Serum concentrations of polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyl (PBB) in the United States population: 2003-2004

Polybrominated diphenyl ethers (PBDEs) and 2,2',4,4',5,5'-hexabromobiphenyl (BB-153) are chemicals known as brominated flame retardants. We have assessed the exposure status of the United States population to PBDEs and BB-153 and explored associations with demographic information, including participants' age, sex, and race/ethnicity. A total of 2,062 serum samples, from participants in the National Health and Nutrition Examination Survey (NHANES) 2003-2004 aged 12 years and older, were analyzed for PBDEs and BB-153; stratified and regression analyses were used to examine levels among demographic groups. The congener with the highest serum concentration was 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) [geometric mean 20.5 ng/g lipid]; followed by 2,2',4,4',5,5'-hexaBDE (BDE-153) [5.7 ng/g lipid]; 2,2',4,4',5-pentaBDE (BDE-99) [5.0 ng/g lipid; a value equal to the highest limit of detection for an individual sample]; 2,2',4,4',6-pentaBDE (BDE-100) [3.9 ng/g lipid]; BB-153 [2.3 ng/g lipid]; and 2,4,4'-triBDE (BDE-28) [1.2 ng/g lipid]. For BDE-47, we observed no significant difference in the least-squares geometric mean (LSGM) by sex, but with age we found both a linear decrease (p = 0.01) and a positive quadratic trend (p = 0.01). Its LSGM, 27.9 ng/lipid, in the 12-19 year olds decreased to 17.2 ng/g lipid in the 40-49 year group, and then curved upward to 20.4 ng/g lipid in the > or =60 years olds. Mexican Americans had the highest LSGM of BDE-47 (24.5 ng/g lipid), which was significantly higher than that of non-Hispanic whites (19.7 ng/g lipid, p = 0.01). Adults 60 years and older were twice as likely as adults 20-59 years old to have a serum BDE-47 concentration above the 95th percentile (p = 0.02).These data provide needed exposure assessment data for public health decisions.     

Polybrominated dibenzo-p-dioxins,dibenzofurans, and diphenyl ethers in Japanese human adipose tissue

Human adipose samples collected in Tokyo, Japan in 1970 and 2000 were analyzed for the presence of polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), and diphenyl ethers (PBDEs), and the concentrations in the two groups were compared. As far as we know, the concentrations of the PBDD/Fs in adipose tissue from the general Japanese population are reported for the first time. Three PBDD/F congeners were found in the following adipose tissues: 2,3,7,8-TeBDD, 2,3,7,8-TeBDF, and 2,3,4,7,8-PeBDF. The median concentrations (ranges) of three PBDD/Fs in 1970 and 2000 were 5.1 (3.4-8.3) and 3.4 (1.9-5.3) pg/g lipid wt (l.w.), respectively. For PBDEs, seven PBDE congeners were determined in the following samples: 2,4,4'-tribromodiphenyl ether (BDE-28), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), 2,2',4,4',6-pentabromodiphenyl ether (BDE-100), 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153), 2,2',4,4',5',6-hexabromodiphenyl ether (BDE-154), and 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183). Median concentrations (ranges) of PBDEs showed a significant increase from 29.2 (6.8-78.4) pg/g l.w. in 1970 to 1288 (466-2,753) pg/g l.w. in 2000. BDE-47, the major congener of PBDEs, was 56.2% and 35.6% of the total in 1970 and 2000, respectively, whereas the BDE-153 was < 1% and 29.7% of the total in 1970 and 2000, respectively. This may indicate that the source of PBDEs had changed during this period. Further analysis of archived human samples from 1970 to 2000 is needed to describe the details of the contamination trends of PBDD/Fs and PBDEs in the Japanese population. Furthermore, PBDD/F monitoring, particularly 2,3,7,8-TeBDD and 2,3,7,8-TeBDF, may give more toxicological information based on TeCDD toxic equivalents (TEQs).     

