated receptor alfa (PPARA/NR1C1) is a ligand activated nuclear receptor that is a key regulator of lipid metabolism in tissues with high fatty acid catabolism such as the liver. Here, we cloned PPARA from polar bear liver tissue and studied in vitro transactivation of polar bear and human PPARA by environmental contaminants using a luciferase reporter assay. Six hinge and ligand-binding domain amino acids have been substituted in polar bear PPARA compared to human PPARA. Perfluorocarboxylic acids (PFCA) and perfluorosulfonic acids induced the transcriptional activity of both human and polar bear PPARA. The most abundant PFCA in polar bear tissue, perfluorononanoate, increased polar bear PPARA-mediated luciferase activity to a level comparable to that of the potent PPARA agonist WY-14643 (~8-fold, 25 µM). Several brominated flame retardants were weak agonists of human and polar bear PPARA. While single exposures to polychlorinated biphenyls did not, or only slightly, increase the transcriptional activity of PPARA, a technical mixture of PCBs (Aroclor 1254) strongly induced the transcriptional activity of human (~8-fold) and polar bear PPARA (~22-fold). Polar bear PPARA was both quantitatively and qualitatively more susceptible than human PPARA to transactivation by less lipophilic compounds.

Contaminants in Atlantic walruses in Svalbard Part 2: Relationships with endocrine and immune systems.

Marine mammals in the Barents Sea region have among the highest levels of contaminants recorded in the Arctic and the Atlantic walrus (Odobenus rosmarus rosmarus) is one of the most contaminated species within this region. We therefore investigated the relationships bewteen blubber concentrations of lipophilic persistent organic pollutants (POPs) and plasma concentrations of perfluoroalkyl substances (PFASs) and markers of endocrine and immune functions in adult male Atlantic walruses (n = 38) from Svalbard, Norway. To do so, we assessed plasma concentrations of five forms of thyroid hormones and transcript levels of genes related to the endocrine and immune systems as endpoints; transcript levels of seven genes in blubber and 23 genes in blood cells were studied. Results indicated that plasma total thyroxine (TT4) concentrations and ratio of TT4 and reverse triiodothyronine decreased with increasing blubber concentrations of lipophilic POPs. Blood cell transcript levels of genes involved in the function of T and B cells (FC like receptors 2 and 5, cytotoxic T-lymphocyte associated protein 4 and protein tyrosine phosphatase non-receptor type 22) were increased with plasma PFAS concentrations. These results suggest that changes in thyroid and immune systems in adult male walruses are linked to current levels of contaminant exposure.

Contaminants in Atlantic walruses in Svalbard part 1: Relationships between exposure, diet and pathogen prevalence.

This study investigated relationships between organohalogen compound (OHC) exposure, feeding habits, and pathogen exposure in a recovering population of Atlantic walruses (Odobenus rosmarus rosmarus) from the Svalbard Archipelago, Norway. Various samples were collected from 39 free-living, apparently healthy, adult male walruses immobilised at three sampling locations during the summers of 2014 and 2015. Concentrations of lipophilic compounds (polychlorinated biphenyls, organochlorine pesticides and polybrominated diphenyl ethers) were analysed in blubber samples, and concentrations of perfluoroalkylated substances (PFASs) were determined in plasma samples. Stable isotopes of carbon and nitrogen were measured in seven tissue types and surveys for three infectious pathogens were conducted. Despite an overall decline in lipophilic compound concentrations since this population was last studied (2006), the contaminant pattern was similar, including extremely large inter-individual variation. Stable isotope ratios of carbon and nitrogen showed that the variation in OHC concentrations could not be explained by some walruses consuming higher trophic level diets, since all animals were found to feed at a similar trophic level. Antibodies against the bacteria Brucella spp. and the parasite Toxoplasma gondii were detected in 26% and 15% of the walruses, respectively. Given the absence of seal-predation, T. gondii exposure likely took place via the consumption of contaminated bivalves. The source of exposure to Brucella spp. in walruses is still unknown. Parapoxvirus DNA was detected in a single individual, representing the first documented evidence of parapoxvirus in wild walruses. Antibody prevalence was not related to contaminant exposure. Despite this, dynamic relationships between diet composition, contaminant bioaccumulation and pathogen exposure warrant continuing attention given the likelihood of climate change induced habitat and food web changes, and consequently OHC exposure, for Svalbard walruses in the coming decades.

