Polybrominated diphenyl ethers contamination of United States food

Elevated levels of polybrominated diphenyl ethers (PBDEs), a type of brominated flame retardant, were recently detected in U.S. nursing mothers' milk. These halogenated compounds chemically and toxicologically resemble others such as polychlorinated biphenyls (PCBs), whose route of intake is almost exclusively through food of animal origin. This study is the first to report the levels of PBDEs in U.S. foods in a market basket survey of 30 food types (total of 32 food samples) from three major supermarket chains in Dallas, TX. Food samples were almost exclusively foods of animal origin: meat, fish, and dairy products. Thirteen PBDE congeners were measured for each sample. Levels were then compared to existing PBDE food studies from other countries where available. In this study, levels of PBDEs are highest in fish, then meat, and lowest in dairy products; median levels were 1725 (range 8.5-3078), 283 (range 0.9-679), and 31.5 (0.2-1373), parts per trillion (ppt), or pg/g, wet weight, respectively. Nonfat milk did not have any detectable PBDE levels. In fish, PBDE congener 47 (2,2',4,4'-tetraBDE) contributes up to 70% of the total PBDEs, followed by congeners 100 (2,2',4,4',6) and 99 (2,2',4,4',5). In meat congener 99 predominates, followed by 47. In dairy, BDE 47 predominates followed by 99. U.S. food PBDE levels measured in this study are higher than reported in two other published market based studies from Spain and Japan. Although these findings are preliminary and will be updated with analyses of new samples, they suggest that food is a major route of intake for PBDEs.     

Survey of polybrominated diphenyl ether levels in Spanish commercial foodstuffs

Concentrations of 15 BDEs flame retardants have been determined in a large variety of food samples purchased in different markets across Spain. This is the first time that BDEs 184, 191, 196, and 197; impurities from BDEs formulations; and/or degradation products of BDE 209, have been detected in foodstuffs. Values ranged from <0.01 to 2482 pg/g fresh weight. The highest total BDE concentrations were found in fish samples (median of 189, range of 24-880 pg/g f.w.), followed by oils (median of 119, range of 14.8-2958 pg/g f.w.), meats (median of 75.9, range of 6.82-2518 pg/g f.w.), shellfish (median of 75.7, range of 3.29-677 pg/g f.w.), eggs (median of 73.5, range of 12.8-557 pg/g f.w.), and dairy products (median of 66.1, range of 3.24-1588 pg/g f.w.). The total BDE values found in this study are consistent with research reported elsewhere. They are in the same range as those recently reported by other European and Asian studies and lower than those conducted in the U.S. BDE 47 was the predominant congener in fish, shellfish, dairy products (except butter), and meats, while BDE 209 was the predominant in oil and egg samples. The most remarkable findings in this study were the large contribution of the highest brominated BDEs (hepta- to deca-BDE), and principally BDE 209, to the total BDE concentration found in Spanish foods, except fish and shellfish, and the presence of BDE 184, 191, 196, and 197 in many of the samples. The calculated intake of 38.5 ng/day of BDEs was comparable to intake assessment from other UE countries.     

Polybrominated diphenyl ether flame retardants in foodstuffs and human milk

Polybrominated diphenyl ethers (PBDEs) have been used worldwide as additive flame retardants in polymeric materials. Commercial products consist predominantly of deca-, octa-, and pentabromodiphenyl ether mixtures. PBDEs are resistant to degradation in the natural environment and Penta-BDE in particular accumulates in the fatty tissues of fish, birds and mammals (including humans). Several toxic effects on the thyroid system or on neurodevelopment have been reported in experimental animals exposed to PBDEs. It is likely that human exposure is predominantly through the ingestion of contaminated food and/or mother's milk. The potential health effects of dietary exposure to PBDEs have now become a great concern because of the increasing PBDE levels in the biosphere. In this review, published information on the toxicology of PBDEs, levels in foodstuffs and human milk, and analytical methods has been compiled.     

