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The brominated flame retardants (BFRs) hexabromocyclododecane (HBCDD), eight polybrominated diphenyl ethers (PBDEs), and decabromodiphenyl ethane (DBDPE) were measured in 16 pools of human milk from Ireland. Concentrations of BDEs-47, -99, -100, -153, and HBCDD were significantly lower (p < 0.05) than those in Irish human milk collected in 2011. In contrast, concentrations of BDE-209 in our study exceeded those in 2011, and while decabromodiphenyl ethane (DBDPE) was not detected in 2011 it was detected in 3 of our samples. This suggests increased use of DBDPE and that while restrictions on the Penta- and Octa-BDE formulations are reducing human exposure, those on Deca-BDE use have yet to reduce body burdens. Estimated exposures for nursing infants to all target BFRs do not suggest a health concern. A one compartment pharmacokinetic model was used to predict body burdens arising from BFR intakes via air, dust and diet. While for most targeted BFRs, predicted and observed body burdens derived from our human milk data compared reasonably well; predicted BDE-209 and DBDPE values were substantially lower than observed. This suggests exposure pathways not included in the model like dermal uptake from fabrics may be important, and highlights knowledge gaps about the human half-lives and bioavailability of these contaminants., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Despite extensive application in consumer products and concerns over their adverse health effects, how external exposure to brominated flame retardants (BFRs) contributes to their human body burdens is not yet fully understood. While recent studies focused on inadvertent indoor dust ingestion and diet as potential major pathways of exposure, dermal uptake has been largely overlooked. We provide the first experimentally-based assessment of dermal uptake of BFRs via contact with indoor dust and flame-retarded furniture fabrics. Results reveal substantial uptake from furniture fabrics (e.g. 8.1 ng pentaBDE/kg bw/day for adults in summer), exceeding the overall adult intake of pentaBDE estimated previously via other exposure pathways. For HBCDs, despite the low absorption fraction (<2.5%) from the studied fabrics, the estimated dermal uptake of UK adults and toddlers (101 and 76.9 ng/kg bw/day) exceed the reported average daily intakes of 7.9 and 43.0 ng/kg bw/day for these UK age groups. Conversely, uptake from dust was low (0.05 and 0.19 ng pentaBDE/kg bw/day for adults and toddlers, respectively), indicating previous pharmacokinetic approaches may have overestimated the significance of this route. Future exposure and risk assessment studies should consider dermal contact with treated products as a significant pathway of human exposure to BFRs and related chemicals., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Concentrations of 27 emerging (EFRs) and legacy flame retardants (LFRs) were measured in samples of indoor air (n = 35) and indoor dust (n = 77) from UK homes and offices. All target compounds were detected in indoor air and dust samples. Relatively volatile EFRs (e.g., tetrabromoethylcyclohexane-DBE-DBCH) were more frequently detected in indoor air (detection frequencies >60%), while less volatile EFRs (e.g., tetrabromobisphenolA-bis(2,3-dibromopropyl ether (TBBPA-BDBPE) and decabromodiphenyl ethane (DBDPE)) were predominant in dust. Concentrations of some EFRs (e.g., DBDPE) exceeded significantly those reported previously in UK dust (p < 0.05), while concentrations of BDE-209 in office dust were significantly lower (p < 0.05) than those reported previously in UK offices, consistent with the application of DBDPE as an alternative to the Deca-BDE formulation, of which BDE-209 is the principal constituent. Moreover, concentrations of BDEs-47 and -99 (both major constituents of the Penta-BDE product) in office air were significantly lower (p < 0.05) than those in previous UK studies. Our results constitute important early evidence that restrictions on PBDEs have increased demand for EFRs in the UK, with the result that human exposure to PBDEs in UK homes and offices has decreased while exposure to EFRs has risen.

