Luminescence Lifetime-Based Sensing Platform Based on Cyclometalated Iridium(III) Complexes for the Detection of Perfluorooctanoic Acid in Aqueous Samples.

Luminescence lifetimes are an attractive analytical method for detection due to its high sensitivity and stability. Iridium probes exhibit luminescence with long excited-state lifetimes, which are sensitive to the local environment. Perfluorooctanoic acid (PFOA) is listed as a chemical of high concern regarding its toxicity and is classified as a "forever chemical". In addition to strict limits on the presence of PFOA in drinking water, environmental contamination from industrial effluent or chemical spills requires rapid, simple, accurate, and cost-effective analysis in order to aid containment. Herein, we report the fabrication and function of a novel and facile luminescence sensor for PFOA based on iridium modified on gold surfaces. These surfaces were modified with lipophilic iridium complexes bearing alkyl chains, namely, IrC6 and IrC12, and Zonyl-FSA surfactant. Upon addition of PFOA, the modified surfaces IrC6-FSA@Au and IrC12-FSA @Au show the largest change in the red luminescence signal with changes in the luminescence lifetime that allow monitoring of PFOA concentrations in aqueous solutions. The platform was tested for the measurement of PFOA in aqueous samples spiked with known concentrations of PFOA and demonstrated the capacity to determine PFOA at concentrations >100 µg/L (240 nM).

Impact of Legislation on Brominated Flame Retardant Concentrations in UK Indoor and Outdoor Environments: Evidence for Declining Indoor Emissions of Some Legacy BFRs.

Concentrations of polybrominated diphenyl ethers, hexabromocyclododecane (HBCDD), and novel brominated flame retardants (NBFRs) were measured in indoor dust, indoor air, and outdoor air in Birmingham, UK. Concentrations of ΣBFRs ranged from 490 to 89,000 ng/g, 46-14,000 pg/m3, and 22-11,000 pg/m3, respectively, in UK indoor dust, indoor air, and outdoor air. BDE-209 and decabromodiphenyl ethane (DBDPE) were the main contributors. The maximum concentration of DBDPE (10,000 pg/m3) in outdoor air is the highest reported anywhere to date. In contrast with previous studies of outdoor air in Birmingham, we observed significant correlations between concentrations of tri- to hepta-BDEs and HBCDD and temperature. This may suggest that primary emissions from ongoing use of these BFRs have diminished and that secondary emissions (e.g., evaporation from soil) are now a potentially major source of these BFRs in outdoor air. Conversely, the lack of significant correlations between temperature and concentrations of BDE-209 and DBDPE may indicate that ongoing primary emissions from indoor sources remain important for these BFRs. Further research to clarify the relative importance of primary and secondary sources of BFRs to outdoor air is required. Comparison with earlier studies in Birmingham reveals significant (p < 0.05) declines in concentrations of legacy BFRs, but significant increases for NBFRs over the past decade. While there appear minimal health burdens from BFR exposure for UK adults, dust ingestion of BDE-209 may pose a significant risk for UK toddlers.

Novel Insights into the Dermal Bioaccessibility and Human Exposure to Brominated Flame Retardant Additives in Microplastics.

In this study, we optimized and applied an in vitro physiologically based extraction test to investigate the dermal bioaccessibility of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD), incorporated as additives in different types of microplastics (MPs), and assess human dermal exposure to these chemicals. The dermal bioaccessibility of PBDEs in polyethylene (PE) MPs was significantly higher (P < 0.05) than in polypropylene (PP) MPs. Both log Kow and water solubility influenced the dermal bioaccessibility of PBDEs. For HBCDDs in polystyrene MPs, the dermally bioaccessible fractions were 1.8, 2.0, and 1.6% of the applied dose for α-, ß-, and γ-HBCDDs, respectively. MP particle size and the presence of cosmetic formulations (antiperspirant, foundation, moisturizer and sunscreen) influenced the bioaccessibility of PBDEs and HBCDDs in MP matrices at varying degrees of significance. Human exposure to ∑PBDEs and ∑HBCDDs via dermal contact with MPs ranged from 0.02 to 22.2 and 0.01 to 231 ng (kg bw)-1 d-1 and from 0.02 to 6.27 and 0.2 to 65 ng (kg bw)-1 d-1 for adults and toddlers, respectively. Dermal exposure to PBDEs and HBCDDs in MPs is substantial, highlighting for the first time the significance of the dermal pathway as a major route of human exposure to additive chemicals in microplastics.