Polychlorinated dibenzo-p-dioxins,dibenzofurans and dioxin-like polychlorinated biphenyls in food and feed in Latvia in 2009–2011

During 2009–2011 a monitoring programme for 17 polychlorinated dibenzo-p-dioxins (PCDDs)/polychlorinated dibenzofurans (PCDFs) and 12 dioxin-like polychlorinated biphenyls (DL-PCBs) was conducted in the Latvian food and feed market. Using ISO 17025-accredited analytical methodology, investigation of 121 food (milk, dairy products, meat, eggs, fish, fish products) and 66 feed samples (fish meal and oil, compound and mineral feed, vegetable and animal fats) was performed. Most samples showed contamination below the European Commission (EC) Regulation No. 1881/2006 and Commission Directive 2006/13/EC limits. Average total toxicological equivalent (total-TEQ₍₁₉₉₈₎) concentrations within the food sample groups, except fish and fish products, ranged between 0.41 and 15.1 pg total-TEQ₍₁₉₉₈₎ g^?1 fat. Fish and fish products showed contamination levels from 0.18 to 46.0 pg total-TEQ₍₁₉₉₈₎ g^?1 fresh weight (f.w.). Fifty-seven per cent of cod liver samples were non-compliant. The most contaminated feed samples were fish meal and fish oil. A comparison with WHO-TEF₍₂₀₀₅₎ data is given.     

Polybrominated diphenyl ethers (PBDEs) in US meat and poultry: 2012–13 levels,trends and estimated consumer exposures

ABSTRACT

Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants whose use has contaminated foods and caused subsequent human exposures. To address the issue of possible human exposure, samples from a 2012–13 US meat and poultry (beef, pork, chicken, turkey) study were analysed for seven PBDEs. The mean summed concentrations of the seven BDE congeners (ΣPBDE) from beef, pork, chicken and turkey were 0.40, 0.36, 0.19, and 0.76 ng g^–1 lipid weight (lw). The range of ΣPBDEs for all meat classes was 0.01–15.78 ng g^–1 lw. A comparison of this study with a 2007–08 study revealed a decline in the median ΣPBDEs for all four meat classes, a reduction of 25.9% to 70.0%, with pork, chicken and turkey PBDE residues being statistically lower relative to the 2007–08 study. BDEs 47 and 99 contributed the most to the ΣPBDE concentrations, indicating likely animal exposures to the penta-BDE formulation. Based on the reported data an estimate of US consumer daily intake of PBDEs from meat and poultry was 6.42 ng day^–1.     

Dietary exposure of secondary school students in Hong Kong to polybrominated diphenyl ethers from foods of animal origin

This paper reports levels of polybrominated diphenyl ethers (PBDEs) in a wide range of foods of animal origin and estimates their dietary exposure for secondary school students in Hong Kong, China. Dietary exposure to PBDEs was estimated using local food consumption data obtained from secondary school students in 2000 and the concentrations of PBDEs in food samples taken from local market in 2008. The PBDE levels on a fresh weight basis for fish ranged from 13 to 6600 pg g^?1, for seafood and seafood products ranged from 15 to 1200 pg g^?1, for meat and meat products ranged from 23 to 3500 pg g^?1, for poultry ranged from 68 to 670 pg g^?1, for eggs ranged from 280 to 800 pg g^?1, and for dairy products ranged from 12 to 480 pg g^?1. The dietary exposures of secondary school students for the average and high consumers were estimated to be 2.6 and 6.4 ng kg^?1 body weight day^?1, respectively. According to the Joint FAO/WHO Expert Committee on Food Additives (JECFA), for the more toxic PBDE congeners, adverse effects would be unlikely to occur in laboratory animals at doses of less than approximately 100 µg kg^?1 body weight day^?1. The resulting margins of exposures (38,000 for average consumers and 16,000 for high consumers) showed that the estimated dietary exposures of secondary school students were far below any adverse effect dose observed in laboratory animals and were therefore of low concern for human health.     

Polychlorinated naphthalenes in foods: estimated dietary intake by the population of Catalonia,Spain

