Biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) in harbour seals and harbour porpoises from the Southern North Sea

Harbour seals and harbour porpoises are top predator species from the North Sea, have long life spans and hence, are known to accumulate high levels of anthropogenic contaminants. To gain knowledge about the behaviour of naturally-produced compounds in these marine mammals, the biomagnification of naturally-produced methoxylated polybrominated diphenyl ethers (MeO-PBDEs) was assessed. The biomagnification of MeO-PBDEs (2′-MeO-BDE 68 and 6-MeO-BDE 47) was lower in harbour seals (all biomagnification factors (BMFs) < 1) compared to the same age–gender groups of the harbour porpoises (all BMFs > 1). This may indicate a better metabolic breakdown of MeO-PBDEs in harbour seals, as was previously suggested for polybrominated diphenyl ethers (PBDEs). In both predators, 6-MeO-BDE 47 had the highest concentrations (range: 45–483 ng/g lw and 2–38 ng/g lw for harbour porpoises and seals, respectively) compared to 2′-MeO-BDE 68 (range: 2–28 ng/g lw and 1–6 ng/g lw for harbour porpoises and seals, respectively). In general, the highest concentrations were found in juveniles, suggesting an increased biotransformation capacity with age or the influence of dilution by growth for both species. Here we show that naturally-produced brominated organic compounds can biomagnify and accumulate in North Sea top predators, although to a lesser extent than anthropogenic lipophilic contaminants, such as polychlorinated biphenyls (PCBs) or PBDEs.     

Concentrations of polybrominated diphenyl ethers (PBDEs) and 2,4,6-tribromophenol in human placental tissues

Legacy environmental contaminants such as polybrominated diphenyl ethers (PBDEs) are widely detected in human tissues. However, few studies have measured PBDEs in placental tissues, and there are no reported measurements of 2,4,6-tribromophenol (2,4,6-TBP) in placental tissues. Measurements of these contaminants are important for understanding potential fetal exposures, as these compounds have been shown to alter thyroid hormone regulation in vitro and in vivo. In this study, we measured a suite of PBDEs and 2,4,6-TBP in 102 human placental tissues collected between 2010 and 2011 in Durham County, North Carolina, USA. The most abundant PBDE congener detected was BDE-47, with a mean concentration of 5.09 ng/g lipid (range: 0.12–141 ng/g lipid; detection frequency 91%); however, 2,4,6-TBP was ubiquitously detected and present at higher concentrations with a mean concentration of 15.4 ng/g lipid (range:1.31–316 ng/g lipid; detection frequency 100%). BDE-209 was also detected in more than 50% of the samples, and was significantly associated with 2,4,6-TBP in placental tissues, suggesting they may have a similar source, or that 2,4,6-TBP may be a degradation product of BDE-209. Interestingly, BDE-209 and 2,4,6-TBP were negatively associated with age (r_s = − 0.16; p = 0.10 and r_s = − 0.17; p = 0.08, respectively). The results of this work indicate that PBDEs and 2,4,6-TBP bioaccumulate in human placenta tissue and likely contribute to prenatal exposures to these environmental contaminants. Future studies are needed to determine if these joint exposures are associated with any adverse health measures in infants and children.     

Inverse age-dependent accumulation of decabromodiphenyl ether and other PBDEs in serum from a general adult population

Polybromodiphenyl ethers (PBDEs), including the decabromodiphenyl congener (BDE-209), were determined in the serum of 731 individuals from a general adult population (18–74 years) collected in 2002 in Catalonia (north-eastern Spain). The BDE-209 was the predominant congener (median 3.7 ng/g lipid) followed by BDE-47 (2.6 ng/g lipid) and BDE-99 (1.2 ng/g lipid). PBDEs in this population (median 15.4 ng/g lipid) ranked amongst the highest of previously described concentrations in populations in Europe, Asia, New Zealand and Australia, yet it was lower than those found in North American reports. Age was clearly the socio-demographic factor of highest influence on the PBDE distributions. However, unlike usual trends of higher accumulation of POPs through age, the higher concentrations were found in young individuals (< 30 years) rather than in adults (≥ 30 years), with differences of 14%, 31% and 46% in the most abundant congeners (i.e. BDE-209, BDE-99 and BDE-47, respectively). This age-dependent distribution of PBDEs (including the case for BDE-209, which is shown for the first time in this study) is explained by the higher and widespread use of these compounds since the 1980s. In view that these compounds remain highly used, this accumulation pattern is likely to evolve, anticipating an increasing level of PBDE concentrations in future general population surveys, yet probably assuming an age-dependent increase pattern. Socio-economic level was also a determinant of BDE-47 concentrations, but only relevant for the least affluent class, suggesting that lifestyle and environmental conditions in the dwelling place may also contribute to exposure. Nonetheless, gender, body mass index, place of birth, parity and education level did not show any statistically significant influence on the observed PBDE distributions.     

