Hydroxylated and methoxylated polybrominated diphenyl ethers in a Canadian Arctic marine food web

Residues of hydroxylated (OH-) and methoxylated (MeO-) polybrominated diphenyl ethers (PBDEs) have been previously detected in precipitation, surface waters, wildlife, and humans. We report measured concentrations of OH-PBDEs, MeO-PBDEs, and Br3-Br7 PBDEs in sediments and biota from a Canadian Arctic marine food web. PBDEs exhibited very low trophic magnification factors (TMFs between 0.1-1.6), compared to recalcitrant PCBs (TMFs between 3 and 11), indicating biotransformation via debromination and/or cytochrome P450 mediated metabolism. OH-PBDEs were not detectable in samples of blood, muscle, and/or liver of fish and marine wildlife. Five OH-PBDEs were detected at very low concentrations (range: 0.01-0.1 ng x g(-1) lipid equivalent) in beluga whale blubber and milk. The data indicate negligible formation/retention of OH-PBDEs in these Arctic marine organisms. Appreciable levels of several MeO-PBDEs were observed in bivalves, Arctic cod, sculpin, seaducks, and beluga whales (mean range 0.1-130 ng x g(-1) lipid equivalent). 2'-MeO-BDE-68 and 6-MeO-BDE-47 exhibited the highest concentrations among the brominated compounds studied (including BDE-47 and BDE-99) and biomagnified slightly in the food web, with TMFs of 2.3 and 2.6, respectively. OH- and MeO-PBDEs in this Arctic marine food web may occur via metabolic transformation of PBDEs or bioaccumulation of PBDE degradation products and/or natural marine products. We observed no evidence of a local natural source of OH- or MeO-PBDEs, as no measurable quantities of those compounds were observed in ambient environmental media (i.e., sediments) or macroalgae. Further investigations of PBDEs and their hydroxylated and methoxylated analogues would be useful to better understand sources, fate, and mechanisms governing biotransformation and bioaccumulation behavior of these compounds.     

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.     

Occurrences and fates of hydroxylated polybrominated diphenyl ethers in marine sediments in relation to trophodynamics

While occurrences and origins of hydroxylated (OH-) polybrominated diphenyl ethers (PBDEs) in organisms have been reported, the fates of these compounds in abiotic matrixes and related trophodynamics are unclear. The present study measured concentrations of nine OH-PBDEs, twelve methoxylated (MeO-) PBDEs, and eleven PBDEs in marine sediments and explored the trophodynamics of OH-PBDEs in five invertebrates, eight fish, and two species of birds from Liaodong Bay, north China. While concentrations of PBDEs were less than the limit of quantification in sediments, concentrations of ΣOH-PBDEs and ΣMeO-PBDEs were 3.2-116 pg/g dry weight (dw) and 3.8-56 pg/g dw, respectively. When the detected compounds were incubated in native marine sediments the interconversion between 6-OH-BDE47 and 6-MeO-BDE47 was observed. This result is consistent with the similar spatial distributions and significant correlation between the concentrations of these naturally occurring compounds. 6-OH-BDE47 and 2'-OH-BDE68 were detected as the two major congeners in organisms collected from Liaodong Bay, and concentrations were 0.24 ± 0.005 ng/g lw (lipid weight) and 0.088 ± 0.006 ng/g lw, respectively. Biota-sediment accumulation factors (BSAFs) for invertebrates of 6-OH-BDE47 and 2'-OH-BDE68 were 0.017-0.96 and 0.19-1.5 (except for short-necked clam: 6.3), respectively. Lipid-normalized concentrations of 6-OH-BDE47 and 2'-OH-BDE68 decreased significantly with trophic level with TMFs of 0.21 and 0.15, respectively. The fates of OH-PBDEs in sediment together with their trophodynamics in marine food webs suggested that OH-PBDEs are partitioned into sediment and undergo biodilution in the marine food web.     

