Debromination of polybrominated diphenyl ether congeners BDE 99 and BDE 183 in the intestinal tract of the common carp (Cyprinus carpio)

Polybrominated diphenyl ether (PBDE) congener patterns in biota are often enriched in tetra-, penta-, and hexabrominated diphenyl ethers, which is believed to result from the use of the commercial "pentaBDE" formulation. However, our evidence suggests that debromination of PBDEs occurs within fish tissues leading to appreciable accumulation of less brominated congeners. This suggests that PBDE body burdens can reflect both direct uptake from exposure and debromination of more highly brominated congeners. We conducted two independent dietary exposure studies using the common carp (Cyprinus carpio) to trace the fate of 2,2',4,4',5-pentabromodiphenyl ether (BDE 99) and 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE 183) in fish tissues. Carp were fed food spiked with individual BDE congeners for 62 d, and depuration was monitored during the following 37 d. Significant debromination was observed, converting BDE 99 to 2,2',4,4'-tetrabromodiphenyl ether (BDE47) and BDE 183 to 2,2',4,4',5,6-hexabromodiphenyl ether (BDE 154) and another as yet unidentified hexa-BDE congener. The BDE 99 concentration rapidly declined from 400 +/- 40 ng/g ww in the food to 53 +/- 12 ng/g ww in the gut content material sampled 2.5 +/- 1 h following feeding. At least 9.5 +/- 0.8% of the BDE 99 mass in the gut was debrominated to BDE 47 and assimilated in carp tissues. In the BDE 183 exposure, approximately 17% of the BDE 183 mass was debrominated and accumulated in carp tissues in the form of two hexa-BDE congeners. In both exposure studies, the concentration of the exposure compound decreased significantly in the gut within 2.5 +/- 1 h following ingestion. This rapid decrease in the concentration of the BDE congeners could not be explained entirely by debromination to quantified products or fecal egestion. Reactions occurring within the gut transform BDE congeners to other products that may accumulate or be excreted. Further studies are needed to identify and determine the effects of these BDE metabolites.     

Investigation of selected persistent organic pollutants in farmed Atlantic salmon (Salmo salar), salmon aquaculture feed,and fish oil components of the feed

There is extensive literature documenting the bioaccumulation of persistent organic pollutants in the marine environment, but relatively little data are available on contamination pathways in aquaculture systems such as that for farmed salmon. In recent years,the salmon industry has grown significantly in Europe. This study reports on the determination of a wide range of polychlorinated biphenyls (PCBs), organochlorine pesticides, and polybrominated diphenyl ethers (PBDEs) in farmed and wild European Atlantic salmon fish, aquaculture feeds, and fish oils used to supplement the feeds. The study confirms previous reports of relatively high concentrations of PCBs and indicates moderate concentrations of organochlorine pesticides and PBDEs in farmed Scottish and European salmon. Concentrations of the selected persistent organic pollutants varied among the samples: PCBs (salmon, 145-460 ng/g lipid; salmon feeds, 76-1153 ng/g lipid; fish oils, 9-253 ng/g lipid), S DDTs (salmon, 5-250 ng/g lipid; salmon feeds, 34-52 ng/g lipid; fish oils, 11-218 ng/g lipid), and PBDEs (salmon, 1-85 ng/g lipid: salmon feeds, 8-24 ng/g lipid; fish oils, ND-13 ng/g lipid). Comparison of the samples for all groups of contaminants, except for HCHs, showed an increase in concentration in the order fish oil < feed < salmon. Homologue profiles were similar, with an increase in contribution of hepta- and octa-PCBs in the fish, and profiles of DDTs were similar in all three types of samples. With a constant contribution to the total PCB content, the ICES 7 PCBs appear to be reliable predictors of the PCB contamination profile through all the samples. For PBDEs, BDE 47 dominated the profiles, with no significant difference in the PBDE profiles for the three matrixes. Samples with higher PCB contents generally showed higher levels of the pesticide residues, but this was not the case with the PBDEs, indicating the existence of different pollution sources.     