Emerging and historical brominated flame retardants in peregrine falcon (Falco peregrinus) eggs from Canada and Spain

Comparisons of brominated flame retardants (BFRs) in the eggs of peregrine falcons (Falco peregrinus) recently collected (2003–2007), are made between Canada (N = 12) and Spain (N = 13). Overall, concentrations of sum (Σ) polybrominated diphenyl ethers (PBDEs; 16 di-deca-BDE congeners) exceeded Σhexabromocyclododecane (HBCD) and were an order of magnitude higher than 2,2′4,4′,5,5′-hexabromobiphenyl (BB-153) > hexachlorocyclopentenyl-dibromocyclooctane (HCBDCO) > 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) > decabromodiphenylethane (DBDPE) > octabromotrimethylphenyllindane (OBIND) > hexabromobenzene (HBB) > bis(2-ethyl-1hexyl)tetrabromophthalate (BEHTBP). This is the first report of detectable HBCDCO and BEHTBP concentrations in biota, and the highest in ovo concentration of ∑ HBCD (14,617 ng/g lw; Montreal, Canada) to date. There were significantly greater egg concentrations of BB-153, ΣHBCD, and ΣPBDE including BDE-153, -99, -100 and -183, in Canadian than Spanish peregrines with a terrestrial diet. HBB, BTBPE, and OBIND were detected in eggs from both countries, but only Canadian peregrine eggs had detectable levels of HCDBCO (25%) and DBDPE (N = 1). The in ovo PBDE congener profile was dominated by BDE-153 > BDE-99 > BDE-47 > BDE-183 > BDE-100 > BDE-209, with the isomeric HBCD pattern being α-HBCD > γ-HBCD (β-HBCD undetected). The Canadian peregrine eggs had lower enantiomeric HBCD values consistent with their higher fractions of (−) α-HBCD, suggesting selective enantiomeric enrichment or that the (+) α-isomer is more readily metabolized and so deposited in the egg through maternal transfer. Continental differences in egg burdens of peregrines are discussed relative to BFR usage patterns and exposure of peregrines on their breeding grounds.     

Levels and congener profiles of polybrominated diphenyl ethers (PBDEs) in breast milk from Shanghai: Implication for exposure route of higher brominated BDEs

Breast milk has been widely used as a bioindicator to assess the extent of human exposure to PBDEs via various exposure routes. In this study, 48 breast milk samples were collected from primiparous women in Shanghai city, and 14 PBDEs congeners (BDE-28, − 47, − 99, − 100, − 153, − 154, − 183, − 196, − 197, − 203, − 206, − 207, − 208, and − 209) were quantified using gas chromatography-electron capture negative ionization-mass spectrometry. The mean concentration of total PBDEs was 8.6 ng/g lipid weight, and ranged from 1.8 to 26.7 ng/g lipid weight. These concentration levels were similar to those reported in Europe and Asia, but one order of magnitude lower than those in North America. The congener profiles in this study exhibited a specific pattern in human milk found worldwide, BDE-153 and BDE-28 accounted for a relatively higher proportion of lower brominated BDEs (from tri- to hepta-BDEs), whereas higher brominated BDEs (from octa- to deca-BDEs) contributed more than 70% of the total PBDEs. The Spearman's correlation coefficient among higher brominated BDEs showed a positive relationship, and concentration levels of higher brominated BDEs were statistically different between office workers and housewives. Due to relatively higher proportion of PBDEs from octa- to deca-BDEs were detected, air inhalation and dust ingestion might be the major exposure routes of higher brominated BDEs. Further research is needed to clarify the major exposure route of higher brominated BDEs to humans.     