Trophodynamics of polybrominated diphenyl ethers in the marine food web of Bohai Bay, North China

Polybrominated diphenyl ethers (PBDEs) are of great environmental concern due to the exponential increase of the concentrations in the environment, especially in high trophic level organisms, and the trophodynamics of these chemicals in aquatic food webs is an important criterion for assessing their ecological risk. This study analyzed 13 PBDEs in the zooplankton, five invertebrate species, six fish species, and one marine bird species collected from Bohai Bay. PBDE concentrations in organisms from Bohai Bay (sigmaPBDEs: 0.15-32.8 ng/g lipid weight) were low compared with other marine organisms worldwide, and BDE-47 wasthe predominant compound in most samples,followed by BDE-28, BDE-99/BDE-100, and BDE-119. Correlation between lipid-normalized concentrations of PBDEs, and trophic levels determined by stable nitrogen isotope technologies confirmed that PBDEs were biomagnified in the marine food web. Significantly positive relationships were found fortotal PBDEs and four PBDE compounds (BDE-28, BDE-47, BDE-100, and BDE-119), and their trophic magnification factors (TMFs) were 3.53, 3.57, 7.24, 3.23, and 2.60, respectively. The concentration ratios between congeners (BDE-99/BDE-100 and BDE-99/BDE-47) were found to decrease with increasing trophic levels, suggesting that trophic-level-dependent concentrations ratios between BDE-99 and BDE-100 would be contributed by trophic level-dependent biotransformation between BDE-99 and BDE-47, and therefore resulting in the dominance of BDE-100 compared with BDE-99 and the relatively high trophic magnification of BDE-47 in the marine food web.     

Polybrominated diphenyl ethers, hydroxylated polybrominated diphenyl ethers, and measures of thyroid function in second trimester pregnant women in California

Prenatal exposure to polybrominated diphenyl ethers (PBDEs) may disrupt thyroid function and contribute to adverse neurodevelopmental outcomes. We conducted a pilot study to explore the relationship between serum concentrations of lower-brominated PBDEs (BDE-17 to -154), higher-brominated PBDEs (BDE-183 to -209), and hydroxylated PBDE metabolites (OH-PBDEs) with measures of thyroid function in pregnant women. Concentrations of PBDEs, OH-PBDEs, thyroid-stimulating hormone (TSH), total thyroxine (T(4)), and free T(4) were measured in serum samples collected between 2008 and 2009 from 25 second trimester pregnant women in California. Median concentrations of lower-brominated PBDEs and OH-PBDEs were the highest reported to date in pregnant women. Median concentrations of BDE-47 and the sum of lower-brominated PBDEs (ΣPBDE(5)) were 43.1 ng/g lipid and 85.8 ng/g lipid, respectively, and the sum of OH-PBDEs (ΣOH-PBDE(4)) was 0.084 ng/mL. We observed a positive association between the weighted sum of chemicals known to bind to transthyretin (ΣTTR binders) and TSH levels. We also found positive associations between TSH and ΣPBDE(5), ΣOH-PBDE(4), BDE-47, BDE-85, 5-OH-BDE47, and 4'-OH-BDE49, and an inverse association with BDE-207. Relationships with free and total T(4) were weak and inconsistent. Our results indicate that PBDE exposures are elevated in pregnant women in California and suggest a relationship with thyroid function. Further investigation is warranted to characterize the risks of PBDE exposures during pregnancy.     

Development of a multichemical food web model: application to PBDEs in Lake Ellasjoen, Bear Island, Norway

