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As a large group of chemicals with diverse properties, per- and polyfluoroalkyl substances (PFAS) have found extensive application throughout consumer products, including cosmetics. Little is known about the importance of dermal uptake as a human exposure pathway for PFAS. Here we investigate a suite of listed-ingredient and residual PFAS in cosmetic products, along with their dermal bioaccessibility using in vitro incubations with artificial sweat. Concentrations of volatile listed ingredients (including cyclic perfluorinated alkanes, perfluorinated ethers, and polyfluorinated silanes) in three products ranged from 876–1323 μg g−1, while polar listed ingredients (i.e., polyfluoroalkyl phosphate esters [PAPs]) in a single product occurred at up to 2427 μg g−1 (6 : 2/6 : 2 diPAP)). Residual perfluoroalkyl carboxylic acids (PFCAs) were also measured at concentrations ranging from 0.02–29 μg g−1. When listed ingredients were included, our targeted analysis accounted for up to 103% of the total fluorine, while highlighting ambiguous and/or incorrect International Nomenclature of Cosmetic Ingredient (INCI) names used in several products. Bioaccessibility experiments revealed that residual PFCAs readily partitioned to artificial sweat (bioaccessible fractions ranging from 43–76% for detectable substances) while listed ingredients (i.e., PAPs and neutral/volatile PFAS) displayed negligible partitioning. This work provides new insight into the occurrence of PFAS in cosmetic products, while furthering our understanding on their mechanisms of dermal uptake. [ABSTRACT FROM AUTHOR]

Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and hexabromocyclododecane (HBCDD) are regulated under the Stockholm Convention of the United Nations' Environment Programme; with similar concerns emerging about alternative halogenated flame retardants (alt-HFRs), the use of which is increasing as replacements for PBDEs and HBCDD. While the presence in indoor dust of PCBs, PBDEs, and HBCDDs has been reported previously in a few African locations including Lagos, Nigeria, we are unaware of similar data for alt-HFRs. The present study thus aimed to provide the first information on alt-HFRs in indoor dust in sub-Saharan Africa, and to evaluate the impact of restrictions on the use of PBDEs, HBCDD, and PCBs on their concentrations in house dust in Lagos, Nigeria. Concentrations of ∑8PBDEs, ∑HBCDDs, ∑7alt-HFRs, and ∑8PCBs in 15 samples of dust from homes in Lagos, Nigeria were found to be: 43–810 (median = 300) ng g−1,

−1, 32–2600 (median = 320) ng g−1 and 3.8–61 (median = 18) ng g−1 respectively. The dominant PBDE was BDE-209, its replacement decabromodiphenyl ethane (DBDPE) was the predominant alt-HFR, while PCB-138 displayed the highest concentration of the 8 PCBs targeted. Likely due to their higher vapour pressures, concentrations of the non-arochlor PCB 11, as well as those of PCB 28, and PBDE 28 were below detection limits. Concentrations of PBDEs and PCBs reported are generally below those reported previously for Lagos, Nigeria; suggesting restrictions on their manufacture and use have been effective. In contrast, while concentrations of BDE-209 in this study were lower than in one previous study in Lagos, they exceeded those in another; implying that the more recent restrictions on the deca-BDE product have yet to be fully effective. The evidence presented here of concentrations of alt-HFRs in Nigerian house dust provide a valuable benchmark against which future trends in their concentrations may be evaluated. [ABSTRACT FROM AUTHOR]

Surface riverine sediment samples were collected along the course of the River Medway, UK, between Yalding and the mouth of the estuary at 40 different sites. The samples were then analysed for hexabromocyclododecane (HBCDD) concentrations using a liquid chromatography system coupled to a high-resolution, accurate mass Orbitrap™ mass spectrometer. After normalisation to the sediment organic carbon (OC) content, average ΣHBCDD was 270 ng g−1 OC with a maximum concentration of 1006 ng g−1 OC. Spatial trend analysis revealed that industrial and residential land uses have significantly influenced HBCDD concentrations and profiles in riverine sediments. Higher concentrations of ΣHBCDD were found in sites near construction and maritime port locations, and these included freight ports, new builds and demolition sites. The HBCDD isomer profile reflected that of the commercial mixture with a comparatively high γ-HBCDD to α-HBCDD and β-HBCDD. The isomer profiles of sites located near construction activities indicate recent pollution events, with increased γ-HBCDD and decreased α-HBCDD compared to the study area's average profile. HBCDD isomer concentrations also indicated that the non-tidal portions of the river caused by locks showed a profile that was typical of older HBCDD contamination, indicating a possible sediment and HBCDD trap. [ABSTRACT FROM AUTHOR]