Dermal bioaccessibility of perfluoroalkyl substances from household dust; influence of topically applied cosmetics.

PFAS are known contaminants of indoor dust. Despite the adherence of such dust to skin, the dermal penetration potential of PFAS is not well understood. By applying in vitro physiologically based extraction tests, the bioaccessibility of 17 PFAS from indoor dust to synthetic human sweat sebum mixtures (SSSM) was assessed. The composition of the SSSM substantially impacted the bioaccessibility of all target compounds. PFAS bioaccessibility in a 1:1 sweat:sebum mixture ranged from 54 to 92% for perfluorocarboxylic acids (PFCAs) and 61-77% for perfluorosulfonic acids (PFSAs). Commonly applied cosmetics (foundation, sunscreen, moisturiser, and deodorant) significantly impacted the dermal bioaccessibility of target PFAS, e.g., the presence of moisturiser significantly decreased the total bioaccessibility of both PFCAs and PFSAs. Preliminary human exposure estimates revealed dermal contact with indoor dust could contribute as much as pathways such as drinking water and dust ingestion to an adult's daily intake of PFAS. While further research is needed to assess the percutaneous penetration of PFAS in humans, the current study highlights the potential substantial contribution of dermal exposure to human body burdens of PFAS and the need for further consideration of this pathway in PFAS risk assessment studies.

Dermal uptake of chlorinated organophosphate flame retardants via contact with furniture fabrics; implications for human exposure.

The chlorinated organophosphate flame retardants (Cl-PFRs): tris-(2-chloroethyl)-phosphate (TCEP), tris-(1-chloro-2-propyl)-phosphate (TCIPP) and tris-(1,3-dichloropropyl)-phosphate (TDCIPP), have been widely used in upholstered furniture despite their carcinogenic potential. Although Cl-PFRs are mainly added to furniture foam, they are present in the fabrics likely due to migration from the foam. While several studies have assessed human exposure to Cl-PFRs via different pathways, no information exists on dermal uptake of these chemicals through contact with fabrics. In the current study, dermal absorption of TCEP, TCIPP and TDCIPP from 3 UK domestic furniture fabrics was experimentally assessed for the first time using in vitro 3D-human skin equivalents (EpiSkin™) under different real-life exposure scenarios. Results revealed all 3 target Cl-PFRs were dermally bioavailable to varying degrees (3.5%-25.9% of exposure dose) following 24 h contact with the studied fabrics. Estimated permeability coefficients (KP, cm h-1) showed TCEP had the highest percutaneous penetration potential followed by TCIPP, then TDCIPP. Further investigation revealed human dermal uptake of Cl-PFRs can be influenced by several factors including: the specific physicochemical properties of the compound, the type of exposure matrix, the exposure dose and the degree of skin hydration at the point of contact. Exposure assessment revealed UK adults and toddlers can be exposed to 20.4 and 14.1 ng TCIPP/kg bw/day via contact with furniture fabrics in summer, which is higher than international average exposures via inhalation and dust ingestion for adults and dietary exposure for toddlers. Therefore, risk assessment studies for Cl-PFRs and future replacements should consider dermal contact with consumer products (e.g. furniture fabrics) as a potential significant human exposure pathway.

Microplastics in freshwater sediments: Analytical methods, temporal trends, and risk of associated organophosphate esters as exemplar plastics additives.