Concentrations of polychlorinated naphthalenes (PCNs) were measured in foodstuffs randomly acquired in seven cities of Catalonia, Spain. A total of 108 samples, belonging to 11 food groups (vegetables, tubers, fruits, cereals, pulses, fish and shellfish, meat and meat products, eggs, milk, dairy products, and oils and fats), were analyzed by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The levels of tetra-, penta-, hexa-, and hepta-CNs, those of octachloronaphthalene, and the mean sum concentration of tetra-octa-CN were determined. The highest concentration of total PCNs was found in oils and fats (447 pg/g), followed by cereals (71 pg/g), fish and shellfish (39 pg/g), and dairy products (36 pg/g). In general, tetra-CN was the predominant homologue in all food groups except for fruits and pulses, which had greater proportions of hexa-CNs. The dietary intake of total PCNs was subsequently determined. For calculations, recent data on consumption of the selected food items were used. Intake of PCNs was estimated for five population groups of Catalonia: children, adolescents, male and female adults, and seniors. When the dietary intake of total PCNs was expressed in nanogram per kilogram of body weight per day, it was age-dependent, with the highest and lowest values corresponding to children (1.65) and seniors (0.54), respectively. The largest contribution to the daily PCNs intake came from oils and fats and from cereals. The result of the current study is the first published report concerning human exposure to PCNs through the diet.     

Assessment of human exposure to polybrominated diphenyl ethers in China via fish consumption and inhalation

This study examined human exposure to polybrominated diphenyl ethers (PBDEs) associated with fish consumption and inhalation in China. The median intake of sigma7 PBDEs via human milk was 48.2 ng/day for nursing infants (0-1 years old) (a range of 23.4-99.1 ng/day). For all other age groups, the median intake of sigma11 PBDEs via fish consumption was 1.7-12.9 ng/day with a range of 0.59-56.3 ng/g. Additionally, human exposure to PBDEs via inhalation was 2.7-9.2 ng/day (a range of 0.72-108 ng/day). The median total sigma11 PBDEs intakes for nursing infants (6874 and 7372 pg/ kg b.w./day for males and females, respectively) were much higher than other age groups (215-608 pg/kg b.w./ day). No significant difference in the total PBDEs intakes was found between males and females. Of the 11 PBDEs congeners, BDE-47 was predominant in the total intake for nursing infants with a mean contribution of 38%, whereas BDE-209 was the dominant congener of total intake for other age groups, varying from 44 to 61%. Currently, the PBDEs levels in Chinese consumer fish and the total intakes of PBDEs via fish consumption were at the lower end of the global range. Compared with similar studies in other countries, however, human exposure to PBDEs via inhalation in China was relatively high. Overall, estimated daily intake of total PBDEs in the Chinese population was far below the LOAEL. However, studies are needed to further understand the fate and impact of PBDEs as PBDE-containing products are still used widely in large quantities in China.     

Determination of some specific isomers of polychlorinated biphenyl congeners in fatty foods of the Canadian diet

A total of 93 fatty food composites from the cities of Ottawa and Halifax (Canada) were analyzed for 34 selected isomers of polychlorinated biphenyls (PCBs). All fatty foods contained some PCB isomers with the 2,3,4,2',4',5'- and 2,4,5,2',4',5'-hexachlorobiphenyls present in all samples, except in skim milk and some dehydrated soups. The overall lowest PCB residues of all food commodities were found in skim milk, lamb, margarine and soups. Among the dairy products the highest PCB isomer levels were found in cheese and butter. The sum of all PCB isomers in these two commodities gave residue levels on a wet basis of 2.0 and 3.4 ng/g respectively. In the meat, fish and poultry class the highest specific PCB isomer levels were found in fish, especially freshwater fish, which contained a total of 21.0 ng PCB/g fish. In addition 28 out of the 34 selected PCB isomers were present in freshwater fish. Residue levels in canned fish were the second highest of all food commodities. The observed total PCB residue levels were below the Canadian guidelines for fish, dairy products, poultry, eggs and beef. A comparison of the percentage distribution of PCB isomers in fatty foods and human milk was difficult to evaluate due to the large variation of the fatty food data. However out of 31 PCB isomers reported in fatty foods, 25 were also found in human milk, although not to the same extent.     

Polychlorinated dioxins, furans, and biphenyls, and polybrominated diphenyl ethers in a U.S. meat market basket and estimates of dietary intake