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) were measured in dust from 16 cars, 12 homes, and 18 offices in Lagos, Nigeria. These represent the first and second reports respectively of contamination of Nigerian indoor dust with these contaminants, and the second report on PCBs in car dust worldwide. Concentrations of BDE-47 and BDE-99 in two car dust samples (9300 and 3700 ng g(-1) for BDE-47 and 4200 and 19,000 ng g(-1) for BDE-99), are amongst the highest ever reported in car dust. ANOVA comparison with Canada, New Zealand, the UK, and the USA; reveals concentrations of BDEs-28, 49, 47, 66, 100, 99, 154, and 153 in Nigerian house dust, to be significantly lower than in Canada and the USA, with those of BDE-49 and 154 significantly lower than in New Zealand and the UK. Concentrations of BDE-209 in Nigeria were significantly lower than concentrations in the UK and the USA; while concentrations of PCB-180 were significantly greater than those in New Zealand, the UK, and the USA. Median concentrations of PCBs in cars were substantially higher than in the only previous study (in Kuwait and Pakistan). While median concentrations of PBDEs in cars generally exceeded those in homes, this was significant only for BDEs-49, 154, and 197, with concentrations in cars significantly greater than those in offices for BDEs-49 and 154. Contrastingly, concentrations of all target PCBs in offices exceeded significantly those in cars. This study underlines the truly global distribution of indoor contamination with PBDEs and PCBs., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Conflicting evidence exists about whether concentrations of persistent organic chemicals in human milk decrease over the course of lactation. This has implications for the timing of sampling human milk for exposure assessment purposes. We examined this issue by measuring concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), the HBCD degradation products tetrabromocyclododecenes (TBCDs), and tetrabromobisphenol-A (TBBP-A) in human milk collected in 2010-2011 from 10 first-time mothers from Birmingham, UK. To evaluate whether concentrations varied significantly over the first 12 months postpartum, 12 samples were taken-one per month-from each mother, amounting to 120 samples overall. While concentrations of most of our target contaminants displayed no significant variation (p > 0.1) over the duration of our study, significant increases were detected in concentrations of ∑TBCDs (p = 0.029, average increase 1.4%/month) and BDE-153 (p = 0.058, average increase 4.2%/month). When compared to data obtained from a different set of UK mothers from a related but geographically wider catchment area sampled contemporaneously to this study, the ratio of median concentrations of BDE-153 to BDE-99 was markedly lower in the current study (0.46 compared to 1.32). This may reflect unidentified differences in exposure of the participants in the two studies.

The in vitro oxidative metabolism of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and the individual α-, β- and γ-hexabromocyclododecane (HBCD) isomers catalyzed by cytochrome P450 (CYP) enzymes was studied using chicken liver microsomes (CLMs). Metabolites were identified using a liquid chromatography-tandem mass spectrometry method and authentic standards for the oxidative metabolites of BDE-47 and BDE-99. Six hydroxylated tetra-BDEs, namely 4-hydroxy-2,2',3,4'-tetrabromodiphenyl ether (4-OH-BDE-42), 3-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (3-OH-BDE-47), 5-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (5-OH-BDE-47), 6-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (6-OH-BDE-47), 4'-hydroxy-2,2',4,5'- tetrabromodiphenyl ether (4'-OH-BDE-49), and 2'-hydroxy-2,3',4,4'-tetrabromodiphenyl ether (2'-OH-BDE-66), were identified and quantified after incubation of BDE-47 with CLMs. 4'-OH-BDE-49 was the major metabolite formed. Three hydroxylated penta-BDEs (5'-hydroxy-2,2',4,4',5-pentabromodiphenyl ether (5'-OH-BDE-99), 6'-hydroxy-2,2',4,4',5- pentabromodiphenyl ether (6'-OH-BDE-99), and 4'-hydroxy-2,2',4,5,5'-pentabromodiphenyl ether, 4'-OH-BDE-101, were formed incubating BDE-99 with CLMs. Concentrations of BDE-99 metabolites were lower than those of BDE-47. More than four mono-hydroxylated HBCD (OH-HBCD), more than four di-hydroxylated HBCD (di-OH-HBCD), more than five mono-hydroxylated pentabromocyclododecenes (OH-PBCD), and more than five di-hydroxylated pentabromocyclododecenes (di-OH-PBCD) were detected when α-, β-, or γ-HBCD were individually incubated with CLMs. Response values (the ratio between the peak areas of the target compound and its internal standard) for OH-HBCD were 1-3 orders of magnitude higher than those for OH-PBCD, di-OH-HBCD, and di-OH-PBCD, suggesting that OH-HBCD might be the major metabolites of α-, β- and γ-HBCD produced by CLMs. No diastereoisomeric or enantiomeric bioisomerisation was observed incubating α-, β- or γ-HBCD with CLMs. Collectively, our data suggest that (i) BDE-47 is metabolized at a faster rate than BDE-99 by CLMs, (ii) OH-HBCD are the major hydroxylated metabolites of α-, β- and γ-HBCD produced by CLMs and (iii) the diastereoisomeric or enantiomeric bioisomerisation of α-, β- and γ-HBCD is not mediated by chicken CYP enzymes., (Copyright © 2015 Elsevier Inc. All rights reserved.)