It has been estimated that over 28 million tonnes of plastics end up in water bodies annually. These plastics degrade into microplastics (MPs), which along with microbeads and MPs from other sources such as wastewater treatment plants continue to threaten the aquatic system. At such small sizes, and corresponding larger surface areas per unit mass/volume, MPs exhibit enhanced capacity for absorbing and desorbing toxic chemicals/additives. Therefore, MPs can serve as vectors through which additives as well as other persistent, bio-accumulative, and toxic chemicals can enter the food chain. Additives are a significant component of most plastic products with some identified as hazardous to health and the environment. One group of additives that has continued to attract interest is organophosphate esters (OPEs), which are used both as flame retardants and plasticizers. Some of these OPEs are suspected carcinogens and endocrine disruptors and have been reported to exert serious toxic effects on freshwater biota. Separate studies on the presence and fate in the freshwater environment of these additives and MPs have emerged recently. However, no studies exist that examine the extent to which plastics additives such as OPEs in sediments are sorbed to MPs as opposed to the sediment itself. This has potentially important implications for the bioavailability of such additives and studies to examine this are recommended. This paper reviews critically the current state-of-knowledge on MPs in freshwater sediments, methods for their analysis, as well as their occurrence, temporal trends, and risks to the freshwater aquatic environment. Moreover, to facilitate the study of additives associated with MPs that have been extracted from sediments, we consider the possible effect of MP isolation methods on the determination of concentrations of associated additives like OPEs.

Atmospheric concentrations of polychlorinated biphenyls, brominated flame retardants, and novel flame retardants in Lagos, Nigeria indicate substantial local sources.

Polychlorinated biphenyls (PCBs), brominated flame retardants (BFRs) like polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCDD), and novel flame retardants (NFRs) like decabromodiphenyl ethane (DBDPE) are ubiquitous environmental pollutants. Despite this, little is known about their concentrations in outdoor air in the African continent. To address this knowledge gap, concentrations of BFRs, NFRs, and PCBs were measured in outdoor air at 8 sites located within the metropolitan area of Lagos, Nigeria. Concentrations of ∑8BDEs, ∑HBCDD, ∑7NFRs and ∑8PCBs were: 21-750 (median = 100) pg/m3, <12-180 (median = < 12) pg/m3, 34-900 (median = 300) pg/m3 and 85-460 (median = 300) pg/m3, respectively. Decabromodiphenyl ether (BDE-209, range: <16-620 pg/m3, median = 71 pg/m3) and DBDPE (range: <37-890 pg/m3, median = 280 pg/m3) were the dominant BFRs detected, while the non-Arochlor PCB 11 (range: 49-220 pg/m3, median = 100 pg/m3) was the dominant PCB. To the authors' knowledge, these are the first data on the non-Arochlor PCB 11 in outdoor air in Africa. In general, concentrations of all target contaminants in this study were within the range reported elsewhere in Africa and worldwide. Likely due to the tropical climate of Lagos, no seasonal variation in concentrations was discernible for any of the target contaminants. While concentrations of PBDEs and some NFRs were correlated with population density, concentrations of PCBs appear more impacted by leaks from electrical transformers and for PCB 11 to proximity to activities like textile factories that produce and use dyes.

Emerging and legacy brominated flame retardants in the breast milk of first time Irish mothers suggest positive response to restrictions on use of HBCDD and Penta- and Octa-BDE formulations.

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.

Concentrations of Brominated Flame Retardants in Indoor Air and Dust from Ireland Reveal Elevated Exposure to Decabromodiphenyl Ethane.

Concentrations of decabromodiphenyl ethane (DBDPE), 13 polybrominated diphenyl ethers (PBDEs), and hexabromocyclododecane (HBCDD) were measured in indoor air and dust collected from Irish homes, cars, offices, and primary schools during 2016-2017. Median concentrations of DBDPE in air (88 pg/m3) and dust (6500 ng/g) significantly exceed those previously reported internationally, with concentrations highest in offices and schools, suggesting that DBDPE is widely used in Ireland. Median concentrations of BDE-209 in air (340 pg/m3) and dust (7100 ng/g) exceed or are within the range of concentrations reported recently for the same microenvironments in the U.K., and exceed those reported in many other countries. Concentrations of BDE-209 in cars exceeded significantly (p < 0.05) those in other microenvironments. HBCDD was detected in all dust samples (median: 580 ng/g), and in 81% of air samples (median: 24 pg/m3) at concentrations similar to those reported recently for the U.K. and elsewhere. Estimates of exposure to DBDPE of Irish adults (92 ng/day) and toddlers (210 ng/day) as well as to BDE-209 (220 ng/day and 650 ng/day for adults and toddlers, respectively) substantially exceed those reported for the U.K. population. Moreover, our estimates of exposure of the Irish population to Σtrideca-PBDEs exceed previous estimates for Ireland via dietary exposure.