A multichemical food web model has been developed to estimate the biomagnification of interconverting chemicals in aquatic food webs. We extended a fugacity-based food web model for single chemicals to account for reversible and irreversible biotransformation among a parent chemical and transformation products, by simultaneously solving mass balance equations of the chemicals using a matrix solution. The model can be applied to any number of chemicals and organisms or taxonomic groups in a food web. The model was illustratively applied to four PBDE congeners, BDE-47, -99, -100, and -153, in the food web of Lake Ellasj?en, Bear Island, Norway. In Ellasj?en arctic char (Salvelinus alpinus), the multichemical model estimated PBDE biotransformation from higher to lower brominated congeners and improved the correspondence between estimated and measured concentrations in comparison to estimates from the single-chemical food web model. The underestimation of BDE-47, even after considering bioformation due to biotransformation of the otherthree congeners, suggests its formation from additional biotransformation pathways not considered in this application. The model estimates approximate values for congener-specific biotransformation half-lives of 5.7,0.8,1.14, and 0.45 years for BDE-47, -99, -100, and -153, respectively, in large arctic char (S. alpinus) of Lake Ellasj?en.     

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.     

Bioaccumulation and metabolism of polybrominated diphenyl ethers in carp (Cyprinus carpio) in a water/sediment microcosm: important role of particulate matter exposure

Microcosms were built up to simulate a pond system with polybrominated diphenyl ether (PBDE) contaminated sediment and bioorganisms. The microcosms were divided into groups A and B. In group A, both benthic invertebrates (tubificid worms) and carp (Cyprinu carpio) were added, while in group B, only fish were added. After exposure for 20 d, the fish were sampled (exposure I). A net was fixed in the microcosms, and new fish were added (exposure II). These fish were prohibited from contacting the sediment by the net, and the accumulation and depuration of PBDEs in the fish were investigated. Among 11 monitored PBDE congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, BDE-206, BDE-207, BDE-208, and BDE-209), only 5 congeners (BDE-28, BDE-47, BDE-100, BDE-153, and BDE-154) were detected in the carp fillets and liver. BDE-99 and BDE-183 were not detected in the fish because of the efficient metabolic debromination in carp tissues. The uptake of PBDEs in exposure I was significantly higher/faster than that in exposure II, since the fish in exposure I had an opportunity to take in more of the highly contaminated particles. The uptake kinetics (k(s)) and elimination (k(e)) rate coefficients showed a general trend of decreasing with increasing log K(ow). No significant difference was observed in uptake/depuration kinetics between groups A and B, indicating that the tubificids' reworking does not affect the bioaccumulation of sediment-associated PBDEs in fish significantly. All the PBDE congeners, including nona- and deca-BDEs, were bioaccumulated in the tubificid worms. The PBDE concentrations in the worms were significantly higher than those in the fish, and the congener profile of the sevem major congeners (BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, and BDE-183) was distinctly different from that of fish tissues. The biota-sediment accumulation factors in the worms ranged from 0.01 to 5.89 and declined with increasing bromination and log K(ow.).     

Higher brominated diphenyl ethers and hexabromocyclododecane found in eggs of peregrine falcons (Falco peregrinus) breeding in Sweden

Several brominated flame retardants (BFRs) were analyzed in peregrine falcon eggs collected in 1987-1999, including the constituents of the technical polybrominated diphenyl ether (PBDE) products Penta (BDE-47, -99, -100, -153, -154), Octa (BDE-183), and Deca (BDE-209), hexabrominated biphenyl (BB-153), and hexabromocyclododecane (HBCD). The eggs represented females from three different breeding populations, northern Sweden, southwestern Sweden, and a captive breeding population. All BFRs analyzed for were found, including BDE-183 and -209, and concentrations were much higher in wild falcons (geometric mean sigmaPBDE, BB-153, and HBCD for northern/southern populations of 2200/2700, 82/77, and 150/250 ng/g lw, respectively) than in captive falcons (39, 8 ng/g lw, and not detected, respectively). This is the first time, to our knowledge, that BDE-183 and -209 have been quantified in high trophic level wildlife.     