Bioaccumulation and biotransformation of brominated and chlorinated contaminants and their metabolites in ringed seals (Pusa hispida) and polar bears (Ursus maritimus) from East Greenland

We report on the comparative bioaccumulation, biotransformation and/or biomagnification from East Greenland ringed seal (Pusa hispida) blubber to polar bear (Ursus maritimus) tissues (adipose, liver and brain) of various classes and congeners of persistent chlorinated and brominated contaminants and metabolic by-products: polychlorinated biphenyls (PCBs), chlordanes (CHLs), hydroxyl (OH-) and methylsulfonyl (MeSO₂-) PCBs, polybrominated biphenyls (PBBs), OH-PBBs, polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) flame retardants and OH- and methoxyl (MeO-) PBDEs, 2,2-dichloro-bis(4-chlorophenyl)ethene (p,p′-DDE), 3-MeSO₂-p,p′-DDE, pentachlorophenol (PCP) and 4-OH-heptachlorostyrene (4-OH-HpCS). We detected all of the investigated contaminants in ringed seal blubber with high frequency, the main diet of East Greenland bears, with the exception of OH-PCBs and 4-OH-HpCS, which indicated that these phenolic contaminants were likely of metabolic origin and formed in the bears from accumulated PCBs and octachlorostyrene (OCS), respectively, rather than being bioaccumulated from a seal blubber diet. For all of the detectable sum of classes or individual organohalogens, in general, the ringed seal to polar bear mean BMFs for ΣPCBs, p,p′-DDE, ΣCHLs, ΣMeSO₂-PCBs, 3-MeSO₂-p,p′-DDE, PCP, ΣPBDEs, total-(α)-HBCD, ΣOH-PBDEs, ΣMeO-PBDEs and ΣOH-PBBs indicated that these organohalogens bioaccumulate, and in some cases there was tissue-specific biomagnification, e.g., BMFs for bear adipose and liver ranged from 2 to 570. The blood-brain barrier appeared to be effective in minimizing brain accumulation as BMFs were ≤ 1 in the brain, with the exception of ΣOH-PBBs (mean BMF = 93 ± 54). Unlike OH-PCB metabolites, OH-PBDEs in the bear tissues appeared to be mainly accumulated from the seal blubber rather than being metabolic formed from PBDEs in the bears. In vitro PBDE depletion assays using polar bear hepatic microsomes, wherein the rate of oxidative metabolism of PBDE congeners was very slow, supported the probability that accumulation from seals is the main source of OH-PBDEs in the bear tissues. Our findings demonstrated from ringed seal to polar bears that organohalogen biotransformation, bioaccumulation and/or biomagnification varied widely and depended on the contaminant in question. Our results show the increasing complexity of bioaccumulated and in some cases biomagnified, chlorinated and brominated contaminants and/or metabolites from the diet may be a contributing stress factor in the health of East Greenland polar bears.     

Polybrominated diphenyl ether (PBDE) levels in dust from previously owned automobiles at United States dealerships

The levels of BDE-28, BDE-47, BDE-99, BDE-100, BDE-153, BDE-154, BDE-183, and BDE-209 were determined in the dust sampled from 60 automobiles that were available for resale at U.S. dealerships. The dominant congener in automobile dust was BDE-209 comprising 95% of the total PBDE levels with a median level of 48.1 µg g^? 1. Statistical analysis of the vehicle attributes indicates that the BDE-209 levels are different (p < 0.05) with respect to groupings by vehicle model year, vehicle manufacturer, and the country of manufacture. Vehicle dust samples contained the characteristic profile of the PBDE congeners that comprise the PentaBDE formulation. While DecaBDE use is banned in Maine and Washington and is targeted for restriction in the near future by six U.S. states, vehicles and airplanes are exempt from the ban. It is anticipated that the human exposure potential to PBDEs from automobile dust ingestion will continue for an indefinite future period in the U.S. population.     