Occupational exposure to commercial decabromodiphenyl ether in workers manufacturing or handling flame-retarded rubber

Commercial decabromodiphenyl ether (DecaBDE) is commonly used as a flame retardant in different electrical and textile applications. It is also used in the production of flame-retarded rubber compound. DecaBDE is the major technical polybrominated diphenyl ether (PBDE) in use today and consists mainly of decabromodiphenyl ether (BDE-209). PBDEs, including BDE-209, are well-known environmental pollutants, ubiquitous both in aquatic and terrestrial environments. The aim of the present study was to assess the exposure to PBDEs in workers manufacturing or handling rubber which was flame retarded with DecaBDE. A referent group, abattoir workers (slaughterhouse workers), with no occupational exposure to PBDEs, was also investigated. Moreover, the methodology for analysis of PBDEs in serum was refined, with special emphasis on congeners with a high number of bromine substituents, i.e., octa- to decaBDEs. The highest BDE-209 concentration observed among the rubber workers was 280 pmol/g lipid weight (I.w.) (270 ng/g I.w.). The median concentration of BDE-209 among rubber workers was 37 pmol/g I.w. (35 ng/g I.w.). Among referents, the median was 2.5 (range 0.92-9.7) pmol/g I.w. (median 2.4 ng/g I.w.). In rubber workers the BDE-209 concentrations were up to 32% (median 4%) of the 2,2',4,4',5,5'-chlorobiphenyl (CB-153) concentrations, on a molar basis, whereas the referents had BDE-209 concentrations which were similar to that of 2,2',4,4'-bromodiphenyl ether (BDE-47), below 1.4% (median 0.3%) of the CB-153 concentration. Concentrations of all nonabromodiphenyl ethers (nonaBDEs) and several octabrmodiphenyl ethers (octaBDEs) congeners, including BDE-203, were also elevated among the rubber workers, with 2.5- to 11-fold higher median concentrations, compared to the referents. The results confirm a significant uptake of BDE-209 in the workers exposed to DecaBDE and indicate a potential for in vivo formation of lower BDEs in these persons.     

Brominated flame retardants in archived serum samples from Norway: a study on temporal trends and the role of age

The temporal trends and influence of age and gender on levels of selected brominated flame retardants (BFRs) in human serum have been assessed by analyzing archived samples from Norway. Serum from 40 to 50 year old men collected at six time periods during 1977 to 1999 and from eight groups of differing age and gender sampled in 1998 were pooled into six and eight samples, respectively. The BFRs were isolated using solid-phase extraction (SPE) and the serum lipids decomposed bytreatmentwith concentrated sulfuric acid directly on the polystyrene-divinylbenzene SPE column, prior to elution of the BFRs. Following diazomethane derivatization, the samples were analyzed by gas chromatography-electron capture mass spectrometry. Eight BFRs were quantified in the serum samples: 2,4,4'-tribromodiphenyl ether (BDE-28), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), 2,2',4,4',6-pentabromodiphenyl ether (BDE-100), 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE-154), 2,4,6-tribromophenol (TriBP), and tetrabromobisphenol A (TBBP-A). The serum concentrations of all the BFRs, increased during the entire period with the exception of TriBP, and the sum of the six polybrominated diphenyl ethers increased from 0.44 ng/g lipids in 1977 to 3.3 ng/g lipids in 1999. The BFR concentrations in the serum from the different age groups were relatively similar, except for the age group 0-4 years, which had 1.6-3.5 times higher serum concentrations. Women older than 25 years had lower serum concentrations of BFRs compared to the corresponding group of men. No trend related to age or gender, nor time during the period 1977 to 1999 was observed for TriBP. The present study indicates an ongoing increase in human exposure to BFRs, and the current body burden appears to be independent of age, except for infants (0-4 years old), who seem to experience elevated exposure.     