Human dermal absorption of eight mono- to deca-brominated diphenyl ethers (PBDEs) was investigated for the first time using EPISKIN human skin equivalent tissue. Using a standard in vitro protocol, EPISKIN tissues mounted in specially designed diffusion cells were exposed to the target PBDEs for 24 h. Estimated steady-state flux (Jss) and permeation coefficients (Papp) across the skin increased with decreasing bromine substitution from BDE-153 (Papp = 4.0 × 10(-4) cm/h) to BDE-1 (Papp = 1.1 × 10(-2) cm/h). This was accompanied by an increase in the time required to traverse the skin tissue into the receptor fluid (lag time) from 0.25 h for BDE-1 to 1.26 h for BDE-153. Papp values for the studied PBDEs were correlated significantly (P < 0.05) with physicochemical parameters like water solubility and log KOW. While less brominated congeners achieved faster dermal penetration, higher PBDEs displayed greater accumulation within the skin tissue. The PBDEs thus accumulated represent a contaminant depot from which they may be slowly released to the systemic circulation over a prolonged period. Maximal percutaneous penetration was observed for BDE-1 (∼ 30% of the applied 500 ng/cm(2) dose). Interestingly, BDE-183 and BDE-209 showed very low dermal absorption, exemplified by a failure to reach the steady state within the 24 h exposure period that was studied.

Concentrations of tri-to-hexa-BDEs were determined in water samples taken from 9 English lakes on 13 occasions between April 2008 and February 2012. Across all sites, concentrations of ΣBDEs in individual samples ranged from 9.2 to 171.5pgL(-)(1), with an average of 61.9pgL(-)(1). Notwithstanding the far greater use of the Penta-BDE commercial formulation in the USA, concentrations in this study are comparable to the limited data available for the Great Lakes. PBDE concentrations showed no evidence of a decline at any monitored location over the study period. This may be because this study commenced 4years after the introduction of restrictions on the Penta- and Octa-BDE formulations. While concentrations normalised to water volume at the different locations were statistically indistinguishable; significant spatial variation was apparent when the data were normalised to total suspended solids (TSS) content. However, this spatial variation was not correlated with factors such as population density and lake catchment area, suggesting that concentrations of PBDEs in lake water in this study are a complex integral of numerous factors. BDE-47:99 ratios and concentrations of ΣBDEs respectively decreased and increased significantly with increasing TSS content. As TSS content was elevated in colder compared with warmer periods, such seasonal variation in TSS content appears a major contributor to the observed elevation of ΣBDE concentrations in colder periods, and higher BDE-47:99 ratios in warmer periods., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In this paper, we have compiled and reviewed the most recent literature, published in print or online from January 2010 to December 2012, relating to the human exposure, environmental distribution, behaviour, fate and concentration time trends of polybrominated diphenyl ether (PBDE) and hexabromocyclododecane (HBCD) flame retardants, in order to establish their current trends and priorities for future study. More data are now becoming available for remote areas not previously studied, Indian Ocean islands, for example. Decreasing time trends for penta-mix PBDE congeners were seen for soils in northern Europe, sewage sludge in Sweden and the USA, carp from a US river, trout from three of the Great Lakes and in Arctic and UK marine mammals and many birds, but increasing time trends continue in polar bears and some birds at high trophic levels in northern Europe. This may be partially a result of the time delay inherent in long-range atmospheric transport processes. In general, concentrations of BDE209 (the major component of the deca-mix PBDE product) are continuing to increase. Of major concern is the possible/likely debromination of the large reservoir of BDE209 in soils and sediments worldwide, to yield lower brominated congeners which are both more mobile and more toxic, and we have compiled the most recent evidence for the occurrence of this degradation process. Numerous studies reported here reinforce the importance of this future concern. Time trends for HBCDs are mixed, with both increases and decreases evident in different matrices and locations and, notably, with increasing occurrence in birds of prey. Temporal trends for both PBDEs and HBCD in Asia are unclear currently. A knowledge gap has been noted in relation to metabolism and/or debromination of BDE209 and HBCD in birds. Further monitoring of human exposure and environmental contamination in areas of e-waste recycling, particularly in Asia and Africa, is warranted. More data on temporal trends of BDE and HBCD concentrations in a variety of matrices and locations are needed before the current status of these compounds can be fully assessed, and the impact of regulation and changing usage patterns among different flame retardants determined., (Crown Copyright © 2014. Published by Elsevier Ltd. All rights reserved.)