Halogenated flame retardants in home-produced eggs from an electronic waste recycling region in South China: Levels,composition profiles,and human dietary exposure assessment

Three regulated halogenated flame retardants (HFRs), i.e., polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and hexabromocyclododecanes (HBCDs), and several alternative HFRs (AHFRs) including Dechlorane Plus (DP), decabromodiphenyl ethane (DBDPE), and 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), were investigated in the home-produced eggs from three recycling sites and a reference site in an electronic waste (e-waste) recycling region, South China. Mean levels of HFRs in eggs from the recycling sites ranged 2640–14 100, 700–1620, 44–350, and 720–3920 ng/g lipid weight for ∑PBDEs, ∑PBBs, ∑HBCDs, and ∑AHFRs, respectively, which were one to two orders of magnitude higher than those examined in the reference site. PBDEs were the predominant HFR in those eggs, with contributions > 50% to the total HFRs; followed by PBBs and the AHFRs (contributing 14–22% in average). The α-HBCD was the predominant diastereoisomers of HBCDs, with preferential enrichment of the (−)-enantiomer in most of the eggs; but no significant stereoselective enrichment of the DP isomers was observed in these eggs. The average estimated daily intakes (EDIs) of PBDEs, PBBs, HBCDs, and the AHFRs via eggs from the recycling sites ranged 4200–20 000, 1120–2440, 80–490, and 970–4530 ng/day, respectively, which were one to two orders of magnitude higher than those reported from other parts of the world. The potential adverse effects of these HFRs to human health in the e-waste sites should be further investigated. This is the first report on the isomer compositions of DP and the chiral signatures of HBCDs in hen eggs.     

Causes of variability in concentrations and diastereomer patterns of hexabromocyclododecanes in indoor dust

The temporal evolution of concentrations of α-, β-, and γ-hexabromocyclododecanes (HBCDs), and pentabromocyclododecenes (PBCDs — degradation products of HBCDs) was studied in separate aliquots of a well-homogenized indoor dust sample. These were: (a) exposed to natural light, and (b) kept in the dark. Results revealed a rapid photolytically-mediated shift from γ-HBCD to α-HBCD that was complete after 1 week of exposure, and a slower degradative loss of HBCDs via elimination of HBr. Under the specific conditions studied in this experiment, calculated half-lives (t_1/2) showed the decay in ΣHBCDs concentration was faster in light-exposed samples (t_1/2 = 12 weeks), than in light-shielded dust (t_1/2 = 26 weeks). Within-room spatial and temporal variability in concentrations and diastereomer patterns were studied in six and three rooms respectively. While in some rooms, little variability was detected, in others it was substantial. In one room, concentrations of ΣHBCDs and the relative abundance of γ-HBCD declined dramatically with increasing distance from a TV. The same TV appears to have influenced strongly the temporal variation in that room; with higher concentrations observed in its presence and when the TV was moved closer to the area sampled. Significant negative correlation was observed in one room between concentrations of ΣHBCDs and dust loading (g dust m^? 2 floor), implying “dilution” occurs at higher dust loadings.     

Determination of polybrominated diphenyl ethers in human semen

Some persistent organic pollutants (POPs) have been found in human semen but until this point it was unclear whether polybrominated diphenyl ethers (PBDEs) could be detected in human semen. In this study, PBDEs were found for the first time in human semen samples (n = 101) from Taizhou, China. The concentrations of total PBDEs (∑ PBDEs) varied from 15.8 to 86.8 pg/g ww (median = 31.3 pg/g ww) and 53.2 to 121 pg/g ww (median = 72.3 pg/g ww) in semen and blood samples, respectively. The ∑ PBDE level in semen was about two times lower than in human blood, which was different in the distribution in the two matrices from other POPs. A correlation of ∑ PBDE concentration was found between paired semen and in blood. The results suggest that semen could be used to detect PBDE burden in human body as a non-invasive matrix. In addition, the levels of BDE-209 and BDE-153, especially the latter, were much higher in blood than in semen, while the levels of BDE-28, BDE-47 and BDE-99 were comparable in the two matrices, suggesting that low brominated congeners could be more easily transferred to semen than high brominated congeners. Considering different toxicities among the PBDE congeners, it might be more significant to measure PBDEs in semen than in blood for evaluating male reproduction risks of PBDEs.     

