Flame retardants and their associations with thyroid hormone-related variables in northern fulmars from the Faroe Islands.

Flame retardants (FRs) are widely reported in tissues of seabirds including birds sampled from remote areas. There is evidence that FRs can disrupt the hypothalamic-pituitary-thyroid (HPT) axis in seabirds, although information is limited on thyroid-related mechanisms and effects. This study investigated the associations between concentrations of polybrominated diphenyl ethers (PBDEs) and other FRs, and changes in the HPT axis in northern fulmars (Fulmarus glacialis) from the Faroe Islands (North Atlantic). Plasma concentrations of thyroid hormones (THs), hepatic deiodinase type 1 (D1) activity, and transcription of selected TH-related genes in liver were used as markers of HPT axis changes. Liver concentrations of a certain PBDE congeners and other FRs including pentabromoethylbenzene (PBEB), dechlorane 602 (Dec-602), and dechlorane plus (DP) were associated with changes in thyroid status. Specifically, liver PBDE, PBEB and Dec-602 concentrations were associated with plasma TH levels (free thyroxine [FT4] and total triiodothyronine [TT3]). Liver DP concentrations were positively correlated with the TT4:FT4 ratios and mRNA levels of UDP-glucuronyltransferase-1, while those of PBEB were negatively associated with TT4:TT3 ratios and D1 activity. D1 activity was also positively associated with the tri-, tetra- and hexa-BDE congeners. Moreover, transcription of ABCC2, a hepatic TH transporter, was associated with certain liver PBDE concentrations. Although PBDEs and other FRs may be potential inhibitors of D1 activity, only a few of the targeted FRs had modest associations with hepatic D1 activity. Regardless, the relationships reported herein indicated that exposure to moderate levels of FRs can be associated with thyroid axis perturbation at the molecular/biochemical levels in this North Atlantic seabird species.

The fate of poly- and perfluoroalkyl substances in a marine food web influenced by land-based sources in the Norwegian Arctic.

Although poly- and perfluorinated alkyl substances (PFAS) are ubiquitous in the Arctic, their sources and fate in Arctic marine environments remain unclear. Herein, abiotic media (water, snow, and sediment) and biotic media (plankton, benthic organisms, fish, crab, and glaucous gull) were sampled to study PFAS uptake and fate in the marine food web of an Arctic Fjord in the vicinity of Longyearbyen (Svalbard, Norwegian Arctic). Samples were collected from locations impacted by a firefighting training site (FFTS) and a landfill as well as from a reference site. Mean concentration in the landfill leachate was 643 ± 84 ng L-1, while it was 365 ± 8.0 ng L-1 in a freshwater pond and 57 ± 4.0 ng L-1 in a creek in the vicinity of the FFTS. These levels were an order of magnitude higher than in coastal seawater of the nearby fjord (maximum level , at the FFTS impacted site). PFOS was the most predominant compound in all seawater samples and in freshly fallen snow (63-93% of ). In freshwater samples from the Longyear river and the reference site, PFCA ≤ C9 were the predominant PFAS (37-59%), indicating that both local point sources and diffuse sources contributed to the exposure of the marine food web in the fjord. concentrations increased from zooplankton (1.1 ± 0.32 µg kg-1 ww) to polychaete (2.8 ± 0.80 µg kg-1 ww), crab (2.9 ± 0.70 µg kg-1 ww whole-body), fish liver (5.4 ± 0.87 µg kg-1 ww), and gull liver (62.2 ± 11.2 µg kg-1). PFAS profiles changed with increasing trophic level from a large contribution of 6:2 FTS, FOSA and long-chained PFCA in zooplankton and polychaetes to being dominated by linear PFOS in fish and gull liver. The PFOS isomer profile (branched versus linear) in the active FFTS and landfill was similar to historical ECF PFOS. A similar isomer profile was observed in seawater, indicating major contribution from local sources. However, a PFOS isomer profile enriched by the linear isomer was observed in other media (sediment and biota). Substitutes for PFOS, namely 6:2 FTS and PFBS, showed bioaccumulation potential in marine invertebrates. However, these compounds were not found in organisms at higher trophic levels.

Rapid determination of thyroid hormones in blood plasma from Glaucous gulls and Baikal seals by HybridSPE®-LC-MS/MS.

A rapid hybrid solid phase extraction (HybridSPE®) protocol tailored to liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) analysis, was developed for the determination of four thyroid hormones, L-Thyroxine (T4), 3,3',5-triiodo-L-thyronine (T3), 3,3',5'-triiodo-L-thyronine (rT3) and 3,3'-diiodo-L-thyronine (T2) in blood plasma from Glaucous gulls (Larus hyperboreus) and Baikal seals (Phoca sibirica). The use of target analyte specific 13C internal standards allowed quantification to be performed through the standard solvent calibration curves and alleviated the need to perform quantification with matrix match curves. The relative recoveries were 100.0-110.1 % for T4, 99.1-102.2 % for T3, 100.5-108.0 % for rT3, and 100.5-104.6 % for T2. The matrix effects ranged from -1.52 to -6.10 %, demonstrating minor signal suppression during analysis. The method intra-day precision (method repeatability, RSD %, N = 5, k = 1 day) and inter-day precision (method reproducibility, RSD %, N = 10, k = 2 days) at the 1 ng/mL concentration of fortification were 8.54-15.4 % and 15.4-24.8 %, respectively, indicating acceptable chromatographic peak stabilities for all target THs even at trace level concentrations. The method limit of detection (LOD) for T4, T3, rT3 and T2 was 0.17, 0.16, 0.30 and 0.17 ng/mL, respectively. The HybridSPE® protocol was simple and rapid (<1 min) upon application, while the HybridSPE® cartridge did not require (as in classical SPE cartridges) any additional equilibration nor conditioning step prior sample loading. A total of 46 blood plasma samples, 30 samples collected from Glaucous gulls and 16 samples collected from Baikal seals, were analyzed for thyroid hormones to demonstrate the applicability of the developed method in these wildlife species. The concentrations of T4 and T3 in blood plasma from the Glaucous gulls were 5.95-44.2 and 0.37-5.61 ng/mL, respectively, whereas those from Baikal seals were 3.57-46.5 and 0.45-2.07 ng/mL, respectively. In both species, rT3 demonstrated low detection rate, while T2 was not detected. Furthermore, cross-array comparison between the HybridSPE®-LC-MS/MS protocol and an established routine radioimmunoassay (RIA) kit-based method was performed for T4 and T3 concentrations from selected Baikal seal plasma samples.

Evidence of avian influenza virus in seabirds breeding on a Norwegian high-Arctic archipelago.

BACKGROUND: Wild aquatic birds serve as the natural reservoir for avian influenza virus (AIV), a disease with significant implications for avian and mammalian health. Climate change is predicted to impact the dynamics of AIV, particularly in areas such as the Arctic, but the baseline data needed to detect these shifts is often unavailable. In this study, plasma from two species of gulls breeding on the high-Arctic Svalbard archipelago were screened for antibodies to AIV. RESULTS: AIV antibodies were found in black-legged kittiwake (Rissa tridactyla) samples from multiple years, as well as in glaucous gulls (Larus hyperboreous) samples. CONCLUSIONS: Despite small sample sizes, evidence of exposure to AIV was found among Svalbard gulls. A wider survey of Svalbard avian species is warranted to establish knowledge on the extent of AIV exposure on Svalbard and to determine whether active infections are present.

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.