Several unknown, abundant brominated compounds (BCs) were recently detected in the blubber of dolphins and other marine mammals from Queensland (northeast Australia). The BCs were interpreted as potential natural products due to the lack of anthropogenic sources for these compounds. This study investigated whether some of the BCs accumulated by diverse marine mammal species are identical with natural BCs previously isolated from sponges (Dysidea sp.) living in the same habitat. Isolates from sponges and mollusks (Asteronotus cespitosus) were compared with the signals detected in the mammals' tissue. Mass spectra and gas chromatography retention times on four different capillary columns of the isolates from sponges and mammals were identical in all respects. This proves that the chemical name of the compound previously labeled BC-2 is 4,6-dibromo-2-(2',4'-dibromo)phenoxyanisole and that the chemical name of BC-11 is 3,5-dibromo-2-(3',5'-dibromo,2'-methoxy)phenoxyanisole. Using a quantitative reference solution of BC-2, we established that the concentrations of the brominated metabolites found in the marine mammals are frequently >1 mg/kg. The highest concentration (3.8 mg/kg), found in a sample of pygmy sperm whale (Kogia breviceps), indicates that BC-2 is a bioaccumulative, natural organohalogen compound. This is supported by the concentrations of the BCs in our samples being equal to the highest concentrations of anthropogenic BCs in any environmental sample. The quantitative determination of BC-2 in blubber of marine mammals from Africa and the Antarctic suggests that BC-2 is widespread. These results are direct proof that marine biota can produce persistent organic chemicals that accumulate to substantial concentrations in higher trophic organisms.
A sample cleanup procedure using microwave-assisted extraction (MAE) with focus open vessel (FOV-MAE) technique was validated for the determination of organohalogen compounds in the blubber of a Weddell seal (Leptonychotes Weddelli) from the Antarctic (King George Island, 62 degrees 14' S, 58 degrees 40' W). Good reproducibility in replicate analysis of samples confirms the suitability of the method for samples with very low persistent organic pollutant (POP) concentrations. The method was used to analyze three additional blubber samples of Weddell seals from King George Island. This community of Weddell seals showed the lowest DDT (11-19 microg/kg) and PCB (1-2.5 microg/kg) concentrations so far detected in comparable marine mammals from all over the world. The concentrations determined in the four Weddell seals were also typical for the population at King George Island. However, the DDT and PCB concentrations on King George Island were one order of magnitude lower than in samples of the same species from other sites in the Antarctic (located between 69 degrees S and 78 degrees S). This suggests a wide variability of organohalogen levels in the Antarctic, depending on the geographic site. King George Island (62 degrees S) is found at the outskirts of the Antarctic Peninsula, i.e., the region with the mildest climate in the Antarctic. Low organohalogen levels at this site were attributed to a lower degree of condensation in comparison with locations further south. Most of the reference samples were taken in the Weddell and Ross Seas, i.e., from coastlines as close as possible to the pole. Consequently, other sites on the same latitude as the Weddell and Ross Seas are found on the Antarctic continent This raises the question whether high proportions of organohalogens are being deposited on the Antarctic continent where they are not available to marine organisms. Although this hypothesis has to be proven in follow-up studies, our study clearly demonstrates that it is complicated, if not impossible, to derive time trends in concentrations of POPs in biota from different reference sites in the Antarctic.
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