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The assessment of chemical pollution in free-ranging living mammals is viable using remote biopsies and portrays a comprehensive scenario of environmental health. The Southwestern Atlantic Ocean holds incredible biodiversity, but it is under the constant and invisible threat of persistent organic pollutants (POPs) of anthropogenic origin, such as pesticides, brominated flame retardants, and industrial-use compounds (e.g., PCBs). Thus, this study aimed to assess the bioaccumulation of POPs (PCBs, DDTs, HCB, mirex and PBDEs) and natural organobromine compounds (MeO-BDEs) using gas-chromatography coupled to mass spectrometry in biopsy samples of Atlantic spotted dolphins (Stenella frontalis, n = 20) that inhabit and forage both inside and in adjacent areas to degraded (Guanabara Bay) and conserved (Ilha Grande Bay) coastal bays in the Southeastern Brazil. Among the studied compounds, PCBs were predominant in the contamination profile with median concentration of 97.0 μg.g -1 lipid weight (lw), followed by the sum of the p,p' isomers of DDT, DDD, and DDE of 11.0 μg.g -1 lw, the brominated flame retardants PBDEs of 1.6 μg.g -1 lw, and the other organochlorine pesticides mirex of 0.78 μg.g -1 lw, and HCB of 0.049 μg.g -1 lw. The MeO-BDEs were detected with a median concentration of 22.8 μg.g -1 lw. 85 % of the Atlantic spotted dolphins analyzed in this study presented PCB concentration that exceeded even the less conservative threshold limits for adverse health effects (41 μg.g -1 lw). This study shows that despite the conservation status of preserved bays, cetacean species foraging in these locations are still under increased threat. Hence chemical pollution demands local and global efforts to be mitigated., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Guiana dolphins, Sotalia guianensis, are vulnerable to extinction along their distribution on the Brazilian coast and assessing chemical pollution is of utmost importance for their conservation. For this study, 51 carcasses of Guiana dolphins were sampled across the Brazilian coast to investigate legacy and emerging brominated flame retardants (BFRs) as well as the naturally-produced MeO-BDEs. PBDEs and MeO-BDEs were detected in all samples analyzed, whereas emerging BFRs were detected in 16 % of the samples, all in Rio de Janeiro state. PBDE concentrations varied between 2.24 and 799 ng.g -1 lipid weight (lw), emerging BFRs between 0.12 and 1.51 ng.g -1 lw and MeO-BDEs between 3.82 and 10,247 ng.g -1 lw. Concentrations of legacy and emerging BFRs and natural compounds varied considerably according to the sampling site and reflected both the local anthropogenic impact of the region and the diversity/mass of biosynthesizers. The PBDE concentrations are lower than what was found for delphinids in the Northern Hemisphere around the same sampling period and most sampling sites presented mean concentrations lower than the limits for endocrine disruption known to date for marine mammals of 460 ng.g -1 lw, except for sampled from Santa Catarina state, in Southern Brazil. Conversely, MeO-BDE concentrations are higher than those of the Northern Hemisphere, particularly close to the Abrolhos Bans and Royal Charlotte formation, that are hotspots for biodiversity. Despite the elevated concentrations reported for this group, there is not much information regarding the effects of such elevated concentrations for these marine mammals. The distinct patterns observed along the Brazilian coast show that organobrominated compounds can be used to identify the ecological segregation of delphinids and that conservation actions should be planned considering the local threats., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Organic contaminants with toxic effects, like the conventional brominated flame retardants (BFRs) and BFRs of emergent concern, and their synergistic effects with other micropollutants, can be an additional threat to delphinids. Rough-toothed dolphins (Steno bredanensis) populations strongly associated with coastal environments already face a potential risk of decline due to high exposure to organochlorine pollutants. Moreover, natural organobromine compounds are important indicators of the environment's health. Polybrominated diphenyl ethers (PBDEs), pentabromoethylbenzene (PBEB), hexabromobenzene (HBB) and the methoxylated PBDEs (MeO-BDEs) were determined in the blubber of rough-toothed dolphins from three ecological populations from the Southwestern Atlantic Ocean (Southeastern, Southern and Outer Continental Shelf/Southern populations, SE, S, and OCS/S, respectively). The profile was dominated by the naturally produced MeO-BDEs (mainly 2'-MeO-BDE 68 and 6-MeO-BDE 47), followed by the anthropogenic BFRs PBDEs (mainly BDE 47). Median ΣMeO-BDE concentrations varied between 705.4 and 3346.0 ng g -1 lw among populations and ΣPBDE from 89.4 until 538.0 ng g -1 lw. Concentrations of anthropogenic organobromine compounds (ΣPBDE, BDE 99 and BDE 100) were higher in SE population than in OCS/S, indicating a coast - ocean gradient of contamination. Negative correlations were found between the concentration of the natural compounds and age, suggesting their metabolization and/or biodilution and maternal transference. Conversely, positive correlations were found between the concentrations of BDE 153 and BDE 154 and age, indicating low biotransformation capability of these heavy congeners. The levels of PBDEs found are concerning, particularly for SE population, because they are similar to concentrations known for the onset of endocrine disruption in other marine mammals and may be an additional threat to a population in a hotspot for chemical pollution., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Liver samples from 51 cetaceans, comprising 10 species, stranded between 1994 and 2006 in a highly industrialized and urbanized region in Southeast Brazil, were analyzed for polybrominated diphenyl ethers (PBDEs) and methoxylated-PBDEs (MeO-PBDEs). A concentration range of PBDEs (3-5960ng/g lw) similar to that observed in Northern Hemisphere dolphins was found. MeO-PBDE concentrations in continental shelf (CS) dolphins from Brazil are among the highest detected to date in cetaceans (up to 250microg/g lw). Higher SigmaMeO-PBDE concentrations were measured in CS and oceanic dolphins than in estuarine dolphins. The SigmaPBDE/SigmaMeO-PBDE ratio varied significantly ranging from a mean value of 7.12 to 0.08 and 0.01 for estuarine, CS and oceanic species, respectively. A positive correlation was observed between SigmaPBDE and year of stranding of male estuarine dolphins (Sotalia guianensis), which suggests temporal variation in the exposure. Placental transfer of organobrominated compounds was also evidenced in S. guianensis.