Probabilistic intake assessment of polybrominated diphenyl ethers and omega-3 fatty acids through fish consumption

Food intake is one of the principal exposure routes of polybrominated diphenyl ethers (PBDEs) in humans. This study focuses on fish consumption as a PBDE exposure route. A probabilistic intake assessment of PBDEs and healthy long chain omega-3 PUFAs (LC n-3 PUFAs) was conducted for Belgian fish consumers in order to study the balance of the intake of LC n-3 PUFAs and PBDEs. Based on the observed fish consumption level in the sample, the mean intake of brominated diphenyl ether (BDE)-28, 47, 99, 100, 153, and 154 via fish was 0.85 ng/kg body weight (bw)/day and the intake of LC n-3 PUFAs was 3.45 mg/kg bw/day, being low compared to the recommendations. Scenario analyses showed that consuming 150 g salmon twice a week is advisable to achieve the recommended LC n-3 PUFA intake with a rather low PBDE intake. When replacing 150 g salmon by herring, the PBDE intake is higher without an increase in LC n-3 PUFAs. In contrast, the combination of cod and salmon leads to a similar PBDE intake compared to twice a week salmon, but to a lower LC n-3 PUFA intake. In conclusion, the methodology presented in the paper allows balancing benefits and risks related to fish consumption.     

Effects of river flooding on polybrominated diphenyl ether (PBDE) levels in cows' milk, soil, and grass

The first investigation into PBDE levels in food produced from flood-prone land on industrial river catchments was conducted. In August 2008 samples of cows' milk, along with grass and soil were taken from 5 pairs of flood-prone and control farms on the River Trent (Central UK). The sum of 7 BDE congeners (28, 47, 99, 100, 153, 154, and 183) was calculated. Higher PBDE levels occurred in soil on flood-prone compared to control farms (median 770 vs 280 ng/kg dry weight). These higher levels were not reflected in the grass samples indicating that PBDE contamination on soils is not transferred efficiently to grass. This observation alongside the fact that cows on flood-prone farms spend time on non-flood-prone land and are fed substantial quantities of commercial feed are reasons why higher PBDE levels were not found in milk from flood-prone farms (median 300 vs 250 ng/kg fat weight). Similar BDE47/BDE99 ratios were observed in soil and grass samples compared to the PBDE product commonly used in the UK, indicating few differences in source-pathway transfer efficiencies between congeners. The BDE47/BDE99 ratio in the milk samples was greater than those in the grass and feed indicating differential food to milk transfer efficiencies between congeners.     

Comparison of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in Lake Michigan salmonids

Polybrominated diphenyl ethers (PBDEs) have been used extensively over the past two decades as flame retardants in most types of polymers. Many measurements of PBDEs in various environmental matrices from Sweden, Holland, Japan, and elsewhere have been reported, but few measurements are available for North America. PBDEs in 21 coho and chinook salmon taken from Lake Michigan tributaries in 1996 were measured for this study. The salmon samples were extracted and initially analyzed for polychlorinated biphenyl (PCB) congeners. It was demonstrated for these samples that the same extract fraction contains PBDEs. Six PBDE congeners were observed in all 21 samples, and the rank order of concentration of these congeners was similar to that in commercial mixtures of PBDEs. The average concentration across all samples of the sum of PBDE congeners was 80.1 ng/g of wet weight or 2,440 ng/g of lipid. This is much less than the average sum PCB concentration (1,450 ng/g of wet weight; 43,100 ng/g of lipid). However, the average concentration of the most abundant PBDE congener (IUPAC BDE-49: 52.1 ng/g wet, 1,590 ng/g of lipid) was about one-third of the average concentration of the most abundant PCB congener (IUPAC CB-153: 149 ng/g wet, 4,550 ng/g of lipid). On the basis of an extensive literature survey, the concentrations of PBDEs reported here are among the highest in the world for salmon in open waters. The concentrations of PBDEs and PCBs are both correlated with fish length and mass, but not with lipid content. The concentrations of PBDEs and PCBs are highly correlated in individual fish, implying that PBDEs are as prevalent as PCBs in Lake Michigan.     