Concentrations of polybrominated diphenyl ethers (PBDEs) in matched samples of human milk,dust and indoor air

Polybrominated diphenyl ethers (PBDEs) are lipophilic, persistent pollutants found worldwide in environmental and human samples. Exposure pathways for PBDEs remain unclear but may include food, air and dust. The aim of this study was to conduct an integrated assessment of PBDE exposure and human body burden using 10 matched samples of human milk, indoor air and dust collected in 2007–2008 in Brisbane, Australia. In addition, temporal analysis was investigated comparing the results of the current study with PBDE concentrations in human milk collected in 2002–2003 from the same region.PBDEs were detected in all matrices and the median concentrations of BDEs -47 and -209 in human milk, air and dust were: 4.2 and 0.3 ng/g lipid; 25 and 7.8 pg/m³; and 56 and 291 ng/g dust, respectively. Significant correlations were observed between the concentrations of BDE-99 in air and human milk (r = 0.661, p = 0.038) and BDE-153 in dust and BDE-183 in human milk (r = 0.697, p = 0.025). These correlations do not suggest causal relationships — there is no hypothesis that can be offered to explain why BDE-153 in dust and BDE-183 in milk are correlated. The fact that so few correlations were found in the data could be a function of the small sample size, or because additional factors, such as sources of exposure not considered or measured in the study, might be important in explaining exposure to PBDEs. There was a slight decrease in PBDE concentrations from 2002–2003 to 2007–2008 but this may be due to sampling and analytical differences. Overall, average PBDE concentrations from these individual samples were similar to results from pooled human milk collected in Brisbane in 2002–2003 indicating that pooling may be an efficient, cost-effective strategy of assessing PBDE concentrations on a population basis.The results of this study were used to estimate an infant's daily PBDE intake via inhalation, dust ingestion and human milk consumption. Differences in PBDE intake of individual congeners from the different matrices were observed. Specifically, as the level of bromination increased, the contribution of PBDE intake decreased via human milk and increased via dust. As the impacts of the ban of the lower brominated (penta- and octa-BDE) products become evident, an increased use of the higher brominated deca-BDE product may result in dust making a greater contribution to infant exposure than it does currently.To better understand human body burden, further research is required into the sources and exposure pathways of PBDEs and metabolic differences influencing an individual's response to exposure. In addition, temporal trend analysis is necessary with continued monitoring of PBDEs in the human population as well as in the suggested exposure matrices of food, dust and air.     

Umbilical cord blood PBDEs concentrations are associated with placental DNA methylation

BackgroundIn utero polybrominated diphenyl ethers (PBDEs) exposure has been associated with adverse fetal growth. Alterations in placental DNA methylation might mediate those adverse effects.ObjectivesTo examine the associations between in utero PBDEs exposure and DNA methylation in human placenta.MethodsEighty apparently healthy mother-newborn pairs delivering at the Second Affiliated Hospital of Wenzhou Medical College were enrolled in this study. Placental DNA methylation of LINE1, NR3C1 and IGF2 was measured by quantitative polymerase chain reaction-pyrosequencing. In utero PBDEs exposure was assessed by measuring umbilical cord blood PBDEs concentrations.ResultsFor LINE-1, higher levels of BDE-66 exposure were associated with decreased DNA methylation (β = − 0.9, 95% CI, − 1.8 to − 0.1); For NR3C1, BDE-153 concentrations was significantly inversely associated with DNA methylation (β = − 2.0, 95% CI, − 3.7 to − 0.2); For IGF2, elevated concentrations of both BDE-153 (β = − 1.7; 95% CI, − 3.0 to − 0.4) and BDE-209 (β = − 1.0; 95% CI, − 1. 9 to − 0.1) were significantly associated with decreased DNA methylation.ConclusionsWe found that placental DNA methylation is associated with in utero PBDEs exposure. Changes in placental DNA methylation might be part of the underlying biological pathway between in utero PBDEs exposure and adverse fetal growth.     

Personal exposure to HBCDs and its degradation products via ingestion of indoor dust

Personal exposures via ingestion of indoor dust to α-, β-, and γ-hexabromocyclododecanes (HBCDs) and the degradation products (pentabromocyclododecenes (PBCDs) and tetrabromocyclododecadienes (TBCDs)) were estimated for 21 UK adults. Under an average dust ingestion scenario, personal exposures ranged from 4.5 to 1851 ng ΣHBCDs day^? 1; while the range under a high dust ingestion scenario was 11 to 4630 ng ΣHBCDs day^? 1. On average, personal exposure to ΣHBCDs via dust ingestion in this study was 35% α-, 11% β-, and 54% γ-HBCD. However, while exposure to β-HBCD (4–18% of ΣHBCDs) was relatively consistent with the proportion of this diastereomer in the HBCD commercial formulation; exposures to α- and γ-isomers (11–58% and 29–82% of ΣHBCDs respectively) showed substantial variation from the commercial formulation pattern. Personal exposures to ΣTBCDs (median = 0.2 ng day^? 1 under an average dust ingestion scenario) and ΣPBCDs (1.4 ng day^? 1) were significantly lower (p < 0.05) than for ΣHBCDs (48 ng day^? 1). Despite this, the exposure of one participant to ΣPBCDs exceeded the exposure to ΣHBCDs received by 85% of the other participants. On average, house dust provided the major contribution to personal exposure via dust ingestion to all target compounds due to the large time fraction spent in houses. In contrast, although participants spent less time in cars than in offices, car dust makes a higher average contribution (17%) to ΣHBCDs exposure than office dust (13%).     