Persistent environmental contaminants including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), non-ortho-polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) were analyzed in 65 meat samples collected from supermarkets across the U.S. in 2001. The samples included hamburger, sirloin steaks, pork chops, bacon, and whole chickens from nine different cities. The average PCDD/F/non-ortho-PCB toxic equivalency (TEQ) for all the samples was 0.55 pg/g of lipid (nd (nondetect) = DL (detection limit)/2) with a range from nondetectable to 3.21 pg/g of lipid. For PBDEs, eight congeners were routinely found in the meat samples with an average sum of 1.71 ng/g of lipid (nd = DL/2) and a range from nondetectable to 16.6 ng/g of lipid. While average TEQs were similar to recent values reported in Europe and Asia, the sums of PBDEs in chicken and pork were 3-20 times higher than levels reported in Spain and Japan for these foods. The presence of a few outliers raised the average PBDE sums and indicated that isolated sources of contamination may exist that, if identified, could be removed from the U.S. animal production chain. Using these TEQ and PBDE values and USDA food consumption data, the estimated dietary intake ranges from meat products were 5.3-16.0 pg TEQ and 14.9-44.7 ng of PBDEs/d or 0.1-0.3 pg TEQ and 0.3-0.5 (ng of PBDEs/kg of body mass)/d for an average individual, similar to intakes in other countries.     

Fate of higher brominated PBDEs in lactating cows

Dietary intake studies of lower brominated diphenyl ethers (BDEs) have shown that fish and animal products are important vectors of human exposure, but almost no data exist for higher brominated BDEs. Therefore, the fate of hepta- to decaBDEs was studied in lactating cows exposed to a naturally contaminated diet by analyzing feed, feces, and milk samples from a previous mass balance study of PCB. Tissue distribution was studied in one cow slaughtered after the experiment. BDE-209 was the dominant congener in feed, organs, adipose tissues, and feces, but not in milk. In contrast to PCBs and lower brominated BDEs, concentrations of hepta- to decaBDEs in adipose tissue were 9-80 times higher than in milk fat and the difference increased with degree of bromination/log K(OW). The congener profiles in adipose tissue and feed differed; BDE-207, BDE-196, BDE-197, and BDE-182 accumulated to a surprisingly greater extent in the fat compared to their isomers, suggesting metabolic debromination of BDE-209 to these BDEs. The results indicate that meat rather than dairy product consumption may be an important human exposure route to higher brominated BDEs.     

Determination of brominated flame retardants and brominated dioxins in fish collected from three regions of Japan

The concentrations of brominated dioxins which are polybrominated dibenzo-p-dioxins/polybrominated dibenzofurans (PBDD/DFs) and mono-bromo polychlorinated dibenzo-p-dioxins/dibenzofurans, polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA) were investigated in a total of 45 fish samples collected from three regions in Japan. In the brominated dioxins, 1,2,3,4,6,7,8-heptabromodibenzofuran (HpBDF) was the most abundant congener, and it was found in seven fish samples at 0.10-25.6 pg/g wet weight (ww). The highest concentration of 1,2,3,4,6,7,8-HpBDF was found in the pike eel. Regarding other congeners, 2,3,7,8-tetrabromodibenzo-p-dioxin was detected in the sea bream at 0.02 pg/g ww, and 2,3,7,8-tetrabromodibenzofuran was detected in the conger eel at 0.03 pg/g ww. 3-Bromo-2,7,8-trichlorodibenzofuran was detected in the Sardinella zunasi and the conger eel at 0.01 pg/g ww and 0.02 pg/g ww, respectively. Using toxic equivalency factors of chlorinated dioxins, we calculated the PBDD/DFs concentrations of these fish samples at 0.001-0.256 pg TEQ/g ww. PBDEs were detected in all of the fish samples. The concentrations of total PBDEs were 0.01-2.88 ng/g ww. The seerfish and the yellowtail containd PBDEs in high concentrations. The most dominant congener in most of the fish was 2,2',4,4'-tetrabromo diphenyl ether. TBBPA was detected in 29 fish samples at 0.01-0.11 ng/g ww. The mean level of TBBPA was about one-tenth or less of the total level of PBDEs. A good correlation was obtained between total PBDEs and fat content. On the other hand, no correlation was obtained between TBBPA and fat content. The daily intakes from fish were estimated to be 0.58 ng/kg body weight (bw)/day for total PBDEs, 0.03 ng/kg bw/day for TBBPA, and 0.01 pg TEQ/kg bw/day for brominated dioxins in the case assuming that the average bw of a Japanese adult person is 50 kg and that the average fish consumption is 82 g/day. For PBDEs, the provisionally calculated value was much less than the lowest observed adverse effect level value (1 mg/kg bw/day). For brominated dioxins, the daily intake was at a very low level compared with the Japanese daily intake of polychlorinated dioxins from fish. Even if the value of PBDD/DFs is added to the amount of chlorinated dioxin exposure, it was estimated that it is less than the tolerable daily intake (4 pg TEQ/kg bw/day) in Japan.     