A preliminary comparison of polybrominated diphenyl ether concentrations relative to lipid content and to levels of dioxins and dioxin-like polychlorinated biphenyls in Norwegian farmed Atlantic salmon (Salmo salar)

Polybrominated diphenyl ethers (PBDEs) are environmental contaminants structurally similar to polychlorinated biphenyls (PCBs), and correlations between PBDE concentrations and concentrations of lipid, PCBs, dioxins and furans in feed and farmed Atlantic salmon filet indicate PBDEs may be derived from similar sources. PBDE concentrations (3.9 ± 0.6 ng g^?1 wet wt) in farmed Atlantic salmon correlated well with lipid content and these other halogenated contaminants, however, lower concentrations of PBDEs (1.6 ± 0.3 ng g^?1 wet wt) showed no correlation. Possible explanations for the non‐linear behaviour of PBDE concentrations in Atlantic salmon are discussed.     

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.     

Modeling atmospheric vegetation uptake of PBDEs using field measurements

Polybrominated diphenyl ethers (PBDEs) are flame retardants used in a variety of consumables. Models indicate that air-vegetation exchange plays an important role in their global distribution. The present study surveyed PBDEs in spruce needles and air (gaseous and particulate-bound) over an annual cycle to model accumulation of PBDEs in vegetation. Air-particulate distributions revealed that penta and higher BDE congeners were mainly associated with particulates even in warmer temperatures, whereas for the tri- and tetra-BDE congeners, a significant temperature dependence was observed. Using measured vegetation and atmospheric concentrations from bud burst 2004 to June 2005, a modeling concept was developed to determine PBDE deposition velocities to vegetation. Particulate-bound deposition velocity was calculated to be 3.8 m/h. Net gaseous transfer velocities ranged from 2.4 to 62.2 m/h and correlated significantly with log K(OA). These derived values were used to model PBDE accumulation by vegetation through time, and these agreed well with measured values. This study provides the necessary background for modeling PBDE transport between air and coniferous vegetation globally.     

Polybromodiphenyl ether flame retardants in fish from lakes in European high mountains and Greenland

Individual polybromodiphenyl ethers (PBDEs) were investigated in liver and muscle tissue of trout from 11 high mountain lakes in Europe and one in Greenland. Trouts in these lakes [brown trout (Salmo trutta), brook trout (Salvelinus fontinalis) and arctic char (Salvelinus alpinus)] are important sentinel species because they are located in the top of the food chain and pollution can only reach these ecosystems by atmospheric transport. The major PBDE congeners were BDE 47 and BDE 99, followed by BDE 100, BDE 153, BDE 154, and BDE 28. These compounds were found in all the samples examined. Their average concentrations [110-1300 and 69-730 pg g(-1) wet weight (ww) in liver and muscle or 2400-40000 and 2900-41000 pg g(-1) lipid weight (lw), respectively] were in the lower range when compared with those of fish from other less remote locations. The highest levels of PBDEs in liver and muscle are found in Lochnagar, Scotland: 11000 and 1200 pg g(-1) ww, respectively (366 000 and 177000 pg g(-1) lw, respectively). Male specimens exhibited higher PBDE concentrations in liver than female. The concentrations of most PBDEs in liver were correlated with fish age (p < 0.01) and, inversely, with condition factor (p < 0.01). Muscle PBDE concentrations did not correlate with age, and only some congeners showed significant positive correlations with condition factor (p < 0.05). The main differences between species were found in the accumulation of the more abundant PBDEs, brook trout showing the highest concentrations in muscle and the lowest in liver. No correlation between the occurrence of these compounds in high mountain fish and altitude, latitude, or temperature was observed. This fact and the lack of correlation between muscle concentrations and age suggest that the fluxes of PBDEs arriving at high mountain lakes are still not constant. In view of the present use of these compounds, they are probably increasing.     

Levels and temporal trends (1988-1999) of polybrominated diphenyl ethers in beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary, Canada

