Exposure to legacy and alternative flame retardants in two harbor seal populations and the association with blubber fatty acid profiles.

Flame retardants (FRs) are ubiquitously present in various environmental compartments due to widespread application. However, there have been few reports on the alternative FRs in harbor seals, and their relationship with fatty acid (FA) profiles have largely been overlooked. Here, we investigated the levels of legacy and alternative FRs and FA profiles in the blubber of harbor seals from the coasts of South Sweden (2009-2016) and Northeastern US (NE US) (1999-2010). We observed different proportions of mono- and poly-unsaturated FAs (MUFAs and PUFAs) between the two populations, which may reflect variations in the diet. Significantly higher concentrations of ΣPBDE were also observed in harbor seals from US compared to those from Sweden, both dominated by BDE 47. By comparison, the levels of alternative FRs, noticeably HBBZ and PBEB were much lower compared to those of PBDEs. Moreover, we found a positive correlation between BDE 99 and Σn-6/Σn-3 PUFA in harbor seals from Sweden. In addition, BDE 153 and BDE 154 were positively correlated with ΣUFA/ΣSFA in seals from Sweden and US, respectively. Our results imply the influence of diet in FA profiles and FR concentrations in top predators, as well as the importance of blubber FA characteristics in indicating FR exposure. Further investigations are required to assess the risk of exposure in these harbor seals, as well as to elucidate the underlying mechanisms associating FA profiles with FR exposure.

Spatiotemporal Trends of Legacy and Alternative Flame Retardants in Harbor Seals from the Coasts of California, the Gulf of Maine, and Sweden.

Temporal trends of polybrominated diphenyl ethers (PBDEs) have been extensively studied in various environmental compartments globally. However, despite the increasing use of alternative flame retardants following PBDE bans, the spatiotemporal trends of these replacements have rarely been studied, and the available results are often inconsistent. In the present study, we retrospectively investigated the spatiotemporal trends of PBDEs and a suite of alternative brominated FRs (aBFRs) and chlorinated FRs (i.e., dechloranes or DECs) in three harbor seal (Phoca vitulina) populations from the coasts of California, the Gulf of Maine, and southern Sweden during 1999-2016. We observed significantly decreasing trends of ΣPBDEs in all the three populations at an annual rate of 9-11%, which were predominantly driven by the declining concentrations of tetra- and penta-BDEs. The levels of ΣaBFRs decreased significantly in seals from California (mainly 1,3,5-tribromobenzene) and Sweden (mainly hexabromobenzene), while no trend was observed for those from Maine. By contrast, DECs (dominated by DEC 602) did not decrease significantly in any population. Compared with the consistent PBDE congener profiles across regions, aBFRs and DECs exhibited varying compositional profiles between regions, likely indicating region-specific sources of these alternative FR mixtures. Spatial analysis also revealed regional differences in the concentrations of PBDEs, aBFRs, and DECs in harbor seals. Our reconstructed spatiotemporal trends suggest the effective regulation of commercial penta-BDE mix in these regions and warrant further monitoring of the higher brominated BDEs and alternative FRs.

Hepatic Fatty Acid Profiles Associated with Exposure to Emerging and Legacy Halogenated Contaminants in Two Harbor Seal Populations across the North Atlantic.

Fatty acids (FAs) have been extensively used as indicators of foraging ecology in marine mammals, yet their association with exposure to contaminants has rarely been investigated. The present study provided the first characterization of the relationship between hepatic FA profiles and exposure to a suite of contaminants in a sentinel species─the harbor seal (Phoca vitulina)─from the Gulf of Maine and the south coast of Sweden. FA profiles differed in the two seal populations, and the levels of legacy and alternative brominated flame retardants and polyhalogenated carbazoles were significantly elevated in Maine seals. Correlations between individual FAs and multiple flame retardants (FRs) and poly- and perfluoroalkyl substances (PFASs) were found in seals from both populations. Moreover, several FR and PFAS chemicals were significantly associated with the estimated desaturating enzyme activity inferred from the FA profiles. The ratios of poly to monounsaturated FAs (∑PUFAs/∑MUFAs) and those of unsaturated to saturated FAs (∑UFAs/∑SFAs) were significantly associated with HBBZ, PFHxS, or BDE 47 in seals from Maine and Sweden, whereas ∑n - 6/∑n - 3 PUFAs was significantly associated with BDE 154 and 36-CCZ in Swedish and Maine seals, respectively. Our results suggest the lipid metabolism-disrupting potential of these contaminants in marine mammals and warrant continuous biomonitoring and risk assessment, considering the critical role of PUFAs in vital biological processes.

Photodegradation of 1,3,5-Tris-(2,3-dibromopropyl)-1,3,5-triazine-2,4,6-trione and decabromodiphenyl ethane flame retardants: Kinetics, Main products, and environmental implications.

Photodegradation has been demonstrated as one of the important environmental factors affecting the fate of contaminants such as brominated flame retardants (BFRs). However, a number of emerging BFRs, particularly those with high bromine substitution, have rarely been investigated for their photodegradation kinetics. Our study evaluated photodegradation of two highly brominated FRs, 1,3,5-tris-(2,3-dibromopropyl)-1,3,5-triazine-2,4,6-trione (TDBP-TAZTO) and decabromodiphenyl ethane (DBDPE), under various conditions. The results indicated that the degradation kinetics was affected by UV irradiation wavelength, intensity, solvent type, as well as the structural characteristics. TDBP-TAZTO exhibited degradation half-lives (t1/2) of 23.5-6931 min under various UV irradiation conditions and 91.2 days under natural sunlight. Its degradation was much slower than that of DBDPE which exhibited t1/2 of 0.8-101.9 min under UV and 41.3 min under natural sunlight. A variety of degradation products were detected as a result of different breakdown pathways. This indicated that photodegradation could substantially influence the fate of these highly brominated FRs, resulting in a cocktail of degradation products as environmentally occurring contaminants. This could also complicate the evaluation of the ecological risks of these target flame retardants, given that degradation products generally possess physicochemical properties and biological effects different from their parent chemicals.