Fourteen tri-deca polybrominated diphenyl ethers (PBDEs) were investigated in 35 human milk samples from Birmingham, UK. While none of the hepta-nona BDEs (the main components of the octaBDE technical mixture) was above the limit of quantitation (LOQ); BDE-47 (average concentration=3.3ngg(-1) lipid weight (lw)) was quantified in all samples contributing 34-74% to Σtri-hexa BDEs (the principal constituents of the pentaBDE commercial formulation). BDE-209 (the main congener in the decaBDE formulation) was present above the LOQ in 69% of samples (average concentration=0.31ngg(-1) lw). Concentrations of Σtri-hexa BDEs ranged from 0.2 to 26ngg(-1) lw with concentrations of BDE-47>BDE-153>BDE-99. While concentrations of Σtri-hexa BDEs in this study (average=5.95ngg(-1) lw) were at the high end of those reported from other European countries, concentrations of BDE-209 were lower than those reported in human milk from other countries. The average exposure of a UK nursing infant to Σtri-hexa BDEs (35ng (kg bw)(-1)day(-1)) via breast milk exceeded the upper-bound dietary intakes of both UK adults and toddlers. Using a simple one compartment pharmacokinetic model, PBDE intakes of UK adults via inhalation, diet and dust ingestion were converted to predicted body burdens. Predictions compared well with those observed for Σtri-hexa BDEs and BDE-209 in breast milk., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

A selective pressurized liquid extraction (S-PLE) method was developed for rapid determination of 3 classes of halogenated organic contaminants in indoor dust, soil and sediment samples. The optimised method used 3 : 2 v/v n-hexane-dichloromethane for extraction of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). Extraction was performed at 90 °C for 5 min followed by 4 min static time under 1500 psi. Good recoveries of target analytes were obtained after 3 extraction cycles. In-cell cleanup was performed using 10 g of 44% H2SO4 acid silica and 5 g of florisil (secondary fat retainer), while copper powder was used to remove elemental sulfur. The method was validated using NIST SRM2585 and SRM 1941b in addition to an in-house previously characterised soil sample. Measured concentrations of target compounds showed good agreement with the certified values with RSD < 20% indicating the good accuracy and precision of the S-PLE method. Clean extracts provided low noise levels resulting in low method detection limits (<0.03 ng g(-1)) and LOQs (<0.1 ng g(-1)). The method developed was applied successfully to real environmental samples and it provided various advantages over traditional methods including reduced solvent consumption and analysis time, minimal sample contamination and high sample throughput which can be beneficial for environmental monitoring programs dealing with large numbers of samples.

An in vitro colon extended physiologically based extraction test (CEPBET) which incorporates human gastrointestinal tract (GIT) parameters (including pH and chemistry, solid-to-fluid ratio, mixing and emptying rates) was applied for the first time to study the bioaccessibility of brominated flame retardants (BFRs) from the 3 main GIT compartments (stomach, small intestine and colon) following ingestion of indoor dust. Results revealed the bioaccessibility of γ-HBCD (72%) was less than that for α- and β-isomers (92% and 80% respectively) which may be attributed to the lower aqueous solubility of the γ-isomer (2 μg L⁻¹) compared to the α- and β-isomers (45 and 15 μg L⁻¹ respectively). No significant change in the enantiomeric fractions of HBCDs was observed in any of the studied samples. However, this does not completely exclude the possibility of in vivo enantioselective absorption of HBCDs, as the GIT cell lining and bacterial flora--which may act enantioselectively--are not included in the current CE-PBET model. While TBBP-A was almost completely (94%) bioaccessible, BDE-209 was the least (14%) bioaccessible of the studied BFRs. Bioaccessibility of tri-hepta BDEs ranged from 32-58%. No decrease in the bioaccessibility with increasing level of bromination was observed in the studied PBDEs.

Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and tetrabromobiphenol-A (TBBP-A) were measured in a preliminary study of dust from passenger cabins and trunks of 14 UK cars. Concentrations in cabin dust of HBCDs, TBBP-A, and BDEs 47, 85, 99, 100, 153, 154, 183, 196, 197, 202, 203, 206, 207, 208, and 209 exceeded significantly (p<0.05) those in trunk dust. Sampling cabin dust thus appears to provide a more accurate indicator of human exposure via car dust ingestion than trunk dust. Elevated cabin concentrations are consistent with greater in-cabin use of BFRs. In five cars, while no significant differences (p>0.05) in concentrations of HBCDs and most PBDEs were detected in dust sampled from four different seating areas; concentrations of TBBP-A and of PBDEs 154, 206, 207, 208, and 209 were significantly higher (p<0.05) in dust sampled in the front seats. Possible photodebromination of BDE-209 was indicated by significantly higher (p<0.05) concentrations of BDE-202 in cabin dust. In-vehicle exposure via dust ingestion to PBDEs, HBCDs and TBBP-A exceeded that via inhalation. Comparison with overall exposure via diet, dust ingestion, and inhalation shows while in-vehicle exposure is a minor contributor to overall exposure to BDE-99, ΣHBCDs, and TBBP-A, it is a significant pathway for BDE-209., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