Bioaccumulation, biotransformation, and biochemical effects of brominated diphenyl ethers in juvenile lake trout (Salvelinus namaycush)

Juvenile lake trout (Salvelinus namaycush) were exposed to three dietary concentrations (0, approximately 2.5, and approximately 25 ng/g per BDE congener) of 13 BDE congeners (3-10 Br atoms) in the laboratory for 56 days, followed by 112 days of clean food, to examine bioaccumulation parameters and potential biochemical effects. The bioaccumulation of BDEs by the trout was highly influenced by biotransformation, via debromination, which resulted in bioaccumulation parameters that were much different than would be expected based on studies of chlorinated organic compounds (e.g., PCBs). Half-lives (t1/2's) for some BDE congeners (e.g., BDE-85 and -190) were much lower than expected based on their Kow, which was likely due to biotransformation, whereas t1/2's of other BDE congeners (e.g., BDE-66, -77, -153, and -154) were much longer than anticipated based on Kow. This was likely because the metabolites of BDE formed via debromination had the same chemical structure of these BDE congeners, which supplemented measured concentrations. The detection of three BDE congeners (an unknown penta, BDE-140, and an unknown hexa) in the fish that were not present in the food or in the control fish provide further evidence forthe debromination of BDEs. Half-lives of BDEs ranged from 38 +/- 9 to 346 +/- 173 days and biomagnification factors ranged from 1.6 (BDE-190) to 45.9 (BDE-100), but these bioaccumulation parameters need to be viewed with caution because they were highly influenced by debromination and relative abundance of individual BDEs that the fish were exposed to. CYP1A enzyme activity, measured as EROD, and free tri-iodothyronine (T3) concentrations in the plasma of lake trout varied significantly throughout the experiment but were not related to BDE exposure. In contrast, plasma levels of thyroxine levels (T4) were lower in both groups of PBDE-exposed fish compared with control fish after 56 days of exposure, and after 168 days in the high dose, suggesting that PBDEs may influence thyroid homeostasis at levels that are higher than what is normally found in the environment.     

Reconstitution studies of pesticides and surfactants exploring the cause of estrogenic activity observed in surface waters of the san francisco bay delta

To evaluate the potential role of endocrine disruption in the decline of pelagic fishes in the San Francisco Bay Delta of California, various surface water samples were collected, extracted, and found to elicit estrogenic activity in laboratory fish. Chemical analysis of the estrogenic samples indicated 2 pesticides (bifenthrin, diuron), 2 alkyphenols (AP), and mixtures of 2 types of alkyphenol polyethoxylates (APEOs). Evaluation of estrogenic activity was further characterized by in vitro bioassays using rainbow trout hepatocytes (Oncorhynchus mykiss) and in vivo studies with Japanese medaka (Oryzias latipes). In the in vitro bioassays, hepatocytes exposed to the pesticides alone or in combination with the AP/APEO mixtures at concentrations observed in surface waters failed to show estrogenic activity (induction of vitelloginin mRNA). In the in vivo bioassays, medaka exposed to individual pesticides or to AP/APEO alone did not have elevated VTG at ambient concentrations. However, when the pesticides were combined with AP/APEOs in the 7-day exposure a significant increase in VTG was observed. Exposure to a 5-fold higher concentration of the AP/APEO mixture alone also significantly induced VTG. In contrast to earlier studies with permethrin, biotransformation of bifenthrin to estrogenic metabolites was not observed in medaka liver microsomes and cytochrome P450 was not induced with AP/APEO treatment. These results showed that mixtures of pesticides with significantly different modes of action and AP/APEOs at environmentally relevant concentrations may be associated with estrogenic activity measured in water extracts and feral fish that have been shown to be in population decline in the San Francisco Bay Delta.     