Synthesis of octabrominated diphenyl ethers from aminodiphenyl ethers

Polybrominated diphenyl ethers (PBDEs) are additive brominated flame retardants (BFRs), which have become widespread pollutants in abiotic and biotic environments including man. Tetra- to hexaBDEs and decaBDE are the most common environmental PBDE contaminants. Congeners of octabromodiphenyl ethers (octaBDEs) originate from used industrial OctaBDE mixtures and from transformation products of the high-volume industrial BFR mixture "DecaBDE", which most exclusively consists of perbrominated diphenyl ether (BDE-209). The objective of the present work was to develop methods for the synthesis of authentic octaBDE congeners in order to make them available as standards for analytical, toxicological, and stability studies, as well as studies concerning physical-chemical properties. The syntheses of six octaBDEs, 2,2',3,3',4,4',5,5'-octabromodiphenyl ether (BDE-194), 2,2',3,3',4,4',5,6'-octabromodiphenyl ether (BDE-196), 2,2',3,3',4,5,5',6-octabromodiphenyl ether (BDE-198), 2,2',3,3',4,5',6,6'-octabromodiphenyl ether (BDE-201), 2,2',3,3',5,5',6,6'-octabromodiphenyl ether (BDE-202), and 2,2',3,4,4',5,6,6'-octabromdipheny ether (BDE-204), are described, of which BDE-204 was prepared via two different pathways. Syntheses of BDE-198, BDE-201, BDE-202, and BDE-204 are based on octabromination of mono- or diaminodiphenyl ethers followed by diazotization and reduction of the amino group(s). BDE-194 and BDE-196 were prepared by bromination of 3,3',4,4',5,5'-hexabromodiphenyl ether (BDE-169) and 2,3,3',4,4',5',6-heptabromodiphenyl ether (BDE-191), respectively, and BDE-169 and BDE-191 were prepared from 4,4'-diaminodiphenyl ether and 3,4'-diamiodiphenyl ether, respectively. The synthesized PBDE congeners are described by 1H NMR, 13C NMR, electron ionization mass spectra, and their melting points.     

Hydroxy-PCBs, PBDEs, and HBCDDs in serum from an elderly population of Swedish fishermen's wives and associations with bone density

Lack of human exposure data is frequently reported as a critical gap in risk assessments of environmental pollutants, especially regarding "new" pollutants. The objectives of this study were to assess serum levels of the persistent 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153), hydroxylated polychlorinated biphenyl metabolites (OH-PCBs), polybrominated diphenyl ethers (PBDEs), and hexabromocyclodode-canes (HBCDDs) in a group of Swedish middle-aged and elderly women expected to be relatively highly exposed, and to evaluate the impact of potential determinants (e.g., fish intake, age) for the inter-individual variation, as well as to investigate the association between these pollutants and bone density. No associations were found between bone mineral density or biochemical markers of bone metabolism and the analyzed environmental pollutants. Relatively high levels of CB-153 (median 260 ng/g fat) and sigma 3-OH-PCBs (median 1.7 ng/mL serum), and low concentrations of sigma6PBDEs (median 3.6 ng/g fat) were determined. Total level of HBCDDs in serum was quantified by gas chromatography with mass spectrometric detection (median 0.5 ng/g fat). HBCDD diastereomeric and enantiomeric patterns were determined by liquid chromatography with mass spectrometric detection. The dominating stereoisomer was (-)alpha-HBCDD, but 1-3% of gamma-HBCDD was also detected in the serum samples.     

Concentrations of polybrominated diphenyl ethers, polychlonnated biphenyls, and polychlorobiphenylols in serum from pregnant Faroese women and their children 7 years later

The objective of this study was to assess blood concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs), and their polychlorobiphenylol (OH-PCB) metabolites in humans with a high seafood intake. Samples were obtained from pregnant women in the Faroe Islands in 1994-1995 and from their children at 7 years of age to examine maternal transfer of the compounds to their child, age-dependent metabolism, and temporal changes. Maternal serum was dominated by 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), while 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153) prevailed in the children's serum seven years later. DecaBDE was present in both mothers and children up to 3 and 6 ng/g lipid weight, respectively. The sigmaPCB concentration in the children averaged about 60% of the concentrations in their mothers, with median levels for both above 1 microg/g lipid weight and .with similar PCB congener patterns. sigmaOH-PCB serum concentrations from the mothers and their children showed ranges of 1.8-36 ng/g wet weight (ww) and 0.49-22 ng/g ww, respectively, with all OH-PCB congener concentrations being lower in the children, except for 2,3,3',4',5-pentachloro-4-biphenylol (4-OH-CB107). Children at 7 years of age are exposed to PCBs at levels only slightly below those of their mothers, and the increased 4-OH-CB107 concentrations in children could be due to age-related differences in PCB metabolism. The PBDE concentrations were similar in both mothers and their children. The main persistent organic pollutant concentrations in the children are most probably due to other environmental exposure than maternal transfer.     