Levels of polychlorinated biphenyls in foods from Catalonia,Spain: estimated dietary intake

From June to August 2000, food samples were randomly acquired in seven cities in Catalonia, Spain. Polychlorinated biphenyl (PCB) concentrations were determined for 108 samples of vegetables, fruits, pulses, cereals, fish and shellfish, meats and meat products, eggs, milk and dairy products, and oils and fats. Levels of 11 PCB congeners (IUPAC 28, 52, 77, 101, 105, 118, 126, 138, 153, 169, and 180) were determined by high-resolution gas chromatography-high-resolution mass spectrometry. For toxic equivalent (TEQ) calculations, World Health Organization (WHO) toxicity equivalent factors (WHO-TEFs) were used. The highest levels of most congeners were found in fish and shellfish (11,864.18 ng/kg [wet weight]), and the next highest levels, which were substantially lower, were found in milk and dairy products (674.50 ng/kg [wet weight]). For the general population of Catalonia, the total dietary intake of PCBs was found to be 150.13 pg WHO-TEQ/day. The largest contribution to this intake came from fish and shellfish (82.87 pg WHO-TEQ/day) and dairy products (29.38 pg WHO-TEQ per day). A relatively large contribution was also noted for cereals (11.36 pg WHO-TEQ/day). Among the PCB congeners determined in this study, PCB 126 showed the largest contribution to total TEQ intake (50.56%). The data obtained in this study should be useful in risk assessment with regard to human PCB exposure through food in Catalonia.     

多溴联苯醚在食品中的污染及其危害研究进展

多溴联苯醚(polybrominated diphenyl ethers,PBDEs)是一类新型持久性有机污染物,其具有生物蓄积、长距离迁移和污染持久等特点,引起人们的广泛关注。本文概述PBDEs的特性,总结食品中PBDEs的污染来源主要存在于大气、土壤和水体等环境介质中,剖析PDBEs在饮用水、肉类、蛋类、水产品和蔬菜类等食品中的污染状况,进而从甲状腺、神经系统、肝脏和生殖发育毒性等方面总结PBDEs对人体健康的毒性和危害。在此基础上提出控制食品中PBDEs污染的四个具体措施,包括制定PBDEs处理标准、发展新型溴代阻燃剂、加强PBDEs降解方法研究和完善检测分析方法。最后基于现有研究状况展望了PBDEs未来的研究方向,以期为治理食品中PBDEs的污染提供一定参考。     

Brominated and chlorinated dioxins, PCBs and brominated flame retardants in Scottish shellfish: methodology, occurrence and human dietary exposure

The most commonly consumed shellfish species produced in Scotland - mussels, oysters and scallops - were investigated for the occurrence of a range of brominated and chlorinated contaminants in order to establish current levels and estimate human dietary exposure. Flesh from individual sub-samples was representatively pooled and 35 composites were analysed for brominated and chlorinated dioxins (PBDD/Fs, PCDD/Fs), brominated and chlorinated biphenyls (PBBs, PCBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA). The analytical methodology used (13)C(12) labelled surrogates of the target compounds, with GC coupled to (usually) high resolution MS, and LC-MS/MS for HBCD and TBBPA analysis. Positive identifications were made in the majority of samples for most analytes with the exception of TBBPA and most PBDD congeners measured. None of the levels detected for PCDD/F and PCB were above the maximum permitted levels specified in European Union regulations. The levels of brominated furans predominated over brominated dioxins, reflecting the environmental distribution and source emission profiles of these contaminants, and relatively high levels of the tri-brominated congeners were observed. Levels of the flame retardant chemicals reflected current and legacy use, with appreciable concentrations of PBDEs and HBCDs (predominantly alpha-HBCD) but far lower levels of PBBs. TBBPA was not detected in any of the species. In general, mussels and oysters displayed relatively higher levels of contamination than scallops, although the gonad tissue of the latter showed significant levels of brominated dioxins. The estimated adult dietary intakes of PCDD/Fs and PCBs arising from the consumption of a typical portion of these foods in combination with an otherwise average UK diet were in the range 0.5-0.6 pg World Health Organisation (WHO)-toxic equivalent (TEQ)(2005)/kg bodyweight per day. These estimated dietary intakes are well within the Tolerable Daily Intake for dioxins and dioxin-like PCBs of 2 pg WHO-TEQ(2005)/kg bodyweight/day endorsed by the independent expert Committee on Toxicology of Chemicals in Food, Consumer Products and the Environment. The corresponding intakes for sumPBDEs and sumHBCDs were 5.6-6.1 and 5.9-7.9 ng/kg bodyweight/day respectively.     