Polybrominated diphenyl ethers in peregrine falcon (Falco peregrinus) eggs from the northeastern U.S

A total of 114 peregrine falcon eggs from nests in Connecticut, Massachusetts, Maine, New Hampshire, Rhode Island, and Vermont were analyzed for polybrominanted diphenyl ethers (PBDEs). Eggs were collected from 1996 to 2006, excluding 1997 and 1998. Total PBDE concentrations ranged from 74.5 to 6610 ng/g wet weight, with a median of 440. These levels were generally higher than those observed in European peregrine eggs, but comparable to those in North American seabird eggs. Congener patterns differed from such seabirds and were dominated by BDE-153, followed by BDE-99, -183, -209, -197, -207, -154, -100, and -196; with lesser contributions from BDE-47, -208, -203, -201, -206, -202, -138, and -119. Urban and rural falcon eggs contained similar total PBDE concentrations but different congener profiles. Urban eggs exhibited higher BDE-209 concentrations and greater percentages of other highly brominated congeners. BDE-209 was detectable in all eggs, with concentrations ranging from 1.4 to 420 ng/g wet weight Five octa- and three nona-brominated congeners were also frequently detected, some likely derived from the biodegradation of BDE-209. Temporal analyses indicated no significant changes in concentrations of total PBDEs, or most individual congeners, during the study period. An exception was BDE-209. It exhibited a significant increase, with a doubling time of 5 years. Current PBDE burdens may be insufficient to cause noticeable adverse effects at the population level, as the number of territorial pairs increased in the past decade. However, the high BDE-209 concentrations, short doubling time, and likely biodegradation observed in peregrine eggs from the northeastern U.S. may supportthe need for additional deca-BDE regulations.     

Hydroxylated and methoxylated brominated diphenyl ethers in the red algae Ceramium tenuicorne and blue mussels from the Baltic Sea

Methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and hydroxylated PBDEs (OH-PBDEs) have recently been identified in fish and wildlife from the Baltic Sea. Both OH-PBDEs and MeO-PBDEs are known natural products, while OH-PBDEs also may be metabolites of PBDEs. The aim of the present study was to determine if the red macroalga Ceramium tenuicorne could be a source for MeO- and OH-PBDEs in the Baltic environment. Blue mussels (Mytilus edulis) from the same area were also investigated for their content of MeO- and OH-PBDEs. Seven OH-PBDEs and four MeO-PBDEs were present both in the red macroalga and the blue mussels. The mussels also contained a monochlorinated OH-tetraBDE. One of the compounds, 6-methoxy-2,2',3,4,4',5-hexabromodiphenyl ether, has never been reported to occur in the environment. The identification was based on comparison of relative retention times with reference standards, on two gas chromatographic columns of different polarities, together with comparisons of full-scan electron capture negative ionization (ECNI) and electron ionization (EI) mass spectra. It is shown that MeO-PBDEs and OH-PBDEs are present in algae, but at this stage it could not be confirmed if the compounds are produced by the alga itself or by its associated microflora and/or microfauna.     

Polybrominated diphenyl ethers in birds of prey from Northern China

Birds of prey from Northern China (Beijing area) were examined for polybrominated diphenyl ethers (PBDEs). A total of 47 specimens from eight different species were analyzed. Muscle and liver were analyzed separately for each bird. Kidneys were pooled by species. Common kestrels exhibited the highest PBDE levels (mean muscle and liver concentrations of 12300 and 12200 ng/g lipid weight, respectively), with maxima in an individual bird of 31700 in muscle and 40900 ng/g lw in liver. Congener profiles differed between some species, but were generally dominated by the more brominated congeners (e.g., BDE-153, -209, -183, -207). BDE-209 was especially elevated compared to other published reports. Interspecies differences in congener concentrations and profiles may be due to diet, behavior, or biotransformation capacities. BDE-209 was detected in 79.4% of the samples. Common kestrels contained the highest BDE-209 levels (mean/maxima of 2150/6220 in muscle and 2870/12200 ng/g lw in liver). BDE-209 was the dominant congener in tissues from some buzzards, scops owls, and long-eared owls. It was the second most abundant congener in common kestrels. The remarkable levels and dominance of BDE-209 may relate to significant production, usage, or disposal of deca-containing products in China. These observations reinforce the growing view that organisms using terrestrial food chains may have greater exposure to BDE-209.     

