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.
During routine gas chromatography with electron capture detection (GC/ECD) analysis of chicken eggs, we observed that the most prominent peak in some samples did not match the retention time of any of the food contaminants screened. Subsequent GC coupled with mass spectrometry (GC/MS) studies clarified that the mass spectrum of the peak was very similar to hexabromocyclododecane (HBCD), which was also identified by GC/MS in the egg. The unknown compound was positively identified as pentabromocyclododecene (PBCDE), a metabolite of HBCD detected for the first time in foodstuffs. Studies of the analytical method used for the analysis of pesticides and contaminants showed that this cleanup method was suitable for the determination of HBCD and PBCDE, but storage of sample extracts resulted in the loss of HBCD when the sample extracts were not sufficiently purified. The concentrations of HBCD and PBCDE in the high polluted sample were 2.0 and 3.6 mg/kg egg fat. HBCD and PBCDE were also detected in two additional eggs at lower levels (<0.15 mg/kg), whereas 75 eggs did not contain these compounds (<0.02 mg/kg). We also detected HBCD and PBCDE in two samples of whitefish (Coregonus sp.), while an eel sample (Anguilla anguilla) positively tested for HBCD did not contain PBCDE. Surprisingly, the potential metabolite of HBCD, PBCDE, has not been detected before in any food or environmental sample. The present results indicate that more attention should be paid to the detection of HBCD and its metabolite PBCDE in chicken eggs.
An unknown component that caused an intense signal in sample extracts of fish tissue was enriched and investigated using a variety of mass spectrometric techniques coupled to gas chromatographic separation. With the help of electron capture negative ion mass spectrometry (ECNI-MS) and electron impact mass spectrometry (EI-MS) it was established that the component carries 2Br and 3Cl atoms and forms a molecular ion at m/z 396. A concentrated solution of this mixed halogenated compound (MHC-1) was investigated by gas chromatography interfaced to electron impact high-resolution mass spectrometry (GC/EI-HRMS). Using full scan and SIM techniques, the molecular formula of MHC-1 was established to be C10H13Br2Cl3. This points toward MHC-1 having a monoterpene backbone. No chemical with this molecular formula has been synthesized, but two components with this composition have been earlier isolated from marine algae.
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