Perfluoroalkyl Substances in Drinking Water, Indoor Air and Dust from Ireland: Implications for Human Exposure.

Perfluoroalkyl substances (PFASs) were measured in air and dust from cars, homes, offices, and school classrooms in Ireland, along with drinking water from homes and offices. Perfluorooctanoic acid (PFOA) dominated air and drinking water, while perfluorobutane sulfonate (PFBS) dominated dust. This is the first report of PFOA, perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS), PFBS, and perfluorononanoic acid (PFNA) in air inside cars and school classrooms. PFOS concentrations in classroom air exceeded significantly (p ≤ 0.05) those in homes. Atmospheric concentrations of PFOA, PFNA, and methyl perfluorooctane sulfonamido ethanol (MeFOSE) (p ≤ 0.05) were significantly higher in cars containing child car seats than in cars without. PFOS, PFOA, PFBS, and PFHxS were all detected frequently in drinking water, but concentrations of PFASs were low, and although ΣPFASs were 64 ng/L in one bottled water sample, this fell below a Swedish Action Level of 90 ng ΣPFASs/L. The Irish population's exposure to PFOS and PFOA via non-dietary sources is well below estimates of dietary exposure elsewhere in Europe. Moreover, even under a high-end exposure scenario, it falls below the European Food Safety Authority's (EFSA) provisional tolerable weekly intakes for PFOS and PFOA.

Occurrence of legacy and alternative plasticizers in indoor dust from various EU countries and implications for human exposure via dust ingestion and dermal absorption.

Plasticizers are a category of chemicals extensively used in consumer products and, consequently, their presence is ubiquitous in the indoor environment. In the present study, an analytical method has been developed for the quantification of plasticizers (7 legacy phthalate esters (LPEs) and 14 alternative plasticizers (APs)) in indoor floor dust based on ultrasonic and vortex extraction, Florisil fractionation and GC-(EI)-MS analysis. Dust samples (n = 54) were collected from homes, offices, and daycare centers from different EU countries (Belgium, the Netherlands, Ireland and Sweden). Method LOQs ranged from 0.2 to 5 µg/g. Tri-n-hexyl trimellitate (THTM) was not detected in any sample, whereas dimethyl phthalate (DMP), diphenyl phthalate and acetyl triethyl citrate (ATEC) were detected only in 6, 2 and 1 out of 54 samples, respectively. The highest concentrations of plasticizers were measured in Swedish offices, at a mean concentration of total plasticizers of 1800 µg/g, followed by Swedish daycare centers at 1200 and 670 µg/g for winter and spring sampling, respectively. Generally, the contribution of APs was slightly higher than for LPEs for all indoor environments (mean contribution 60% and 40%, respectively based on contributions per indoor environment). For the APs, main contributors were DINP in Belgian homes (28%), Swedish offices (60%), Swedish daycare centers (48%), and Dutch offices (31%) and DEHT in Belgian (28%), Irish (40%) and Dutch homes (37%) of total APs. The predominant LPE was bis-2-ethylhexyl-phthalate (DEHP) with a mean contribution varying from 60% to 85% of total LPEs. Human exposure was evaluated for dust ingestion and dermal absorption using hazard quotients (HQs) of plasticizers (ratio between average daily doses and the reference dose). None of the HQs of plasticizers exceeded 1, meaning that the risk for adverse human health effects from these plasticizers via dust ingestion and dermal absorption is unlikely.

Polybrominated diphenyl ethers (PBDEs) in car and house dust from Thailand: Implication for human exposure.