Photochemical Formation of Brominated Dioxins and Other Products of Concern from Hydroxylated Polybrominated Diphenyl Ethers (OH-PBDEs)

The photochemical conversion of selected hydroxylated polybrominated diphenyl ethers (OH-PBDEs) to dioxins and other products was investigated. OH-PBDEs, which are both transformation products of polybrominated diphenyl ethers and naturally occurring compounds, undergo direct photolysis to yield a number of products that may have a higher toxicity than their parent. The compounds investigated were 6-OH-PBDE 99, 6'-OH-PBDE 100, and 6'-OH-PBDE 118. Of special interest was 6'-OH-PBDE 118, a potential transformation product of PBDE 153 that is capable of photochemically generating 2,3,7,8-tetrabromodibenzo-p-dioxin, the most toxic brominated dioxin congener. Photolysis experiments were conducted at two different pH values to assess the photochemical behavior of both the phenol and phenolate form of the compounds. The percent conversion to dioxin and other photoproducts was determined and the natural product, 6-OH-PBDE 99, was found to have the highest conversion to dioxin (7%). The reaction quantum yields ranged from 0.027 to 0.16 across all photolysis conditions. In addition, it is shown that all three compounds are capable of photochemically generating other compounds of concern, including brominated phenols and a dibenzofuran.     

Temporal trend studies on tetra- and pentabrominated diphenyl ethers and hexabromocyclododecane in guillemot egg from the Baltic Sea

Guillemot eggs from the Baltic Sea, sampled between 1969 and 2001, were analyzed for tetra- and pentabromodiphenyl ethers (2,2',4,4'-tetraBDE (BDE-47), 2,2',4,4',5-pentaBDE (BDE-99), and 2,2',4,4',6-pentaBDE (BDE-100)), and hexabromocyclododecane (HBCD). This temporal trend study indicates that the concentrations of the polybrominated diphenyl ether compounds increased from the 1970s to the 1980s, peaking around the mid- to the late-1980s. These peaks are then followed by a rapid decrease in concentrations during the rest of the study period, with the concentrations of the major BDE congener below 100 ng/g lipid weight at the end of the period. This corresponds to less than 10% of its peak values. The concentrations of HBCD show a different pattern over time. After a peak in the middle of the 1970s followed by a decrease, the concentrations increased during the latter part of the 1980s. During the recent 10-yr period no significant change has occurred, and the annual mean concentrations are more or less stable at a higher level as compared to the beginning of the study period.     

Consumption of fish from a contaminated lake strongly affects the concentrations of polybrominated diphenyl ethers and hexabromocyclododecane in serum

Very high concentrations of polybrominated diphenyl ethers (PBDE) have been reported in fish from Lake Mj?sa in Norway. This study was performed to examine the serum concentrations of PBDE and hexabromocyclododecane (HBCD) in consumers of fish from this lake and to investigate possible relationships between serum concentrations, self-reported fish intake and calculated total dietary PBDE exposure. Serum concentrations of the sum of the seven PBDE (BDE-28, 47, 99, 100, 153, 154 and 183) were significantly higher than those of a reference group of Norwegians eating only food with background levels of contamination (medians: 18 ng/g lipids men, 8.4 ng/g lipids women). The median dietary intake of Sum 7 PBDE was 2549 ng/day (30 ng/kg body weight/day), the highest dietary intake of PBDE reported. The contribution from fish caught from the contaminated lake comprised 98.7% of the total dietary exposure. For men, serum levels of PBDE were strongly correlated with the calculated dietary exposure, except for BDE-209. This suggests that sources other than the diet are important for human BDE-209 exposure. The median serum HBCD concentration was 4.1 and 2.6 ng/g lipids for men and women, respectively, and was also found to be associated with consumption of fish from Lake Mj?sa.     