This review underlines the importance of indoor contamination as a pathway of human exposure to hexabromocyclododecanes (HBCDs), polybrominated diphenyl ethers (PBDEs), and perfluoroalkyl compounds (PFCs). There is ample evidence of substantial contamination of indoor dust with these chemicals and that their concentrations in indoor air exceed substantially those outdoors. Studies examining the relationship between body burden and exposure via indoor dust are inconsistent; while some indicate a link between body burdens and PBDE and HBCD exposure via dust ingestion, others find no correlation. Likewise, while concentrations in indoor dust and human tissues are both highly skewed, this does not necessarily imply causality. Evidence suggests exposure via dust ingestion is higher for toddlers than adults. Research priorities include identifying means of reducing indoor concentrations and indoor monitoring methods that provide the most "biologically-relevant" measures of exposure as well as monitoring a wider range of microenvironment categories. Other gaps include studies to improve understanding of the following: emission rates and mechanisms via which these contaminants migrate from products into indoor air and dust; relationships between indoor exposures and human body burdens; relevant physicochemical properties; the gastrointestinal uptake by humans of these chemicals from indoor dust; and human dust ingestion rates.

Human exposure to polybrominated diphenyl ethers (PBDEs) through food and indoor dust ingestion was assessed for 19 Belgian adults. The intake of PBDEs (sigma-hepta BDEs and BDE 209) in the studied population is influenced mainly by diet Dietary intakes of sigmatri-hepta BDEs (BDEs 28, 47, 99, 100, 153, 154, and 183) were 5.9-22.0 ng/day (median 10.3), while those via dust ingestion were 0.1-1.4 ng/day (median 0.25) or 0.3-3.5 ng/day (average 0.6), assuming dust ingestion rates of 20 and 50 mg/day, respectively. Dietary intakes of BDE 209 were 50-238 ng/day (median 95), whereasthose via dust ingestion were 0.4-11 ng/day (median 1.8) or 1.0-29 ng/day (median 4.6) for dust ingestion rates of 20 and 50 mg/day, respectively. It is important to acknowledge the uncertainty associated with the dust ingestion rates. Concentrations of sigmatri-hepta BDEs measured in blood serum were 0.9-7.2 ng/g lipid weight (lw) (median 1.9). This is similar to other European populations, but lower than for nonoccupationally exposed Americans (average of 19 ng/g lw). When compared with estimates of exposure via both dietary and indoor dust ingestion for Americans, the exposures reported here are consistent with the hypothesis that the difference between European and American body burdens of PBDEs is attributable primarily to greater exposure via dust ingestion for Americans. The total intake of PBDEs through food and dustfor each participant could not be correlated with the corresponding serum concentration. Instead, it is hypothesized that past and episodic current higher intakes of PBDEs are more important determinants of body burden than continuous background exposures at the low levels measured in this study.

Although the presence of polybrominated diphenyl ethers (PBDEs) in house dust has been linked to consumer products, the mechanism of transfer remains poorly understood. We conjecture that volatilized PBDEs will be associated with dust particles containing organic matter and will be homogeneously distributed in house dust. In contrast, PBDEs arising from weathering or abrasion of polymers should remain bound to particles of the original polymer matrix and will be heterogeneously distributed within the dust. We used scanning electron microscopy and othertools of environmental forensic microscopy to investigate PBDEs in dust, examining U.S. and U.K. dust samples with extremely high levels of BDE 209 (260-2600 microg/g), a nonvolatile compound at room temperature. We found that the bromine in these samples was concentrated in widely scattered, highly contaminated particles. In the house dust samples from Boston (U.S.), bromine was associated with a polymer/organic matrix. These results suggest that the BDE 209 was transferred to dust via physical processes such as abrasion or weathering. In conjunction with more traditional tools of environmental chemistry, such as gas chromatography/mass spectrometry (GC/MS), environmental forensic microscopy provides novel insights into the origins of BDE 209 in dust and their mechanisms of transfer from products.