Hexabromocyclododecane in marine species from the Western Scheldt Estuary: diastereoisomer- and enantiomer-specific accumulation

Hexabromocyclododecane (HBCD) is a widely used brominated flame retardant, which is increasingly reported in the environment. Here, we report on the diastereomeric and, for the first time, on the enantiomeric composition of HBCD in muscle and liver of several fish species caught in the Western Scheldt Estuary (The Netherlands). The total HBCD content (sum of alpha-, beta-, and gamma-diastereoisomers), as well as the distribution of diastereoisomers and enantiomers, varied between the species. The levels of total HBCD (9-1110 ng/g lipid weight) found in fish tissues were higher than those measured in fish from European rivers with no known point sources of HBCD but lower than in fish samples collected near factories producing or using HBCD. The concentrations of total HBCD expressed on a lipid weight basis were higher in liver than in muscle for bib and whiting, while in sole, HBCD had no preferential distribution between the tissues. A similar pattern for liver and muscle distribution was already observed for polybrominated diphenyl ethers (PBDEs) in these species. The alpha-HBCD diastereoisomer was most abundant in all fish samples with a higher contribution to the total HBCD levels in liver compared to muscle for bib and whiting. The gamma-HBCD diastereoisomer accumulated less in liver than in muscle of sole, bib, and whiting. For the first time, enantiomer fractions were determined for HBCD diastereoisomers in liver of three fish species and in muscle of two fish species. A significant enrichment of the (+) alpha-HBCD enantiomer was found in whiting and bib liver samples. A high enantioselectivity has also been seen for the gamma-HBCD diastereoisomer in whiting liver.     

Polybrominated diphenyl ethers and hydroxylated and methoxylated brominated and chlorinated analogues in the plasma of fish from the Detroit River

Novel classes and congeners of contaminant residues that are structurally analogous to polybrominated diphenyl ether (PBDE) flame retardants were assessed in the plasma of seven benthic- and six pelagic-feeding fish species from the highly contaminated Detroit River corridor, namely, hydroxylated-PBDEs (OH-PBDEs), methoxylated-PBDEs (MeO-PBDEs), and the antimicrobial OH-trichlorodiphenyl ether, triclosan, and its methylated (MeO) triclosan analogue. In all samples sigmaPBDE concentrations were comprised mainly of BDE47, BDE99, and BDE100 (>85%) and ranged from 155 pg/g wet weight (ww) to 21 069 pg/g ww. Of the 14 OH-PBDE congeners assessed, as many as 10 congeners were identified, although profiles were generally dominated by 6-OH-BDE47 with lesser amounts of 2'-OH-BDE68, 4'-OH-BDE49, and 4-OH-BDE42. sigmaOH-PBDE concentrations ranged from 2.7 to 198 pg/g ww, with sigmaPBDE to sigmaOH-PBDE concentration ratios ranging from 0.0005 to 0.02. OH-PBDEs are likely derived in these freshwater species as metabolites of precursor PBDEs and are subsequently retained in the blood, for example, 6-OH-BDE47, 4'-OH-BDE49, and 4-OH-BDE42 could be derived from BDE47. Portions of concentrations of the OH-PBDEs may also be of alternate origins and are accumulated and retained in these fish. In all samples, the 14 MeO-PBDEs monitored were below detection (<0.01 pg/g ww). Anthropogenic triclosan concentrations ranged from 750 to >10 000 pg/g ww and is clearly a bioaccumulative halogenated phenolic compound in these fish. MeO-triclosan concentrations were considerably lower. In addition to emerging classes of brominated contaminant such as PBDEs, whether of metabolic or anthropogenic origin, fish collected from the Detroit River are exposed to a complex profile of PBDE-like organohalogens.     