Characterizing cytotoxic and estrogenic activity of Arctic char tissue extracts in primary Arctic char hepatocytes.

Contaminants from various anthropogenic activities are detected in the Arctic due to long-range atmospheric transport, ocean currents, and living organisms such as migrating fish or seabirds. Although levels of persistent organic pollutants (POPs) in Arctic fish are generally low, local hot spots of contamination were found in freshwater systems such as Lake Ellasjøen at Bjørnøya (Bear Island, Norway). Higher concentrations of organic halogenated compounds (OHC), and higher levels of cytochrome P450 and DNA-double strand breaks were reported in Arctic char (Salvelinus alpinus) from this lake compared to fish from other lakes on Bjørnøya. Although several of the measured contaminants are potential endocrine disrupters, few studies have investigated potential endocrine disruptive effects of the contaminant cocktail in this fish population. The aim of this study was to compare acutely toxic and estrogenic potency of the cocktail of pollutants as evidenced by cytotoxic and/or estrogenic effects in vitro using extracts of Arctic char livers from contaminated Lake Ellasjøen with those from less contaminated Lake Laksvatn at Bjørnøya. This was performed by in situ sampling and contaminant extraction from liver tissue, followed by chemical analysis and in vitro testing of the following contaminated tissue extracts: F1-nonpolar OHC, F2-polar pesticides and metabolites of OHC, and F3-polar OHC. Contaminant levels were highest in extracts from Ellasjøen fish. The F2 and F3 extracts from Lake Laksvatn and Lake Ellasjøen fish reduced in vitro cell viability at a concentration ratio of 0.03-1 relative to tissue concentration in Arctic char. Only the F3 liver extract from Ellasjøen fish increased in vitro vitellogenin protein expression. Although compounds such as estrogenic OH-PCBs were quantified in Ellasjøen F3 extracts, it remains to be determined which compounds were inducing estrogenic effects.

Environmental Chemicals Modulate Polar Bear (Ursus maritimus) Peroxisome Proliferator-Activated Receptor Gamma (PPARG) and Adipogenesis in Vitro.

We studied interactions between polar bear peroxisome proliferator-activated receptor gamma (pbPPARG) and selected compounds using a luciferase reporter assay and predictions through molecular docking. Furthermore, we studied adipogenesis by liver and adipose tissue extracts from a polar bear and three synthetic mixtures of contaminants in murine 3T3-L1 preadipocytes and polar bear adipose tissue-derived stem cells (pbASCs). PCB153 and p,p'-DDE antagonized pbPPARG, although their predicted receptor-ligand affinity was weak. PBDEs, tetrabromobisphenol A, and PCB170 had a weak agonistic effect on pbPPARG, while hexabromocyclododecane, bisphenol A, oxychlordane, and endosulfan were weak antagonists. pbPPARG-mediated luciferase activity was suppressed by synthetic contaminant mixtures reflecting levels measured in polar bear adipose tissue, as were transcript levels of PPARG and the PPARG target gene fatty acid binding protein 4 (FABP4) in pbASCs. Contaminant extracts from polar bear tissues enhanced triglyceride accumulation in murine 3T3-L1 cells and pbASCs, whereas triglyceride accumulation was not affected by the synthetic mixtures. Chemical characterization of extracts using nontarget methods revealed presence of exogenous compounds that have previously been reported to induce adipogenesis. These compounds included phthalates, tonalide, and nonylphenol. In conclusion, major legacy contaminants in polar bear adipose tissue exert antagonistic effects on PPARG, but adipogenesis by a mixture containing emerging compounds may be enhanced through PPARG or other pathways.

Perfluoroalkylated substances (PFASs) and legacy persistent organic pollutants (POPs) in halibut and shrimp from coastal areas in the far north of Norway: Small survey of important dietary foodstuffs for coastal communities.