Polybrominated diphenyl ethers (PBDEs) were determined in blubber samples of 54 stranded adult beluga whales (Delphinapterus leucas) collected between 1988 and 1999 in the St. Lawrence Estuary (SLE), Quebec, Canada. Summed concentrations of 10 PBDE congeners (sigmaPBDEs) measured in beluga samples varied between 20 and almost 1000 ng/g wet weight. According to the PBDE concentrations in marine mammals reported in the scientific literature, SLE belugas appear to be relatively lightly contaminated. Only a few predominant congeners (namely, PBDE-47, -99, and -100) represent on average more than 75% of sigmaPBDEs in SLE belugas. The accumulation of sigmaPBDEs in both male and female belugas showed significant exponential increase throughout the 1988-1999 time period. The time necessary for beluga to double their blubber concentration of the most prevalent PBDE congeners was no longer than 3 years. The PBDE temporal changes reported in this study are generally faster but in agreement with the trend observed in other organisms collected in Canada, such as lake trout (Salvelinus namaycush) from the Great Lakes, ringed seal (Phoca hispida), and beluga whale from the Canadian Arctic. Some changes in the pattern of PBDEs in belugas were also observed during the time period investigated. The recent and important increase of PBDE levels in SLE belugas could explain the unexpected lack of statistical difference in PBDE contamination between males and females. This suggests that to date PBDEs tend to be accumulated by both male and female belugas, masking the elimination of PBDEs by females through post-natal transfer to their offspring. This study confirms that the growing use of PBDEs as flame retardants has resulted in rising contamination of Canadian aquatic environments. Additional studies are needed to assess the toxicological implications of the PBDE tissue levels found in SLE belugas.     

Species-specific differences and structure-activity relationships in the debromination of PBDE congeners in three fish species

Previous studies have suggested that there may be species-specific differences in the metabolism of polybrominated diphenyl ethers (PBDEs) among different fish species. In this study, we investigated the in vitro hepatic metabolism of eleven individual PBDE congeners (tri- through decaBDEs) in three different fish species: rainbow trout (Oncorhynchus mykiss), common carp (Cyprinus carpio), and Chinook salmon (O. tschwatcha). In addition, we evaluated the influence of PBDE structural characteristics (i.e., bromine substitution patterns) on metabolism. Six of the eleven congeners we evaluated, BDEs 99, 153, 183, 203, 208, and 209, were metabolically debrominated to lower brominated congeners. All of the congeners that were metabolized contained at least one meta-substituted bromine. Metabolites were not detected for congeners without one meta-substituted bromine (e.g., BDEs 28, 47, and 100). Metabolite formation rates were generally 10 to 100 times faster in carp than in trout and salmon. BDEs 47, 49, 101, 154, and 183 were the major metabolites observed in all three species with the exception of BDE 47, which was only detected in carp. Carp demonstrated a preference toward meta-debromination, while trout and salmon debrominated meta- and para-bromine atoms to an equal extent. We compared glutathione-S-transferase (GST) and deiodinase (DI) activity among all three species as these enzyme systems have been hypothesized to play a role in PBDE debromination in teleosts. Carp exhibited a preference for meta-deiodination of the thyroid hormone thyroxine, which was consistent with the preference for meta-debromination of PBDEs observed in carp.     

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.     

Fate, partitioning, and mass loading of polybrominated diphenyl ethers (PBDEs) during the treatment processing of municipal sewage

Sewage treatment plant (STP) effluents are likely a major source of contamination for PBDEs, especially in the receiving water bodies of local aquatic environments surrounding the location of these discharges. Congeners of the pentaBDE mixture, 2,2,',4,4'-tetrabromodiphenyl ether (BDE47), 2,2,',4,4',5-pentabromodiphenyl ether (BDE99), 2,2,',4,4',6-pentabromodiphenyl ether (BDE100), 2,2,',4,4',5,5'-hexabromodiphenyl ether (BDE153), and 2,2,',4,4',5,6'-hexabromodiphenyl ether (BDE154), are of great environmental concern in North America due to their persistence, potential for bioaccumulation, and >97% use of the global production of the mixture in the region. Detailed characterization of the distribution of eight PBDE congeners (2,4,4'-tribromoDE (BDE28) and BDE47, 99, 100, 138, 153, 154, and 183) was carried out at five sites along the treatment process at an activated sludge-type secondary treatment municipal STP facility. PentaBDE mixture congeners, sigma5PBDE (sum of BDE47, 99, 100, 153, and 154) accounted for >98% of the total (sigma 8) PBDE concentration at all sites, with over 80% of the composition being BDE47 and BDE99. Presence of dissolved organic matter affected the mobility of PBDEs during the initial stages of the treatment process. About 9% of the influent mass of sigma5PBDE to the facility is estimated to be discharged into the Little River (leading to the Detroit River) with the final effluent, resulting in an estimated mass loading of approximately 0.7 kg/year. The total mass loading of sigma5PBDE to the Detroit River is expected to be much larger as effluent from this facility accounts for <10% of the total STP discharges to the river.     