Computational toxicological investigation on the mechanism and pathways of xenobiotics metabolized by cytochrome P450: a case of BDE-47

Understanding the transformation mechanism and products of xenobiotics catalyzed by cytochrome P450 enzymes (CYPs) is vital to risk assessment. By density functional theory computation with the B3LYP functional, we simulated the reaction of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) catalyzed by the active species of CYPs (Compound I). The enzymatic and aqueous environments were simulated by the polarizable continuum model. The results reveal that the addition of Compound I to BDE-47 is the rate-determining step. The addition of Compound I to the ipso and nonsubstituted C atoms forms tetrahedral σ-adducts that further transform into epoxides. Hydroxylation of the epoxides leads to hydroxylated polybrominated diphenyl ethers and 2,4-dibromophenol. The addition to the Br-substituted C2 and C4 atoms has a higher barrier than addition to the nonsubstituted C atoms, forming phenoxide and cyclohexadienone which subsequently undergo debromination/hydroxylation. A novel mechanism was identified in which the approach of Compound I to C2 led to formation of a phenoxide and an expelled Br(-) ion. The predicted products were consistent with the metabolites identified by others. As a first attempt to simulate the enzymatic transformation of a polycyclic compound, this study may enlighten a computational method to predict the biotransformation of xenobiotics catalyzed by CYPs.     

Temporal trends, congener patterns, and sources of octa-, nona-, and decabromodiphenyl ethers (PBDE) and hexabromocyclododecanes (HBCD) in Swiss lake sediments

With the recent ban of pentabromodiphenyl ether (technical PentaBDE) and octabromodiphenyl ether (technical OctaBDE) mixtures in the European Union (EU) and in parts of the United States, decabromodiphenyl ether (technical DecaBDE) remains as the only polybrominated diphenyl ether (PBDE) based flame retardant available, today. The EU risk assessment report for DecaBDE identified a high level of uncertainty associated with the suitability of the current risk assessment approach for secondary poisoning by debromination of DecaBDE to toxic lower brominated diphenylethers. Addressing this still open question, we investigated concentrations and temporal trends of DecaBDE, NonaBDE, and OctaBDE congeners in the sediments of Greifensee, a small lake located in an urban area close to Zürich, Switzerland. PBDE appeared first in sediment layers corresponding to the mid 1970s. While total Tri-HeptaBDE (BDE-28, -47, -99, -100, -153, -154 and -183) concentrations leveled off in the mid 1990s to about 1.6 ng/g dw (dry weight), DecaBDE levels increased steadily to 7.4 ng/g dw in 2001 with a doubling time of 9 years. Hexabromocyclododecanes (HBCD) appeared in Greifensee sediments in the mid 1980s. They are an important class of flame retardants that are being used in increasing amounts, today. As was observed for DecaBDE, HBCD concentrations were continuously increasing to reach 2.5 ng/g dw in 2001. Next to DecaBDE, all 3 NonaBDE congeners (BDE-208, BDE-207, and BDE-206) and at least 7 out of the 12 possible OctaBDE congeners (BDE-202, BDE-201, BDE-197/204, BDE-198/203, BDE-196/200, BDE-205, and BDE-194) were detected in the sediments of Greifensee. Highest concentrations were found in the surface sediments with 7.2, 0.26, 0.14, and 1.6 ng/g dw for Deca-, Nona-, Octa-, and the sum of Tri-HeptaBDE, respectively. While DecaBDE and NonaBDE were found to increase rapidly, the increase of OctaBDE was slower. Congener patterns of Octa- and NonaBDE present in sediments of Greifensee did not change with time. Consequently, there was no evidence for sediment mediated long-term transformation of PBDE within the observed time span of almost 30 years. Despite the high persistence of DecaBDE, environmental debromination occurs, as shown by the detection of a shift in congener patterns of Octa- and NonaBDE in sediments, compared to the respective congener patterns in technical PBDE products. The OctaBDE congener BDE-202 was detected in sediments, representing a transformation product that is not reported in any of the technical PBDE products. Comparison of OctaBDE congener patterns in sediments with OctaBDE congener patterns from known sources reveals that (i) they were distinctively different from the congener patterns in technical PBDE products and (ii) that they were similar to the OctaBDE patterns in house dust and photodegradation products of DecaBDE, suggesting contributions from these sources.