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.     

Serum levels of polybrominated diphenyl ethers (PBDEs) in foam recyclers and carpet installers working in the United States

Increased exposure to the flame retardants known as polybrominated diphenyl ethers (PBDEs) may be expected to occur during the recycling of polyurethane foam containing these chemicals. To date, no studies in the United States have investigated occupational exposure to these flame retardants during recycling processes. The objective of the present study was to determine if individuals working in foam recycling facilities, and/or carpet installers who may install carpet padding manufactured from recycled foam, possess significantly higher PBDE serum levels relative to that of the general U.S. population. As a control group, serum was collected from four spouses and one clerical worker. In addition, levels in workers were also compared to the recently published national health and nutrition examination survey (NHANES) data set on PBDEs in the general U.S. population. Serum samples were collected in duplicate and analyzed by two different laboratories as quality control. Total PBDE levels were found to be significantly higher (p < 0.05) in the individuals recycling foam and installing carpet (n = 15) relative to the control group (n = 5). Median sigmaPBDE levels in the foam recyclers, carpet layers, and control group were 160, 178, and 19 ng/g lipid, respectively. In contrast, concentrations of a polybrominated biphenyl (BB-153) and a polychlorinated biphenyl (CB-153) were equivalent among all groups tested. The PBDE congeners BDE-47, 99, 100, and 153 contributed 90% of the sigmaPBDE concentration in serum and no differences in congener patterns were apparent among the different groups. Relative to concentrations measured in the NHANES, foam recyclers and carpet layers have body burdens that are an order of magnitude higher. These data suggest individuals recycling foam-containing products, and/ or using products manufactured from recycled foam (i.e., carpet padding), have higher body burdens of PBDEs, and thus may be at higher risk from adverse health effects associated with brominated flame retardant exposure.     

Brominated organic contaminants in the liver and egg of the common cormorants (Phalacrocorax carbo) from Japan

The contamination profiles of brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs), biphenyls (PBBs), dibenzo-p-dioxins (PBDDs), and dibenzofurans (PBDFs) were determined in the liver and egg of common cormorants from Japan. PBDEs and PBBs were detected in all the samples; especially the former were detected at elevated levels. PBDDs/PBDFs were also detected in cormorants, albeit the concentrations were lower than those of the PBBs. The total concentration of PBDEs ranged from 330 to 2600 in the liver and from 600 to 3300 in the egg on a nanogram per gram of lipid basis. The concentration of PBBs was in the range from 3.0 to 33 (in the liver) and from 3.4 to 82 (in the egg) on a nanogram per gram of lipid basis. The 2,2',4,4',5,5'-hexabromobiphenyl (BB-153) was the most predominant PBB congener in either organ, which corresponds to a major constituent of the BFR FireMaster BP-6. Concentrations of PBDDs/ PBDFs in the liver (range from 21 to 470) were slightly higher than in the egg (range from 31 to 160) on a picogram per gram of lipid basis. The results of this study imply that common cormorants accumulate a high level of PBDEs and PBBs. Comparing the concentrations of brominated organic compounds with those of chlorinated analogues, good relevance between PBBs and coplanar PCBs (r2 = 0.746 [liver] and 0.715 [egg]) was elucidated. To our knowledge, the present study demonstrates the first report of PBDEs, PBBs, and PBDDs/PBDFs in the common cormorant from Japan.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in human adipose tissue from New York