This study examines concentrations of tri- to hexa-bromodiphenylethers (BDEs 17, 28, 47, 49, 66, 85, 99, 100, 153 and 154; Σ10PBDEs (polybrominated diphenyl ethers)) in car (n = 30) and house dust samples (n = 53) collected from different provinces in Thailand. The specific objectives of this study were: (i) to monitor levels of tri- to hexa-bromodiphenylethers (BDEs 17, 28, 47, 49, 66, 85, 99, 100, 153 and 154; Σ10PBDEs) in vehicle and residential dust sampled from various provinces in Thailand; (ii) to compare PBDE concentrations with those detected for domestic and automobile dust in studies from other countries and (iii) to estimate exposure of the Thai population to the target PBDEs via dust ingestion. Levels of Σ10PBDEs in vehicle and domestic dust were 0.68-38 and 0.59-260 ng g-1, respectively. BDEs 99 and 47 were the most abundant congeners in all automobile and residential dust samples. A t-test analysis indicated that Σ10PBDE concentrations in dust samples from dwellings exceeded significantly those from cars (p = 0.001). Furthermore, contents in dust of all PBDEs studied, except for BDE-28, were significantly higher in homes than in vehicles (p = 0.000-0.004). Principal Component Analysis (PCA) demonstrated no differences in PBDE congener patterns between Thai house and automobile dust, but revealed some subtle differences in the congener pattern between household dust samples in Thailand and those reported previously for the United Kingdom. Estimated environmental exposure of Thai adults and children for BDE-99 via dust ingestion were well within a chronic oral reference dose (RfD) for BDE-99 (100 ng/kg bw/day) proposed by the United States Environmental Protection Agency (US EPA).

Palaeotoxicity: reconstructing the risk of multiple sedimentary pollutants to freshwater organisms.

'Real-world' contaminant exposure of sediment-dwelling biota is typically long-term, low-level and to multiple pollutants. However, sediment quality guidelines, designed to protect these organisms, relate only to single contaminants. This study uses radiometrically dated sediment cores from 7 English lakes with varying contamination histories to reconstruct temporal changes in likely risk to biota (herein termed 'palaeotoxicity'). The Probable Effects Concentration Quotient (PEC-Q) approach was used to combine sediment concentrations from multiple contaminants (trace metals; PCBs; PBDEs) to determine risk allocated to metals and persistent organic pollutants (POPs) separately as well as combined (PEC-Q Mean-All). Urban-influenced lakes were considerably more contaminated, exceeding PEC-Q thresholds of 0.5 and 2.0 over long durations (some since the nineteenth century). This has been mainly due to metals (principally lead) and by factors of up to 10 for individual metals and by > 2 for PEC-Q Mean-Metals. In 6 out of 7 lakes, considerable reductions in risk associated with trace metals are observed since emissions reductions in the 1970s. However, at all lakes, PEC-Q Mean-POPs has increased sharply since the 1950s and at 5 out of 7 lakes now exceeds PEC-Q Mean-Metals. These organic pollutants are therefore now the dominant driver behind elevated contaminant risk to sediment-dwelling biota and recent temporal trends in PEC-Q Mean-All remain above threshold values as a result. Finally, PEC-Q Mean-All values were compared to standard biological toxicity tests for surface sediments at each site. While chironomid growth and daphniid reproduction were significantly reduced compared to controls at 5 out of 7, and all lakes, respectively, the scale of these reductions showed only limited quantitative agreement with predicted risk.

Biotransformation of the Flame Retardant 1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) in Vitro by Human Liver Microsomes.

The technical mixture of 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH or DBE-DBCH) and the pure ß-TBECH isomer were subjected to in vitro biotransformation by human liver microsomes (HLM). After 60 min of incubation, 5 potential metabolites of TBECH were identified in microsomal assays of both the TBECH mixture and ß-TBECH using ultraperformance liquid chromatography-Q-Exactive Orbitrap mass spectrometry. These include mono- and dihydroxylated TBECH and mono- and dihydroxylated TriBECH as well as an α-oxidation metabolite bromo-(1,2-dibromocyclohexyl)-acetic acid. Our results indicate potential hepatic biotransformation of TBECH via cyctochrome P450-catalyzed hydroxylation, debromination, and α-oxidation. Kinetic studies revealed that the formation of monohydroxy-TBECH, dihydroxy-TBECH, and monohydroxy-TriBECH were best fitted to a Michaelis-Menten enzyme kinetic model. Respective estimated Vmax values (maximum metabolic rate) for these metabolites were 11.8 ± 4, 0.6 ± 0.1, and 10.1 ± 0.8 pmol min-1 mg protein-1 in TBECH mixture and 4992 ± 1340, 14.1 ± 4.9, and 66.1 ± 7.3 pmol min-1 mg protein-1 in ß-TBECH. This indicates monohydroxy-TBECH as the major metabolite of TBECH by in vitro HLM-based assay. The estimated in vitro intrinsic clearance (Clint) of TBECH mixture was slower (P < 0.05) than that of pure ß-TBECH. While the formation of monohydroxy-TBECH may reduce the bioaccumulation potential and provide a useful biomarker for monitoring TBECH exposure, further studies are required to fully understand the levels and toxicological implications of the identified metabolites.