Levels and trends of persistent organic pollutants in ringed seals (Phoca hispida) from Central West Greenland, with particular focus on polybrominated diphenyl ethers (PBDEs)

Polybrominated diphenyl ethers (PBDEs) and the organochlorine compounds polychlorinated biphenyls (PCBs), DDTs, HCB, chlordane-related pesticides, HCH and toxaphene were analysed in blubber of juvenile ringed seals from Central West Greenland collected between 1982 and 2006. The longest time series could be established for PBDEs, partly based on archived material, while PCBs and DDTs covered a study period from 1994-2006. All organochlorines showed decreasing trends, most pronounced for DDT and HCH with an annual change of 8%. BDE-47 had a significantly increasing trend of 5% annually. It was the only BDE congener consistently above the detection limit, with annual median concentrations between 0.78 ng/g lw to 3.54 ng/g lw, i.e. about 10 times lower than values from East Greenland observed in a similar time trend study on ringed seal blubber [Rigét F, Vorkamp K, Dietz R, Rastogi SC. Temporal trend studies on polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in ringed seals from East Greenland. J Environ Monit 2006; 8: 1000-5]. A clear East>West difference was also found for PCBs and DDTs, but not for chlordanes, toxaphene or HCHs. Sigma 10-PCB, Sigma DDT and Sigma Chlordanes had similar annual median concentrations, typically exceeding SigmaPBDE by two orders of magnitude. The concentrations of HCH and toxaphene were in an intermediate group, with highest annual median concentrations of 135 ng/g lw and 20 ng/g lw, respectively. For most compound groups, the circumpolar trend previously established under for example the Arctic Monitoring and Assessment Programme was confirmed, but apparently, more data are needed for chlordane-related compounds and toxaphene. Statistical analyses of the compound patterns in the ringed seal samples revealed significantly greater differences between seals from East and West than between different sampling years. Higher proportions of PCBs and DDTs and lower proportions of chlordanes and HCHs were found in seals from East Greenland than in those from West Greenland. Based on principal component analysis of individual congener and compounds, seals from East Greenland were found to contain higher proportions of the higher chlorinated CB congeners. Varying patterns between sampling locations may be caused by different exposure situations related to contaminant emissions and transport, but different feeding habits may also affect the contaminant composition.     

Polybrominated diphenyl ethers (PBDEs) in human samples of mother–newborn pairs in South China and their placental transfer characteristics

There are limited data concerning the placenta transfer characteristics and accumulation of polybrominated diphenyl ethers (PBDEs) in infants. However, PBDEs received increasing health concerns due to their endocrine disrupt and neurodevelopment toxicity effects. The present study assessed the accumulation of PBDEs in 30 paired placenta, breast milk, fetal cord blood, and neonatal urine samples collected from five major cities of the South China. The age of mothers ranged from 21 to 39 (mean 27.6 ± 4.56). The ∑ PBDE concentrations were 15.8 ± 9.88 ng g^− 1 lipid in placenta, 13.2 ± 7.64 ng g^− 1 lipid in breast milk, 16.5 ± 19.5 ng g^− 1 lipid in fetal cord blood, and 1.80 ± 1.99 ng ml^− 1 in neonatal urine. BDE-47 was the predominant congener in all types of human sample. Octa-BDEs such as BDE-196/-197 were detected highly in placenta and cord blood while moderately in breast milk and neonatal urine. Significant (p < 0.01) correlations were observed for both total and most individual PBDEs in cord blood–maternal placenta and breast milk–urine paired individual samples. The extent of placental transfer of higher brominated BDEs such as BDE-196/-197 was greater than that of BDE-47. The estimated daily intake (EDI) analysis for breast-fed infants revealed that newborns in these areas were exposed to relatively high levels of PBDEs via breast milk. Our study not only provided systematic fundamental data for PBDE distribution but also revealed the placenta transfer characteristics of PBDE congeners in South China.     