Assessment of polybrominated diphenyl ether exposures and health risks associated with consumption of southern Mississippi catfish

Despite the growing public interest in polybrominated diphenyl ethers (PBDEs), there are relatively few studies in the published literature which characterize and quantify human intake of these compounds. In this study, PBDE concentrations were measured in southern Mississippi catfish to determine background levels, daily intake, and risk associated with the consumption of these chemicals from a primary food source for residents in this region of the United States. A total of 33 wild catfish samples were collected from five sites, and 28 farm-raised catfish samples were purchased, all of which were from locations in southern Mississippi. All samples were analyzed for 43 PBDEs (mono- through deca-congeners) using high-resolution gas chromatography-mass spectrometry. Both PBDE concentrations (sigmaPBDE ranged from 0.3 to 23.3 ng/g wet weight) and congener profiles varied by fish type and location; however, BDE congeners 47, 99, 100, 153, and 154 were the dominant contributors in all samples. The estimated daily intake of PBDEs associated with consumption of the catfish ranged from 0.03 to 1.80 ng/kg-day. Evaluation of the cancer risk for BDE 209 and the noncancer hazard for BDE congeners 47, 99, 153, and 209 indicated that health risks/hazards due to fish consumption in adults are substantially lower than risk levels generally considered to be at the U.S. EPA minimum concern level.     

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.     

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.     

Remarkable findings concerning PBDEs in the terrestrial top-predator red fox (Vulpes vulpes)

In the present study, we have analyzed muscle, liver, and adipose tissue of 33 red foxes from Belgium for their content of polybrominated diphenyl ethers (PBDEs). Median sums of seven tri- to hepta-BDEs (BDE 28, BDE 47, BDE 99, BDE 100, BDE 153, BDE 154, and BDE 183) were 2.2, 2.4, and 3.4 ng/g lipid weight in adipose tissue, liver, and muscle, respectively. These levels were lower than those found in various species of voles and mice, the main prey species of the red fox. This is probably related to the high capacity of the foxes to metabolize and eliminate lower brominated congeners. BDE 209 generally dominated the PBDE congener profiles in the red fox samples. In samples containing BDE 209, this congener contributed, on the average, approximately 70% to the total PBDE content. BDE 209 was measured in concentrations as high as 760 ng/g lipid weight in the liver, but the detection frequency was not more than 40%. In animals with the highest BDE 209 levels, this congener was detected in muscle, liver, as well as in adipose tissue. Other abundant congeners were BDE 153 and BDE 47, which prevail in other terrestrial species. The particular PBDE congener profile observed in the red fox resembles that seen in grizzly bears from Canada, but differs from those previously reported for terrestrial avian species. Our data confirms unambiguously that BDE 209 does bioaccumulate in terrestrial top predators, such as the red fox.     

Regional trend and tissue distribution of brominated flame retardants and persistent organochlorines in raccoon dogs (Nyctereutes procyonoides) from Japan

The present study investigated concentrations and patterns of brominated flame retardants, such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs), and persistent organochlorines (OCs) in liver and adipose tissues of raccoon dogs (RD: Nyctereutes procyonoides) collected from two metropolises and a local prefecture in Japan during 2001-2006. Relatively high concentrations of PBDEs were found in RD livers, while HBCD levels were the lowest among the measured organohalogen compounds. Among PBDE congeners, BDE 209 was predominant in RDs from all the regions, indicating that pollution derived from the technical decaBDE product is extensive across Japan. On the other hand, concentrations of tetra- to nona-BDE congeners in RDs from a metropolis were significantly higher than those from the other two regions, implying that there were regional differences in the past usage of the technical tetraBDE and octaBDE products. Such a regional difference was also observed for HBCD levels. Lipid-normalized concentration ratios of liver to adipose tissue (L/A ratio) for tri to hepta-BDE congeners were lower than 1.0 in the investigated eight RDs, suggesting lipid-dependent accumulation. However, the LA ratios of BDE 209 exceeded 1.0 in all the specimens, suggesting hepatic retention of this compound. In addition, lipid-dependent accumulation of a-HBCD was observed, but the L/A ratios of gamma-HBCD were greater than 1.0 in some specimens. These results indicate that Japanese RDs have been recently exposed to BDE 209 and gamma-HBCD and accumulated both these compounds preferentially in blood-rich organs, probably due to their binding to proteins and/or rapid biotransformation, as reported in experimental rodents.     

