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
"All eight species studied had different ratios of 2'-MeO-BDE 68 to 6-MeO-BDE 47 (Table 1), although in general, 2'-MeO-BDE 68 was found at similar or slightly higher concentrations than 6-MeO-BDE 47, with the exception of yellowfin bream. This agrees with reports of marine mammals and reptiles from Australia (Vetter et al., 2001a, 2002; Melcher, et al., 2005), where 2'-MeO-BDE 68 was the dominant congener. Levels of "
[Show abstract][Hide abstract] ABSTRACT: Polybrominated diphenyl ethers (PBDEs) and naturally-produced organobrominated compounds, such as methoxylated PBDEs (MeO-PBDEs), have been scarcely studied in the Southern Hemisphere. Yet, sources of the latter group of compounds were found in Southern regions, specifically in Australia. The environmental distribution and biomagnification potential of organobrominated compounds were therefore investigated in a representative aquatic food chain (invertebrates and fish) from the Sydney Harbour, Australia. Mean PBDE concentrations ranged from 6.4 ng/g lipid weight (lw) in squid to 115 ng/g lw in flounder. BDE 47 was the dominant congener, followed by BDE 100. Mean levels of MeO-PBDEs (sum of congeners 2’-MeO-BDE 68 and 6-MeO-BDE 47) were as high as 110 ng/g lw in tailor, with a slight dominance of 2’-MeO-BDE 68. Polybrominated hexahydroxanthene derivates (PBHDs), another class of naturally-produced compounds, were found at variable concentrations and ranged from 4.7 ng/g lw in fanbelly and 146 ng/g lw in tailor. The tribrominated PBHD isomer dominated in the samples, except for luderick and squid. The lower levels of PBDEs found in luderick from the harbour compared to those obtained from the upper Parramatta River indicated a terrestrial (anthropogenic) origin of PBDEs, while the higher levels of MeO-PBDEs and PBHDs in the samples from the harbour confirmed the marine (natural) origin of these compounds. The highest trophic magnification factor (TMF) was found for sum PBDEs (3.9), while TMFs for sum MeO-PBDEs and sum PBHDs were 2.9 and 3.4, respectively. This suggests that biomagnification occurs in the studied aquatic food chain for anthropogenic brominated compounds, but also for the naturally-produced organobromines.
Environment international 11/2009; 35(8-35):1142-1149. DOI:10.1016/j.envint.2009.07.008 · 5.56 Impact Factor
"The profile of MeO-triBDEs observed in the dolphin species from Brazil (Fig. 3) agrees with the pattern observed in dolphin samples from Australia (Melcher et al., 2005, Fig. 4). As suggested by Melcher et al. (2005), the mixture of MeO-triBDEs congeners observed in the dolphin samples possibly derive from the debromination of 2′-MeO-BDE 68 and 6- MeO-BDE 47. However, intensities and profiles of the MeO-PBDE congeners observed in the dolphins may differ from those observed from the anaerobic debromination of 2′- MeO-BDE 68 and 6-MeO-BDE 47. "
[Show abstract][Hide abstract] ABSTRACT: Liver samples from 51 cetaceans, comprising 10 species, stranded between 1994 and 2006 in a highly industrialized and urbanized region in Southeast Brazil, were analyzed for polybrominated diphenyl ethers (PBDEs) and methoxylated-PBDEs (MeO-PBDEs). A concentration range of PBDEs (3-5960ng/g lw) similar to that observed in Northern Hemisphere dolphins was found. MeO-PBDE concentrations in continental shelf (CS) dolphins from Brazil are among the highest detected to date in cetaceans (up to 250microg/g lw). Higher SigmaMeO-PBDE concentrations were measured in CS and oceanic dolphins than in estuarine dolphins. The SigmaPBDE/SigmaMeO-PBDE ratio varied significantly ranging from a mean value of 7.12 to 0.08 and 0.01 for estuarine, CS and oceanic species, respectively. A positive correlation was observed between SigmaPBDE and year of stranding of male estuarine dolphins (Sotalia guianensis), which suggests temporal variation in the exposure. Placental transfer of organobrominated compounds was also evidenced in S. guianensis.
Environment international 10/2009; 36(1):60-7. DOI:10.1016/j.envint.2009.10.001 · 5.56 Impact Factor
"For example, 2,3,3¢,4,4¢,5,5¢-heptachloro-1¢-methyl-1,2¢-bi- pyrrole (Q1) reached up to 14 mg/kg in the blubber of marine mammals (Vetter et al. 2003a). Additional marine HNPs frequently detected in environmental samples are halogenated 1,1¢-dimethyl-2,2¢-bipyrroles (Tittlemier et al. 1999), polybrominated phenoxyanisoles (Melcher et al. 2005; Marsh et al. 2004; Teuten et al. 2005), a dimethoxylated tetrabromobiphenyl (Marsh et al. 2005), and the mixed halogenated C 10 H 13 Br 2 Cl 3 compound MHC-1 (Vetter et al. 2001). "
[Show abstract][Hide abstract] ABSTRACT: Purified extracts of five species of Antarctic sponges (Demospongiae: Kirkpatrickia variolosa, Artemisina apollinis, Phorbas glaberrima, and Halichondria sp. and Calcarea: Leucetta antarctica) from King George Island were analyzed by GC/MS for the presence of persistent and lipophilic halogenated compounds to identify bioaccumulative halogenated natural products. Sample extracts were prepared using methods identical for the determination of POPs, namely, microwave-assisted extraction with organic solvents, gel permeation chromatography, and column chromatography on deactivated silica. In addition, samples were treated with sulfuric acid to remove acid-destructible compounds. PCBs were not detectable and only traces of lindane, p,p'-DDE, and alpha-HCH were detected in these samples in decreasing order of abundance, underscoring their uncontaminated state. In contrast, 146 brominated compounds were identified by correct isotopic ratios m/z 79 and 81, 50% of which eluted prior to lindane including the most abundant peaks. Each sponge sample contained > or = 35 brominated compounds of natural origin, 14 of which were detected in all species. Estimated concentrations ranged from the high ng/kg to mg/kg (air-dried weights) and relative distributions of the same compounds in different sponges were highly variable. The high abundance of these compounds relative to known anthropogenic pollutants strongly suggests a natural origin. Multiple mode (EI-, ECNI-, and PCI-) GC/MS enabled identification of an aliphatic ketone tentatively identified as 1,1,2-tribromo-oct-1-en-3-one, present in all species but highest in Phorbas glaberrima. Several halogenated phenols including 2,4,6-tribromophenol were also abundant in Phorbas glaberrima as were halogenated anisoles in lower relative abundances. The halogenated phenols were analyzed without derivatization. The sample of Halichondria sp. contained the dibromotrichloro monoterpene MHC-1, a recently described environmental contaminant in fish and seals. Retrospective analysis of other marine samples confirmed that 2,4,6-tribromophenol was present in seal blubber from both the Arctic and the Antarctic. The presence of naturally occurring organohalogens such as 2,4,6-tribromophenol and MHC-1 in Antarctic marine invertebrates thus provides a link to their occurrence in marine mammals.
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