Human adipose tissue samples (n=52) collected in New York City during 2003-2004 were analyzed for the presence of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). Concentrations of PBDEs in adipose tissues ranged from 17 to 9630 ng/g, lipid wt (median: 77; mean: 399 ng/g, lipid wt; sum all di- through hexaBDE congeners). Average PBDE concentrations in human adipose tissues from New York City were 10- to 100-times greater than those reported for European countries. A concentration of 9630 ng/g, lipid wt, found in a sample of adipose tissue, is one of the highest concentrations reported to date. PBDE 47 (2,2',4,4'-tetraBDE) was the major congener detected in human tissues, followed by PBDE congeners #99 (2,2',4,4',5-penta BDE), 100 (2,2',4,4',6-pentaBDE), and 153 (2,2',4,4',5,5'-hexaBDE). A few individuals contained PBDE 153 as the predominant congener in total PBDE concentrations, suggesting alternative exposure sources, possibly occupational. Principal component analysis of PBDE congener composition in human adipose tissues revealed the presence of five clusters, each characterized by varying composition. No significant difference was found in the concentrations of PBDEs between gender. Concentrations of PBDEs were, on average, similar to those for PCBs in human adipose tissues, and substantially higher when PBDE outliers were retained. PBDE and PCB concentrations were not correlated. PBDE concentrations did not increase with increasing age of the subjects, whereas concentrations of PCBs increased with increasing age in males but not in females in this study. These results suggest differences between PBDEs and PCBs in their sources or time course of exposure and disposition. The presence of comparable or greater concentrations of PBDEs, relative to PCBs, highlights the importance of recentvoluntary and regulatory effortsto cease production of commercial penta- and octa-BDE in North America, although these efforts do not address continuing emissions from existing sources, such as polyurethane foams.     

High postnatal exposures to polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) via breast milk in California: does BDE-209 transfer to breast milk?

Breast milk samples collected during 2003-2005 from 82 first-time mothers in 24 communities located throughout California contained levels of polybrominated diphenyl ethers (∑(tri-hexa (8))PBDEs; median = 53.3 ng/g lw, range = 9.60-1291) and polychlorinated biphenyls (∑(12)PCBs; median = 73.4 ng/g lw, range = 22.2-433) that are among the highest in the world. PBDE levels varied 100-fold. BDE-47 was the dominant PBDE congener, with levels exceeding the U.S.EPA Reference Dose (RfD) for neurodevelopmental toxicity (100 ng/kg/day) in most (60%) breast milk samples. In some samples, BDE-209 (2/82) and/or BDE-153 (5/82) were the dominant congeners, suggesting that BDE-209 can transfer to breast milk and/or break down in the mother and transfer to the nursing infant as the lower-brominated PBDEs associated with adverse effects. PBDE levels in California breast milk are approaching those of PCBs, and the trend PBDEs > PCBs may continue as PBDEs migrate from products to the indoor and outdoor environments.     

Serum concentrations of neutral and phenolic organohalogens in pregnant women and some of their infants in The Netherlands

As part of a large European Union (EU)-funded comparative toxicology and human epidemiology study, EU-Compare, a selection of organohalogen compounds (OHCs) was analyzed in maternal serum, collected at the 35th week of pregnancy, and in cord serum of a number of their infants to determine maternal concentrations and to investigate the extent of transplacental transfer of these compounds. Eight neutral OHCs were analyzed: one polychlorinated biphenyl (PCB: CB-153),4,4'-DDE, five polybrominated diphenyl ethers (PBDEs: BDE-47, BDE-99, BDE-100, BDE-153, and BDE-154), and hexabromocyclododecane (HBCDD). Five phenolic OHCs were analyzed: three hydroxylated PCBs (40H-CB-107, 40H-CB-146, and 40H-CB-187), one hydroxylated PBDE (60H-BDE-47), and pentachlorophenol (PCP). All OHCs, except 60H-BDE-47, were present in maternal and cord serum. The historically identified OHCs showed the highest concentration: 4,4'-DDE (median value 89 ng/g lipid in maternal serum and 68 ng/g lipid in cord serum) and PCP (median value 970 pg/g serum in maternal serum and 1500 pg/g serum in cord serum). HBCDD and the PBDEs were present at much lower concentrations. We conclude that OHCs are present in the serum of pregnant women, and all compounds tested are transferred over the placenta. Because transfer is occurring at a critical stage of infant development, investigation of the health impact is urgent.     