Effects of deBDE and PCB-126 on hepatic concentrations of PBDEs and methoxy-PBDEs in Atlantic tomcod

The biotransformation of high bromosubstituted polybrominated diphenyl ethers (PBDEs) congeners contained in a commercial deca mixture (DeBDE) is of environmental concern because it might lead to the increase of toxic low brominated PBDEs in biota. A few studies have reported that freshwater fish dietary exposed to DeBDE or its main constituent, decabrominated PBDE congener (BDE-209), had their tissues enriched with PBDEs not initially present in fish or feed. In the present study, Atlantic tomcod (Microgadus tomcod) were intraperitoneally (IP) injected with DeBDE to assess hepatic concentration changes of PBDEs and methoxy polybrominated diphenyl ethers (MeO-PBDEs) in a marine fish species. Tomcod were also IP injected with polychlorinated biphenyl (PCB)-126 to evaluate the impact of cytochrome P4501A (CYP1A) induction on the biotransformation of injected PBDEs contained in DeBDE and PBDEs initially present in fish. Besides BDE-209, concentrations of BDE-203 and three other unidentified octabrominated PBDEs and the nonabrominated PBDEs (BDE-206, -207, and -208) were enriched in the liver of fish injected with DeBDE. All these PBDE congeners, essentially absent in control fish, were identified as impurities in DeBDE, and, thus, their presence could not be attributed exclusivelyto biotransformation. Despite a 4.3times increase of EROD activity in the liver of tomcod injected with both PCB-126 and DeBDE, compared to DeBDE alone, no further increases of PBDE hepatic concentrations were observed. However, depleted concentrations of BDE-17 (x 1.5) and 6-MeO-BDE-47 (x 1.4) were found in fish IP injected with DeBDE compared to control fish, likely due to activated hepatic metabolic enzymes other than CYP1A. Fish injected with PCB-126 showed an even more significant depletion of BDE-17 hepatic concentrations (x 3.5) than the one associated with the DeBDE treatment and a significantly lower proportion of fish with quantifiable concentrations of BDE-203. Thus, CYP1A inducers can promote the biotransformation of PBDEs in fish liver. This study shows that exposure of fish to DeBDE is expected to result in the enrichment of high brominated PBDEs in fish liver and that metabolic activities in fish can affect their PBDE bioaccumulation pattern and possibly the toxicity of PBDEs to fish.     

Polybrominated diphenyl ethers in the sediments of the Great Lakes. 1. Lake Superior

Sediment cores were taken in 2001 and 2002 in Lake Superior at six locations away from lakeshores and segmented at 0.5-5 cm intervals. The year of sediment deposition was estimated for each segment of four cores using the 210Pb dating technique. Samples were Soxhlet-extracted and cleaned up by silica gel fractionation, and the concentrations of 10 polybrominated diphenyl ethers (PBDEs) and 19 polychlorinated biphenyls (PCBs) were measured by GC-MS in SIM mode. In contrast to recent declining or level-off trends in PCB fluxes, the sedimentary records of PBDEs generally show a significant increase in recent years. The load of total PBDEs to Lake Superior was estimated to be 2-6 metric tons, and the current loading rate was about 80-160 kg yr(-1). With the exclusion of decabromodiphenyl ether (BDE209), the surficial concentration of sumPBDE (sum of 9 congeners) ranged from 0.5 to 3 ng g(-1), and the current sumPBDEs flux was 8-31 pg cm(-2) yr(-1). The concentrations of BDE209 were about an order of magnitude higher than the sum of other congeners, comprising 83-94% of the total PBDE inventory in the sediments. Among the other nine PBDEs detected, congeners 47 and 99 were the most abundant, and congeners 100, 153, 154, and 183 were also detected in all the cores. Congener analysis demonstrated that the pattern of PBDEs in Lake Superior sediments differs from those in air and fish.