Halibut (Hippoglossus hippoglossus) and shrimps (Pandalus borealis) are regular foodstuffs for communities in northern Norway and important species for the coastal fishing industry. This is the first study to present a comprehensive overview of the contaminant status of these species, with emphasis on unregulated perfluoroalkylated substances (PFAS). The contaminant concentrations were low and within tolerable levels for human dietary exposure. Median Σpolychlorinated biphenyls (PCB) were 4.9 and 2.5ng/g ww for halibut and unpeeled shrimps, respectively. Concentrations of perfluorooctane sulfonate (PFOS) - the most abundant PFASs - were 0.9 and 2.7ng/g ww in halibut and shrimp, respectively. The halibut fillets were dominated by PCBs, which contributed to 50% of the total POPs load, followed by ΣDDTs; 26% and PFASs (18%), whereas shrimps were dominated by PFASs (74%). ΣPBDEs (polybrominated diphenyl ethers) contributed to 1-4% of the total POP load. Local sources are not contributing significantly to the contaminant burden in these species.

A broad cocktail of environmental pollutants found in eggs of three seabird species from remote colonies in Norway.

Eggs of 3 seabird species, common eider (Somateria mollisima), European shag (Phalacrocorax aristotelis aristotelis), and European herring gull (Larus argentatus), were surveyed for a broad range of legacy and emerging pollutants to assess chemical mixture exposure profiles of seabirds from the Norwegian marine environment. In total, 201 chemical substances were targeted for analysis ranging from metals, organotin compounds, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and associated metabolites, chlorinated paraffins, chlorinated and nonchlorinated organic pesticides, per- and polyfluoroalkyl substances (PFAS), dechlorane plus, octachlorostyrene, brominated flame retardants (BFRs), organophosphorous compounds, brominated and alkyl phenols, cyclic siloxanes, and phthalates. Of the chemicals targeted, 149 substances were found above the detection limits, with metals dominating the contaminant profile and comprising 60% of the total contaminant load. Polychlorinated biphenyls, pesticides, organophosphorous compounds, and PFAS were the dominant contaminant classes of organic pollutants found within the seabird species, with the highest loads occurring in herring gulls, followed by shag, and common eider. New generation pollutants (e.g., PFAS, organophosphorous compounds, and alkylphenols) were detected at similar or higher concentrations than the legacy persistent organic pollutants (POPs). Time trends of reported concentrations of legacy POPs appear to have decreased in recent decades from the Norwegian coastal environment. Concentrations of detected pollutants do not appear to have a negative effect on seabird population development within the sampling area. Additional stress caused by pollutants, however, may affect seabird health more at the individual level.

Effect of reduced food intake on toxicokinetics of halogenated organic contaminants in herring gull (Larus argentatus) chicks.

The aim of the present study was to investigate how contaminant exposure and reduced food intake affect tissue distribution and biotransformation of halogenated organic contaminants (HOCs) in Arctic seabirds using herring gull (Larus argentatus) as a model species. Herring gull chicks were exposed for 44 d to cod liver oil containing a typical mixture of contaminants. Following exposure, food intake was reduced for a one-week period in a subgroup of the chicks. Polyclorinated biphenyls, organochlorine pesticides, and brominated flame retardants, as well as a wide range of hydroxy, methyl sulfone, and methoxy compounds were measured in liver, brain, and plasma samples. Additionally, phase I biotransformation enzyme activities and phase I and II messenger ribonucleic acid (mRNA) expression were investigated in the liver, brain, or both. Both contaminant exposure and reduced food intake had an increasing effect on the concentrations of HOCs and their metabolites. The HOC exposure and reduced food intake also led to increased 7-ethoxyresorufin-O-deethylation (EROD) activity, whereas mRNA expression of the biotransformation enzymes increased only following the reduced food intake. Tissue distribution of HOCs and their metabolites was not affected by either contaminant exposure or reduced food intake. In conclusion, the results indicate that biotransformation capacity and formation of HOC metabolites increase during reduced food intake. This finding supports the hypothesis that reduced food intake increases the susceptibility of Arctic animals to the effects of lipophilic HOCs.

Halogenated organic contaminants and their correlations with circulating thyroid hormones in developing Arctic seabirds.