Brominated and chlorinated flame retardants in San Francisco Bay sediments and wildlife

Restrictions on the use of polybrominated diphenyl ethers (PBDEs) have resulted in the use of alternative flame retardants in consumer products to comply with flammability standards. In contrast to PBDEs, information on the occurrence and fate of these alternative compounds in the environment is limited, particularly in the United States. In this study, a survey of flame retardants in San Francisco Bay was conducted to evaluate whether PBDE replacement chemicals and other current use flame retardants were accumulating in the Bay food web. In addition to PBDEs, brominated and chlorinated flame retardants (hexabromocyclododecane (HBCD) and Dechlorane Plus (DP)) were detected in Bay sediments and wildlife. Median concentrations of PBDEs, HBCD, and DP, respectively, were 4.3, 0.3, and 0.2 ng g^− 1 dry weight (dw) in sediments; 1670, < 6.0, and 0.5 ng g^− 1 lipid weight (lw) in white croaker (Genyonemus lineatus); 1860, 6.5, and 1.3 ng g^− 1 lw in shiner surfperch (Cymatogaster aggregata); 5500, 37.4, and 0.9 ng g^− 1 lw in eggs of double-crested cormorant (Phalacrocorax auritus); 770, 7.1, and 0.9 ng g^− 1 lw in harbor seal (Phoca vitulina) adults; and 330, 3.5, and < 0.1 ng g^− 1 lw in harbor seal (P. vitulina) pups. Two additional flame retardants, pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6 tribromophenoxy)ethane (BTBPE) were detected in sediments but with less frequency and at lower concentrations (median concentrations of 0.01 and 0.02 ng g^− 1 dw, respectively) compared to the other flame retardants. PBEB was also detected in each of the adult harbor seals and in 83% of the pups (median concentrations 0.2 and 0.07 ng g^− 1 lw, respectively). The flame retardants hexabromobenzene (HBB), decabromodiphenyl ethane (DBDPE), bis(2-ethylhexyl) tetrabromophthalate (TBPH), and 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), were not detected in sediments and BTBPE, HBB and TBB were not detected in wildlife samples. Elevated concentrations of some flame retardants were likely associated with urbanization and Bay hydrodynamics. Compared to other locations, concentrations of PBDEs in Bay wildlife were comparable or higher, while concentrations of the alternatives were generally lower. This study is the first to determine concentrations of PBDE replacement products and other flame retardants in San Francisco Bay, providing some of the first data on the food web occurrence of these flame retardants in a North American urbanized estuary.     

Polybrominated diphenyl ethers (PBDEs) in marine mammals from Arctic and North Atlantic regions, 1986–2009

A selection of PBDE congeners was analyzed in pooled blubber samples of pilot whale (Globicephala melas), ringed seal (Phoca hispida), minke whale (Balaenoptera acutorostrata), fin whale (Balaenoptera physalus), harbor porpoise (Phocoena phocoena), hooded seal (Cystophora cristata) and Atlantic white-sided dolphin (Lagenorhynchus acutus), covering a time period of more than 20 years (1986–2009). The analytes were extracted and cleaned-up using open column extraction and multi-layer silica gel column chromatography, and the analysis was performed on a GC-MS system operating in the NCI mode. The highest PBDE levels were found in the toothed whale species pilot whale and white-sided dolphin, and the lowest levels in fin whales and ringed seals. One-sided analyses of variance (ANOVA) followed by Tukey comparisons of means were applied to test for differences between years and sampling areas. Due to inter-year sampling variability, only general comparisons of PBDE concentrations between different sampling areas could be made. Differences in PBDE concentrations between three sampling periods, from 1986 to 2007, were evaluated in samples of pilot whales, ringed seals, white-sided dolphins and hooded seals. The highest PBDE levels were found in samples from the late 1990s or beginning of 2000, possibly reflecting the increase in the global production of technical PBDE mixtures in the 1990s. The levels of BDE #153 and #154 increased relative to the total PBDE concentration in some of the species in recent years, which may indicate an increased relative exposure to higher brominated congeners. In order to assess the effect of measures taken in legally binding international agreements, it is important to continuously monitor POPs such as PBDEs in sub-Arctic and Arctic environments.     