Debromination of the flame retardant decabromodiphenyl ether by juvenile carp (Cyprinus carpio) following dietary exposure

The congener 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE 209) is the primary component in a commonly used flame retardant known as decaBDE. This flame retardant constitutes approximately 80% of the world market demand for polybrominated diphenyl ethers (PBDEs). Because this compound is very hydrophobic (log K(ow) approximately 10), it has been suggested that BDE 209 has very low bioavailability, although debromination to more bioavailable metabolites has also been suggested to occur in fish tissues. In the present study, juvenile carp were exposed to BDE 209 amended food on a daily basis for 60 days, followed by a 40-day depuration period in which the fate of BDE 209 was monitored in whole fish and liver tissues separately. No net accumulation of BDE 209 was observed throughout the experiment despite an exposure concentration of 940 ng/day/fish. However, seven apparent debrominated products of BDE 209 accumulated in whole fish and liver tissues over the exposure period. These debrominated metabolites of BDE 209 were identified as penta- to octaBDEs using both GC/ECNI-MS and GC/HRMS. Using estimation methods for relative retention times of phenyl substitution patterns, we have identified possible structures for the hexa- and heptabromodiphenyl ethers identified in the carp tissues. Although exposure of carp to BDE 209 did not result in the accumulation of BDE 209 in carp tissues, our results indicate evidence of limited BDE 209 bioavailability from food in the form of lower brominated metabolites.     

Brominated flame retardants in tree bark from North America

Brominated flame retardants were measured in 87 tree bark samples from 29 locations in North America. The concentrations of total polybrominated diphenyl ethers (PBDEs) ranged from 2.3 to 5700 ng/g lipid weight, with the highest concentrations found near or in Arkansas. A simple radial dilution model nicely describes the distribution of total PBDE concentrations in these samples and indicates the likely sources ofthese chemicals are emissions from the two brominated flame retardant manufacturing facilities, operated by Great Lakes Chemicals and Albemarle, located in southern Arkansas. The congener profiles of PBDEs are similar for all the tree bark samples and can be described by a mixture of the congener profiles of the penta- and deca-BDE commercial products combined in a ratio of 1:2. Two unusual BFRs, 1,2-bis(2,4,6-tribromophenoxy)ethane and decabromodiphenyl ethane, were also detected in tree bark samples collected in Arkansas, suggesting the two manufacturing facilities are the sources of these compounds as well. A polybrominated biphenyl congener (BB-153) was present in most tree bark samples at low levels relative to the PBDEs.     

Polybrominated diphenyl ethers in marine species from the Belgian North Sea and the Western Scheldt Estuary: levels, profiles, and distribution

The Western Scheldt Estuary (SE) is subjected to a variety of suspected PBDE sources, such as a brominated flame retardant manufacturing plant, the Antwerp harbor, and the textile industry located further upstream the river. The Belgian North Sea (BNS) was included in this study to analyze the influence of the SE on the levels found in biota from the BNS locations. Benthic invertebrates, such as shrimp, crab, and starfish, benthic fish, such as goby, dab, plaice, and sole, and gadoid fish, such as bib and whiting, were sampled in the BNS (nonpolluted area) and the SE (polluted area) and analyzed to determine the concentrations and spatial variation of eight polybrominated diphenyl ethers (PBDEs 28, 47, 99, 100, 153, 154, 183, and 209). Levels found in the SE samples were up to 30 times higher than those found in BNS samples, with a gradient increasing toward Antwerp. Levels in BNS ranged from 0.02 to 1.5 ng/g ww in benthic invertebrates and goby, from 0.06 to 0.94 ng/g ww in fish muscle, and from 0.84 to 128 ng/g ww in fish liver. For the SE samples, levels ranged from 0.20 to 29.9 ng/g ww in benthic invertebrates and goby, from 0.08 to 6.9 ng/g ww in fish muscle, and from 15.0 to 984 ng/g ww in fish liver. BDE 209 could only be detected in eight liver samples from the SE and levels ranged between 3.4 and 37.2 ng/g ww. PBDE profiles of the various species at the different locations were compared. Differences in profile were attributed to different exposure and to differences in metabolism among species. Ratios between BDE 99 and 100 were found to be highly location and species dependent, which could be related to differences in metabolism. Some species, such as dab, plaice bib, and whiting, showed preferential accumulation of PBDEs in the liver. Higher brominated congeners in general showed higher affinity for liver than for muscle tissue.