Dramatic changes in the temporal trends of polybrominated diphenyl ethers (PBDEs) in herring gull eggs from the Laurentian Great Lakes: 1982-2006

DecaBDE is a current-use, commercial formulation of an additive, polybrominated diphenyl ether (PBDE) flame retardant composed of > 97% 2,2',3,3',4,4',5,5',6,6'-decabromoDE (BDE-209). Of the 43 PBDE congeners monitored, we report on the temporal trends (1982-2006) of quantifiable PBDEs, and specifically BDE-209, in pooled samples of herring gull (Larus argentatus) eggs from seven colonies spanning the Laurentian Great Lakes. BDE-209 concentrations in 2006 egg pools ranged from 4.5 to 20 ng/g wet weight (ww) and constituted 0.6-4.5% of sigma39PBDE concentrations among colonies, whereas sigma(octa)BDE and sigma(nona)BDE concentrations constituted from 0.5 to 2.2% and 0.3 to 1.1%, respectively. From 1982 to 2006, the BDE-209 doubling times ranged from 2.1 to 3.0 years, whereas for sigma(octa)BDEs and sigma(nona)BDEs, the mean doubling times ranged from 3.0 to 11 years and 2.4 to 5.3 years, respectively. The source of the octa- and nona-BDE congeners, e.g., BDE-207 and BDE-197, are the result of BDE-209 debromination, and they are either formed metabolically in Great Lakes herring gulls and/or bioaccumulated from the diet and subsequently transferred to their eggs. In contrast to BDE-209 and the octa- and nona-BDEs, congeners derived mainly from PentaBDE and OctaBDE mixtures, e.g., BDE-47, -99, and -100, showed rapid increases up until 2000; however, there was no increasing trend post-2000. The data illustrates that PBDE concentrations and congener pattern trends in the Great Lakes herring gull eggs have dramatically changed between 1995 and 2006. Regardless of BDE-209 not fitting the pervasive criteria as a persistent and bioaccumulative substance, it is clearly of increasing concern in Great Lake herring gulls, and provides evidence that regulation of DecaBDE formulations is warranted.     

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.     

Polybrominated diphenyl ethers and polychlorinated biphenyls in a marine foodweb of coastal Florida

Nine species of marine fish, including teleost fishes, sharks, and stingrays, and two species of marine mammals (dolphins) collected from Florida coastal waters were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) to evaluate biomagnification factors (BMF) of these contaminants in a coastal foodweb. In addition, bottlenose dolphins and bull sharks collected from the Florida coast during the 1990s and the 2000s were analyzed for evaluation of temporal trends in PBDE and PCB levels in coastal ecosystems. Mean concentrations of PBDEs in muscle tissues of teleost fishes ranged from 8.0 ng/g, lipid wt (in silver perch), to 88 ng/g, lipid wt (in hardhead catfish), with an overall mean concentration of 43 +/- 30 ng/g, lipid wt. Mean concentrations of PBDEs in muscle of sharks ranged from 37.8 ng/g, lipid wt, in spiny dogfish to 1630 ng/g, lipid wt, in bull sharks. Mean concentrations of PBDEs in the blubber of bottlenose dolphins and striped dolphins were 1190 +/- 1580 and 660 ng/g, lipid wt, respectively. Tetra-BDE 47 (2,2',4,4'-) was the major congener detected in teleost fishes and dolphin samples, followed by BDE-99, BDE-153, BDE-100, and BDE-154. In contrast, BDE-209 was the most abundant congener in sharks. Concentrations of PBDEs and PCBs in dolphins and sharks were 1-2 orders of magnitude greater than those in lower trophic-level fish species, indicating biomagnification of both of these contaminants in the marine foodweb. Based on the analysis of sharks and dolphins collected over a 10-year period, an exponential increase in the concentrations of PBDEs and PCBs has occurred in these marine predators. The doubling time of PBDE and PCB concentrations was estimated to be 2-3 years for bull sharks and 3-4 years for bottlenose dolphin.     

Brominated and fluorinated organic pollutants in the breast milk of first-time Irish mothers: is there a relationship to levels in food?

