Structures of polybrominated hexahydroxanthene derivatives (PBHDs) previously detected in commercial fish from the Mediterranean Sea and mussels from New Zealand were assigned to 2,7-dibromo-4a-bromomethyl-1,1-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-xanthene (TriBHD) and 2,5,7-tribromo-4a-bromomethyl-1,1-dimethyl-2,3,4,4a,9,9a-hexahydro-1H-xanthene (TetraBHD) by comparing their gas chromatography/mass spectrometry (GC/MS) features with isolates from an Australian sponge of the Cacospongia genus. Because of the geographic distance between the Mediterranean Sea in Europe (origin of the fish) and Australia (origin of the sponge), a closely related sponge, Scalarispongia scalaris, was collected in the Mediterranean Sea and analyzed for PBHDs and other halogenated compounds. The Mediterranean sponge contained the PBHDs at 37 mg/kg dry weight. Using quantitative standards for the first time, the PBHD concentrations in fish and mussel samples published earlier were re-examined. Concentrations of up to 1 mg/kg TriBHD and 0.5 mg/kg TetraBHD were determined in the lipids. No correlation with 2,2', 4,4', 5,5'-hexachlorobiphenyl (PCB 153) or p,p'-DDE was found, which is in agreement with other marine halogenated natural products detected in the fish samples. Besides the PBHDs, further unknown halogenated compounds were detected in the Mediterranean sponge, some of which were also detected in commercial fish. GC/electron ionization-MS analysis showed that a major mixed-halogenated compound in the sponge had a molecular ion at m/z 480 and contained three bromines, three chlorines, and 9-10 carbons. No corresponding structure has been described for this feature in the scientific literature. This sponge secondary metabolite and potential novel halogenated natural product was also detected in commercial fish. Another prominent mixed halogenated compound detected both in sponge and fish was the dibromotrichloro monoterpene MHC-1 (C(10)H(13)Br(2)Cl(3)).
During routine analysis of commercial fish on halogenated pollutants, an unknown tribromo component (TriBHD) was initially detected as an abundant peak in sample extracts from the Mediterranean Sea. The molecular formula was established to be C16H19Br3O by gas chromatography with electron ionization high-resolution mass spectrometry (GC/EI-HRMS). GC/EI-MS data were virtually identical with a polybrominated hexahydroxanthene derivative (PBHD) previously isolated from an Australian sponge species known to occur in the Mediterranean Sea as well. A tetrabromo isomer (TetraBHD) was also found in the fish samples. The concentrations of TriBHD and other halogenated compounds in commercial fish (sea bass, gilt head bream, anchovy, sardine, and salmon) were estimated with GC/electron capture detection (ECD). Using the ECD response of trans-nonachlor, the concentration of TriBHD reached up to 90 ng/g lipid weight and accounted for up to >90% of the concentration of p,p'-DDE, which was the most abundant peak in the most samples investigated. On the basis of the GC/ECD response, TetraBHD amounted for approximately 1/7 of TriBHD in all fish samples investigated. The sample with the highest content was a green-lipped mussel from New Zealand (236 ng/g lipid weight). The halogenated natural products TBA, Q1, and MHC-1 were also present in most of the samples. We assume that the bulk of the residues in fish from aquaculture may originate from algae and sponges living in proximity of the fish farms. Detection of TriBHD and TetraBHD in blubber of a monk seal (Monachus monachus) suggests that both HNPs may reach the top predators of food webs and thus also humans.
Some methoxylated polybrominated diphenyl ethers (MeO-BDEs) are known halogenated natural products (HNPs) and are frequently detected in higher organisms of the marine environment. In this study we demonstrate that a prominent MeO-BDE, previously detected in marine mammals from Australia, is identical to 3,5-dibromo-2-(2',4'dibromo)phenoxyanisole (BC-3, 6-MeO-BDE 47). Up to 1.9 mg/ kg of 6-MeO-BDE 47 was present in cetaceans from Australia, 0.2-0.3 mg/kg in two crocodile eggs from Australia, but concentrations of 1 or 2 orders of magnitude lower were found in shark liver oil from NewZealand and in marine mammals from Africa and the Antarctic. Concentrations of 6-MeO-BDE 47 in samples from Australia were in the same range as anthropogenic pollutants such as PCB 153 and p,p'-DDE. Along with 6-MeO-BDE 47 and the known HNP 4,6-dibromo-2-(2',4'-dibromo)phenoxyanisole (BC-2, 2'-MeO-BDE 68), several tribromophenoxyanisoles (MeO-triBDE) were present in tissue of Australian cetaceans. To determine their structure, abiotic debromination experiments were performed using 6-MeO-BDE 47 and 2'-MeO-BDE 68 and superreduced dicyanocobalamine. These experiments resulted in formation of eight MeO-triBDEs, all of which were detected in the cetacean samples. Five of these eight MeO-triBDEs could be identified based on two standard compounds as well as gas chromatographic and mass spectrometric features. It was also shown that the first eluting isomer (compound 1), 6-MeO-BDE 17 (compound 2), and 2-MeO-BDE 39 (compound 5) were the most prominent MeO-triBDEs in the Australian cetacean samples. The concentrations of the MeO-triBDEs in two cetacean samples were 0.20 and 0.36 mg/kg, respectively. Although the reductive debromination with dicyanocobalamine resulted in a different congener pattern than was found in the marine mammals, it could not be excluded that the tribromo
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