Brominated flame retardants and natural organobrominated compounds in a vulnerable delphinid species along the Brazilian coast.

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.

Organochlorine contaminants in Rio skate (Rioraja agassizii), an endangered batoid species, from southeastern coast of Brazil.

A global movement towards decreases in elasmobranch overfishing has been noted in the last decades. However, discussion concerning the effects of POP contamination on the health and survival of these organisms is still recent. These compounds can affect the immune and endocrine systems of both sharks and batoids, impairing reproduction and impacting species recruitment, acting synergistically alongside overfishing effects. In this context, this study investigated the concentration of organochlorine compounds in liver of 29 individuals of Rioraja agassizii, a commercially exploited skate classified as Vulnerable by IUCN and as Endangered in Brazil. Contaminant concentrations were higher in adults compared to juveniles. Distinct contamination profiles were observed, suggesting different groups within the investigated population and revealing contaminants as a potential tool to assess population ecology. PCB levels were considered a concern as they resemble concentrations in ecosystems from the northern hemisphere, where deleterious effects on elasmobranchs have been observed.

Pyrethroid insecticides along the Southwestern Atlantic coast: Guiana dolphin (Sotalia guianensis) as a bioindicator.

The presence of pyrethroid compounds in hepatic tissue of Guiana dolphins (Sotalia guianensis) is reported for the first time. Twelve pyrethroids were determined in 50 animals from eight locations of the Brazilian coast. The highest average concentration of total pyrethroids (∑PYR) was 1166 ng.g-1 lw, with values ranging from 148 to 5918 ng.g-1 lw, in Ilha Grande Bay, Rio de Janeiro State, while the Espírito Santo State had the highest median, 568 ng.g-1 lw. Permethrin was the predominant compound in most areas, contributing for 42% to 81% of the ∑PYR, whereas cypermethrin was the most abundant compound in Guanabara and Sepetiba bays (79% and 81%, respectively), both located in Rio de Janeiro State. Biological factors were not correlated with pyrethroids concentration. Tetramethrin and es/fenvalerate compounds were negatively correlated to the age, suggesting degradation/metabolization capacity in these animals that increases throughout life. Despite being metabolized and excreted, the wide use of these pollutants is reflected in relevant concentrations found in Guiana dolphins. This is the first study evaluating pyrethroids in a representative number of hepatic samples and covering >2600 km of coast. The overall lack of information on pyrethroids in cetaceans highlights the importance of understanding the profile and distribution of these pollutants in dolphins which exclusively inhabit the Southwestern Atlantic coast.

Organochlorine compound accumulation in delphinids from Rio de Janeiro State, southeastern Brazilian coast.

The present study investigated organochlorine compound levels (PCBs, DDTs and HCB) in blubber samples of six delphinid species from Rio de Janeiro State, southeastern Brazilian coast. The species analyzed inhabit the continental shelf (one killer whale, one false killer whale, two bottlenose dolphins, three rough-toothed dolphins, and four long-beaked common dolphins) and open ocean (four Fraser's dolphins). PCBs represented the greatest proportion of the sum of all measured organochlorines (from 0.60 to 257.2 µg g(-1) lw), followed by DDTs (from 0.15 to 125.6 µg g(-1) lw), and, at last, HCB (from

Pyrethroids: a new threat to marine mammals?

The present study constitutes the first investigation to demonstrate pyrethroid bioaccumulation in marine mammals, despite the assumption that these insecticides are converted to non-toxic metabolites by hydrolysis in mammals. Twelve pyrethroids were determined in liver samples from 23 male franciscana dolphins from Brazil. The median concentration values for total pyrethroids were 7.04 and 68.4 ng/g lw in adults and calves, respectively. Permethrin was the predominant compound, contributing for 55% of the total pyrethroids. Results showed a distinct metabolic balance of pyrethroids through dolphin life. High loads are received at the beginning of their lives and, when they reach sexual maturity, these mammals seem to degrade/metabolize pyrethroids. Maternal transfer of these compounds was also evaluated through the analysis of breast milk and placenta samples. Pyrethroids were detected in both matrices, with values between 2.53-4.77 ng/g lw and 331-1812 ng/g lw, respectively. Therefore, for the first time, a study shows mother-to-calf transfer of pyrethroids by both gestational and lactation pathways in dolphins.

High accumulation of perfluorooctane sulfonate (PFOS) in marine tucuxi dolphins (Sotalia guianensis) from the Brazilian coast.

Perfluorooctane sulfonate (PFOS) and other perfluoroalkyl compounds (PFCs) were measured in liver samples from 29 marine tucuxi dolphins from Rio de Janeiro state (RJ), Brazil. PFC measurement combined liquid chromatography and mass spectrometry, using a CapLC system connected to a Quadrupole-LIT mass spectrometer. PFOS was the only PFC detected and it was so in all samples. PFOS concentrations (ng x g(-1) dw) of dolphins (n=23) from the highly contaminated Guanabara Bay (in RJ) varied between 43 and 2431 as well as between 76 and 427 from areas of RJ other than the quoted bay (n=6). Concentrations of three fetuses and one neonate varied between 664 and 1590. Fetus/mother ratios were calculated in two situations (2.75 and 2.62). It seems that mother-to-calf transference plays important role for relationships between PFOS and age. When a one-year-old male calf presenting 2431 ng x g(-1) dw was excluded from the test, significant correlations were observed between PFOS concentrations and both age and total length. Despite the placental transference, PFOS concentrations were not significantly lower in females than in males. PFOS levels in marine tucuxi dolphins from Guanabara Bay are among the highest detected to date in cetaceans, and this may represent a threat to the small population concerned.

Evaluation of cetacean exposure to organotin compounds in Brazilian waters through hepatic total tin concentrations.

In Brazil, there is no restriction to the use of organotins (OTs). Previous investigations have shown that hepatic SigmaSn in cetaceans is predominantly organic. Hepatic SigmaSn concentrations were determined by GFAAS in 67 cetaceans (13 species) that stranded on Rio de Janeiro (RJ) and Espirito Santo (ES) states. Concentrations (in ng/g wet wt.) of marine tucuxis (n=20) from the highly contaminated Guanabara Bay (in RJ) varied from 1703 to 9638. Concentrations of three marine tucuxi foetuses and one newborn calf (all from Guanabara Bay) varied between 431 and 2107. Contrastingly, the maximum level among 19 oceanic dolphins was 346, and 15 out of these 19 specimens presented concentrations below detection limit. The levels of Sn in six marine tucuxis from a less contaminated area (ES) varied from below detection limit to 744. Comparing to the literature, coastal cetaceans from Brazil appear to be highly exposed to OTs.