Thyroid hormones are essential for normal growth and development and disruption of thyroid homeostasis can be critical to young developing individuals. The aim of the present study was to assess plasma concentrations of halogenated organic contaminants (HOCs) in chicks of two seabird species and to investigate possible correlations of HOCs with circulating thyroid hormone (TH) concentrations. Plasma from black-legged kittiwake (Rissa tridactyla) and northern fulmar (Fulmarus glacialis) chicks were sampled in Kongsfjorden, Svalbard in 2006. The samples were analyzed for thyroid hormones and a wide range of HOCs (polychlorinated biphenyls (PCBs), hydroxylated (OH-) and methylsulphoned (MeSO-) PCB metabolites, organochlorine pesticides (OCPs), brominated flame retardants (BFRs), and perfluorinated compounds (PFCs)). Concentrations of HOCs were generally low in kittiwake and fulmar chicks compared to previous reports. HOC concentrations were five times higher in fulmar chicks compared to in kittiwake chicks. PFCs dominated the summed HOCs concentrations in both species (77% in kittiwakes and 69% in fulmars). Positive associations between total thyroxin (TT4) and PFCs (PFHpS, PFOS, PFNA) were found in both species. Although correlations do not implicate causal relationships per se, the correlations are of concern as disruption of TH homeostasis may cause developmental effects in young birds.

Biotransformation of PCBs in Arctic seabirds: characterization of phase I and II pathways at transcriptional, translational and activity levels.

Arctic seabirds are exposed to a wide range of halogenated organic contaminants (HOCs). Exposure occurs mainly through food intake, and many pollutants accumulate in lipid-rich tissues. Little is known about how HOCs are biotransformed in arctic seabirds. In this study, we characterized biotransformation enzymes in chicks of northern fulmars (Fulmarus glacialis) and black-legged kittiwakes (Rissa tridactyla) from Kongsfjorden (Svalbard, Norway). Phase I and II enzymes were analyzed at the transcriptional, translational and activity levels. For gene expression patterns, quantitative polymerase chain reactions (qPCR), using gene-sequence primers, were performed. Protein levels were analyzed using immunochemical assays of western blot with commercially available antibodies. Liver samples were analyzed for phase I and II enzyme activities using a variety of substrates including ethoxyresorufin (cytochrome (CYP)1A1/1A2), pentoxyresorufin (CYP2B), methoxyresorufin (CYP1A), benzyloxyresorufin (CYP3A), testosterone (CYP3A/CYP2B), 1-chloro-2,4-nitrobenzene (CDNB) (glutathione S-transferase (GST)) and 4-nitrophenol (uridine diphosphate glucuronyltransferase (UDPGT)). In addition, the hydroxylated (OH-) polychlorinated biphenyls (PCBs) were analyzed in the blood, liver and brain tissue, whereas the methylsulfone (MeSO(2)-) PCBs were analyzed in liver tissue. Results indicated the presence of phase I (CYP1A4/CYP1A5, CYP2B, and CYP3A) and phase II (GST and UDPGT) enzymes at the activity, protein and/or mRNA level in both species. Northern fulmar chicks had higher enzyme activity than black-legged kittiwake chicks. This in combination with the higher SigmaOH-PCB to parent PCB ratios suggests that northern fulmar chicks have a different biotransformation capacity than black-legged kittiwake chicks.

Quantitative structure - photodegradation relationships of polybrominated diphenyl ethers, phenoxyphenols and selected organochlorines.

Among other developments, the technological revolution has lead to introduction of new chemicals to better serve in instruments and materials. The consequences of the extensive increase in use of new chemicals can be detected in the environment world wide, i.e. in wildlife and humans. To ensure this problem to be minimised in the future, new chemicals need to be subjected to predictive assessments before commercialised. To facilitate screening, qualitative structure-activity relationships, quantitative structure-activity relationships may be applied to describe reactivity of chemicals. Physico-chemical properties of chemicals such as partition coefficients and half-lives for the various environmental compartments are essential input data in multimedia environmental fate models. In this study we examine how structural characteristics can quantitatively describe laboratory determined photolytic half-lives of halogenated compounds of different classes, such as polybrominated diphenyl ethers (PBDEs), hydroxylated brominated diphenyl ethers (OH-PBDEs), and other organohalogens. A total of 30 chemicals with experimentally measured half-lives are used. Results reveal that the most important descriptors for describing the half-lives of the brominated compounds are the energy gap (GAP-1) between HOMO-1 and LUMO, the lowest partial charge on a halogen atom (Qhal-), topological polar surface area (TPSA), the atom with highest radical superdelocalizability (Rad-super+) and LUMO density (LUMO+).