Brominated flame retardants – polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), hexabromocyclododecane (HBCD) and others – have been measured in 11 pooled breast milk samples from 109 first-time mothers in Ireland. Additionally, the study has measured levels of polybrominated dibenzo-p-dioxins and furans (PBDD/Fs), mixed halogenated dioxins (PXCC/Fs) and biphenyls (PXBs), polychlorinated naphthalenes (PCNs) and perfluoroalkylated substances (PFAS) in these samples. The mean sum of 19 PBDEs including BDE-209 was 4.85 ng g^?1 fat, which is comparable with that found in other European countries. BDE-47, BDE-153, BDE-209, BDE-99 and BDE-100 were found at the highest concentrations. The only PBBs detected consistently were BB-77, BB-126 and BB-153, with highest concentrations being found for BB-153 (mean = 0.13 ng g^?1 fat). The mean sum of HBCD enantiomers was 3.52 ng g^?1 fat, with α-HBCD representing over 70% of the total. Of the other brominated flame retardants – tetrabromobisphenol-A (TBBP-A), hexabromobenzene (HBB), decabromodiphenylethane (DBDPE) and bis(2,4,6-tribromophenoxyethane) (BTBPE) – examined, only TBBP-A was detected above the limit of detection (LOD), in two of the 11 pools analysed. All measured PBDF congeners were observed (at 0.02–0.91 pg g^?1 fat), but 2,3,7,8-tetrabromo-dibenzodioxin (TeBDD) was the only PBDD detected, with a mean concentration of 0.09 pg g^?1 fat. The occurrence of the mixed chlorinated/brominated dibenzodioxins, dibenzofurans and biphenyls, 2-B-3,7,8-CDD, 2,3-B-7,8-CDF, 4-B-2,3,7,8-CDF, PXB 105, PXB 118, PXB 126 and PCB 156 in breast milk in the current study may indicate that levels of these contaminants are increasing in the environment. Polychlorinated naphthalenes were detected in all samples, but not perfluorooctane sulfonate (PFOS) and other PFAS. The pattern of occurrence of these brominated and fluorinated persistent organic pollutants (POPs) in Irish breast milk shows a general relationship to their occurrence in food, as reported in a number of surveillance studies carried out by the Food Safety Authority of Ireland.     

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.     

Temporal development of brominated flame retardants in peregrine Falcon (Falco peregrinus) eggs from South Greenland (1986-2003)

A time trend between 1986 and 2003 was found for brominated flame retardants in peregrine falcon eggs from South Greenland, with significantly increasing concentrations of the polybrominated diphenyl ethers (PBDEs) 99, 100, 153, 154, and 209. For BDE-99 and -100, the concentration increased approximately 10% per year. The concentrations of PBDEs were among the highest detected in wildlife so far and ranged from 300 to 12,900 ng/g lipid weight (lw) for sigmaPBDE. While tetrabromobisphenol A (TBBPA) was below the limit of detection in all eggs, hexabromocyclododecane (HBCD), dimethyl-TBBPA, and brominated biphenyl BB-153 were detected in a majority of eggs, with median concentrations of 2.4, 230, and 550 ng/g lw, respectively. Analyses of eggs of the same bird showed no significant intra-clutch variation for PBDEs, BB-153, and HBCD but larger variations for dimethyl-TBBPA. Inter-clutch variations with increasing time trends exist for the BDEs 99, 100, 153, 154, and 209, while a decreasing contamination with the BDEs 183, 49, 47, 66 and 153 was indicated in a subset of eggs.     

Occurrence of polybrominated diphenyl ethers and polychlorinated biphenyls in shark liver oil supplements

Results are reported of a pilot survey of concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in shark liver oil supplements. Eleven brands of dietary supplements were analysed using an isotope dilution GC/MS method. Total concentrations of 10 PBDE congeners (BDE-28, -47, -49, -66, -99, -100, -153, -154, -155 and -183) ranged from 0.1 to 53 ng g^-1 oil weight and total concentrations of six PCB congeners (CB-28/31, -52, -118, -153 and -180) in the samples ranged from 16 to 340 ng g^-1 oil weight (undetected values are not included). Two brands of Japanese deep-sea shark liver oil contained the highest levels of PBDEs (49-53 ng g^-1 oil weight) and PCBs (290-340 ng g^-1 oil weight). These results indicate that PBDEs may have entered Japanese deep-sea waters.