A rapid method for the determination of brominated flame retardant concentrations in plastics and textiles entering the waste stream.

Due to new European legislation, products going to waste are subject to 'low persistent organic pollutant concentration limits'. Concentrations of restricted brominated flame retardants in waste products must be determined. A rapid extraction and clean-up method was developed for determination of brominated flame retardants in various plastics and textiles. The optimised method used vortexing and ultrasonication in dichloromethane followed by sulfuric acid clean-up to determine target compounds. Poly-brominated diphenyl ethers were determined by gas chromatography with mass spectrometry and hexabromocyclododecane by liquid chromatography with tandem mass spectrometry. Good recoveries of target analytes were obtained after three extraction cycles. The method was validated using poly-propylene and poly-ethylene certified reference materials as well as previously characterised textiles, expanded and extruded poly-styrene samples. Measured concentrations of target compounds showed good agreement with the certified values indicating good accuracy and precision. Clean extracts provided low noise levels resulting in low limits of quantification (0.8-1.5 ng/g for poly-brominated diphenyl ethers and 0.3 ng/g for α-, ß- and γ-hexabromocyclododecane). The developed method was applied successfully to real consumer products entering the waste stream and it provided various advantages over traditional methods, including reduced analysis time, solvent consumption, minimal sample contamination and high sample throughput, which is crucial to comply with the implemented legislation.

Human dermal absorption of chlorinated organophosphate flame retardants; implications for human exposure.

Tris-2-chloroethyl phosphate (TCEP), tris (1-chloro-2-propyl) phosphate (TCIPP) and tris-1,3-dichloropropyl phosphate (TDCIPP) are organophosphate flame retardants (PFRs) widely applied in a plethora of consumer products despite their carcinogenic potential. Human dermal absorption of these PFRs is investigated for the first time using human ex vivo skin and EPISKIN™ models. Results of human ex vivo skin experiments revealed 28%, 25% and 13% absorption of the applied dose (500 ng/cm(2), finite dose) of TCEP, TCIPP and TDCIPP, respectively after 24h exposure. The EPISKIN™ model showed enhanced permeability values (i.e. weaker barrier), that were respectively 16%, 11% and 9% for TCEP, TCIPP and TDCIPP compared to human ex vivo skin. However, this difference was not significant (P>0.05). Estimated permeability constants (Kp, cm/h) showed a significant negative correlation with log Kow for the studied contaminants. The effect of hand-washing on dermal absorption of PFRs was investigated. Washing reduced overall dermal absorption, albeit to varying degrees depending on the physicochemical properties of the target PFRs. Moreover, slight variations of the absorbed dose were observed upon changing the dosing solution from acetone to 20% Tween 80 in water, indicating the potential influence of the dose vehicle on the dermal absorption of PFRs. Finally, estimated dermal uptake of the studied PFRs via contact with indoor dust was higher in UK toddlers (median ΣPFRs=36 ng/kg bw day) than adults (median ΣPFRs=4 ng/kg bw day). More research is required to fully elucidate the toxicological implications of such exposure.

Emerging and Legacy Flame Retardants in UK Indoor Air and Dust: Evidence for Replacement of PBDEs by Emerging Flame Retardants?

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.

Concentrations of Polybrominated Diphenyl Ethers, Hexabromocyclododecanes and Tetrabromobisphenol-A in Breast Milk from United Kingdom Women Do Not Decrease over Twelve Months of Lactation.

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.

Effect of Bromine Substitution on Human Dermal Absorption of Polybrominated Diphenyl Ethers.

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.