Concentrations of brominated flame retardants in dust from United Kingdom cars, homes, and offices: causes of variability and implications for human exposure

Average concentrations of polybrominated diphenyl ethers (PBDEs) in dust in 30 homes, 18 offices, and 20 cars were 260,000, 31,000, and 340,000 ng SigmaPBDEs g(-1) respectively. Concentrations of BDEs 47, 99, 100, and 154 in cars exceeded significantly (p<0.05) those in homes and offices. Average concentrations of 1,2-bis(2,4,6-tribromophenoxy)ethane (TBE) and decabromodiphenyl ethane (DBDPE) in homes, offices, and cars respectively were lower at 120, 7.2, and 7.7 ng g(-1) (TBE) and 270, 170, and 400 ng g(-1) (DBDPE). BDE-209 concentrations in three samples are the highest to date at 2,600,000 (car), 2,200,000 (home), and 1,400,000 ng g(-1) (home). UK toddlers daily consuming 200 mg dust contaminated at the 95th percentile concentration, ingest 180 ng (Sigma)tri-hexa-BDEs and 310 microg BDE-209 day(-1). For TBE, exposure was lower than for PBDEs and hexabromocyclododecanes (HBCDs), while that for DBDPE was similar in magnitude to (Sigma)tri-hexa-BDEs, but less than for BDE-209 and HBCDs. BDE-209 concentrations recorded in ten samples taken at monthly intervals in one room varied 400-fold, implying caution when using single measurements of dust contamination for exposure assessment. Significant negative correlation was observed in one room between concentrations of BDE-47, 99, and 153 and dust loading (g dust m(-2) floor), suggesting "dilution" occurs at higher dust loadings.     

Concentrations of polybrominated diphenyl ethers in matched samples of indoor dust and breast milk in New Zealand

Polybrominated diphenyl ethers (PBDEs) are present in many consumer goods. There is evidence that PBDEs are toxic to humans, particular young children. The purpose of this study was to assess indoor dust as an exposure source for PBDEs. Concentrations of 16 PBDEs were determined in dust samples from 33 households in New Zealand, and in breast milk samples from 33 mothers living in these households. Associations between dust and breast milk PBDE concentrations were assessed, and children's PBDE intake from breast milk and dust estimated. Influences of household and demographic factors on PBDE concentrations in dust were investigated. Indoor dust concentrations ranged from 0.1 ng/g for BDE17 to 2500 ng/g for BDE209. Breast milk concentrations were positively correlated (p < 0.05) with mattress dust concentrations for BDE47, BDE153, BDE154, and BDE209 and with floor dust for BDE47, BDE183, BDE206, and BDE209. The correlation for BDE209 between dust and breast milk is a novel finding. PBDE concentrations in floor dust were lower from households with new carpets. The estimated children's daily intake of PBDEs from dust and breast milk was below U.S. EPA Reference Dose values. The study shows that dust is an important human exposure source for common PBDE formulations in New Zealand.     

Determinants of brominated flame retardants in breast milk from a large scale Norwegian study

Brominated flame retardants (BFRs), particularly polybrominated diphenyl ethers (PBDEs), are widely present in human populations. In order to investigate human exposure pathways and associations with socioeconomic and lifestyle factors, 393 breast milk samples from mothers living in various regions throughout Norway were analyzed. Up to ten PBDE congeners were measured in all the samples, hexabromocyclododecane (HBCD) and BDE-209 in subsets of 310 and 46, respectively. The median concentrations of the sum of the seven most prominent PBDEs (BDE-28, 47, 99, 100, 153, 154 and 183), BDE-209 and HBCD were 2.1, 0.32 and 0.86 ng/g lipids, respectively. These concentrations are comparable to the levels generally observed in human populations in Europe. The frequency distributions were quite skewed with long tails towards higher concentrations. Maternal age, parity, education, having a cohabitant employed as electrician, and ventilation were factors significantly associated with some of the BFRs, although these factors only explained a small amount of the variability (R² 0.04–0.16). The mothers' diet was not found to influence the breast milk PBDE and HBCD levels. Our results show that sources other than the diet are important for the variability seen in breast milk BFR concentrations and that exposure from the indoor atmosphere should be emphasized in future studies.