Occurrence of halogenated natural products in highly consumed fish from polluted and unpolluted tropical bays in SE Brazil.

Natural compounds from the metabolism of marine organisms have been detected at high concentrations in environmental samples which are not the producers of these compounds. These natural substances are known as halogenated natural products (HNPs). HNPs are possibly toxic halogenated compounds analogous to POPs that may bioaccumulate and biomagnify along the food web and pose a further risk to human and environmental health. The present study analyzed the occurrence of HNPs in the edible muscle of the three most consumed commercial fish species in the state of Rio de Janeiro: sardine (Sardinella brasiliensis), whitemouth croaker (Micropogonias furnieri) and mullet (Mugil liza) from the highly polluted Guanabara Bay (GB) and the less polluted Ilha Grande Bay (IGB). The analytical steps included Soxhlet extraction, clean-up step and injection in a gas chromatography system coupled to a mass spectrometer operated in the electron-capture negative ion mode (GC/ECNI-MS). The compounds 2,4,6-TBP, 2,4,6-TBA, MHC-1, Q1, 6-MeO-BDE 47 and 2'-MeO-BDE 68 were found in the analyzed fish from both studied areas. Q1, 6-MeO-BDE 47 and 2'-MeO-BDE 68 showed the highest concentrations in samples. Q1 concentrations in the sardines from IGB were higher than the sardines from GB (p < 0.05) and higher than the other IGB species (p < 0.05). The differences found among the species may be related to their characteristic habitat and diet. It is noteworthy that most of these compounds do not have any toxicological reference value. Moreover, the HNPs are being detected in species of low trophic level and since this study has worked only with commercial species, these fish may be considered as a source for human exposure to these natural compounds.

Halogenated Natural Products in Dolphins: Brain-Blubber Distribution and Comparison with Halogenated Flame Retardants.

Halogenated natural products (MHC-1, TriBHD, TetraBHD, MeO-PBDEs, Q1, and related PMBPs) and halogenated flame retardants (PBDEs, HBB, Dec 602, Dec 603, and DP) in blubber and brain are reported from five Alboran Sea delphinids (Spain). Both HNPs and HFRs were detected in brain, implying that they are able to surpass the blood-brain barrier and reach the brain, which represents a new finding for some compounds, such as Q1 and PMBPs, MHC-1, TriBHD, TetraBHD, or Dec 603. Moreover, some compounds (TetraBHD, BDE-153, or HBB) presented higher levels in brain than in blubber. This study evidence the high concentrations of HNPs in the marine environment, especially in top predators. It shows the importance of further monitoring these natural compounds and evaluating their potential toxicity, when most studies focus on anthropogenic compounds only. While no bioaccumulation was found for ∑HNPs, ∑HFRs increased significantly with body size for both common and striped dolphins. Studies evaluating BBB permeation mechanisms of these compounds together with their potential neurotoxic effects in dolphins are recommended.