The legacy flame retardants (LFRs) polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD), together with six emerging flame retardants (EFRs) were measured in United Kingdom (UK) human milk collected in 2010 (n = 25) and 2014–15 (n = 10). These data are the first report of the presence of EFRs in UK human milk. The most abundant EFR was β-tetrabromoethylcyclohexane (DBE-DBCH) (average = 2.5 ng/g lw; geometric mean = 1.5 ng/g lw), which is comparable to the concentrations of the most abundant LFRs i.e. BDE 47 and α-HBCDD at 2.8 and 2.1 ng/g lw, respectively (geometric mean = 2.1 and 1.7). The estimated median dietary intake of ΣEFRs by UK nursing infants was 18 ng/kg bw/day. EFRs were also measured in UK foodstuffs with β-DBE-DBCH again the predominant compound detected, accounting – on average – for 64.5 ± 23.4% of ΣEFRs. Average estimated dietary intakes of ∑ EFRs in the UK were 89 and 26 ng/day (1.3 and 2.6 ng/body weight/day) for adults and toddlers, respectively. Concentrations of Σtri-hexa BDEs in our UK food samples exceeded those reported in UK samples from the same food categories collected in 2003–04 and 2006. Despite this and our recent report elsewhere of significant temporal declines in concentrations of BDE 209 in UK indoor dust (p < 0.05) and HBCDDs in UK indoor dust and air (p < 0.001), no significant temporal differences (p > 0.05) were observed between concentrations of Σtri-hexa BDEs, BDE 209 and HBCDDs in human milk sampled in 2010 and those obtained in 2014–15. UK adult body burdens for EFRs were predicted via inhalation, diet and dust ingestion using a simple pharmacokinetic model. The predicted EFR body burdens compared well with observed concentrations in human milk. [ABSTRACT FROM AUTHOR]

Concentrations of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs) and some organochlorine pesticides (OCPs) were determined in serum of Egyptian colorectal cancer patients (n = 35) and compared to a healthy control group (n = 32). p,p′-DDE (the major metabolite of DDT) was the most frequently detected contaminant with the highest concentration (median = 131 ng/g lw) in all studied serum samples. BDE-209 was the least frequently detected contaminant with a median concentration <0.3 ng/g lw. The contamination profile in patients and controls was almost identical with p,p′-DDE showing the highest median contribution (77%) and oxychlordane the lowest (1%). The low p,p′-DDT/p,p′-DDE ratio (3.7%) in serum implies bioaccumulation and past exposure to DDT (c.f. recent and ongoing intake). Statistical analysis revealed no significant differences ( P > 0.05) between the levels of target contaminants in serum of patients and the control group. Gender, age and body mass index (BMI) were investigated as potential factors influencing serum contaminant levels. ΣDDT, hexachlorobenzene and pentachlorophenol concentrations showed significant positive associations with age and/or BMI of the participants. Comparison with other countries revealed concentrations of PBDEs and PCBs in Egyptian serum among the lowest reported worldwide. [ABSTRACT FROM AUTHOR]

TBBP-A is a high production volume chemical applied widely as a flame retardant in printed circuit boards. Recent studies have raised concern over potential harmful implications of TBBP-A exposure in human and wildlife, leading to its classification under group 2A “Probably carcinogenic to humans” by the International Agency for Research on Cancer. This article provides a comprehensive review of the available literature on TBBP-A analysis, environmental levels and human exposure. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been identified as the method of choice for robust, accurate and sensitive analysis of TBBP-A in different matrices. TBBP-A has been detected in almost all environmental compartments all over the world, rendering it a ubiquitous contaminant. Human exposure studies revealed dust ingestion and diet as the major pathways of TBBP-A exposure in the general population. Toddlers are likely to be more exposed than adults via accidental indoor dust ingestion. Moreover, exposure to TBBP-A may occur prenatally and via breast milk. There are no current restrictions on the production of TBBP-A in the EU or worldwide. However, more research is required to characterise human exposure to TBBP-A in and around production facilities, as well as in e-waste recycling regions. [ABSTRACT FROM AUTHOR]

Humans are routinely exposed to mixtures of flame retardants (FRs) from multiple sources including indoor dust. As a model to explore the potential effects of FR exposure from indoor dust on human health, the molecular responses of human hepatoma cells (HepG2/C3A cells) to a defined mixture of FRs and to a dust extract were investigated using multiple non-targeted omics approaches. A solvent extract of an indoor dust standard reference material SRM2585 was used as the surrogate dust sample, while a mixture of four FRs (TCEP, TCIPP, TDCIPP and HBCD) was used to mimic the FR mixture in the indoor dust. Cytotoxicity tests indicated there were no significant changes to cell viability or cell integrity after a 24- or 72-h exposure of HepG2/C3A cells to the FR mixture or to the dust extract. However, transcriptomics revealed changes in gene expression associated with the metabolism of xenobiotics (e.g. CYP1A1, CYP1A2, CYP2B6 ) in the dust extract group but not in the FR mixture group after a 72-h exposure. Few metabolic or lipidomic changes were detected in response to either the FR mixture or to the dust extract group. Given that the dust extract contained components that elicited a biological response, in contrast to the lack of response induced by the FR mixture, our findings suggest that the most likely causes of the molecular responses to indoor dust exposure lie in components other than the four FRs investigated, e.g. caused by PAHs or PCBs. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Tetrabromobisphenol-A (TBBP-A) and hexabromocyclododecanes (HBCDs) are brominated flame retardants that have been found in human milk and serum throughout the world, but have received comparatively little attention in the United States. The objective of this study is to determine concentrations of these analytes in samples of breast milk collected from first-time mothers in the Greater Boston, Massachusetts area and to explore predictors of exposure. Human milk samples were analyzed by LC-ESI-MS/MS for TBBP-A, HBCDs (the α, β, and γ diastereomers), and HBCD degradation products: pentabromocyclododecanes (PBCDs) and tetrabromocyclododecadienes (TBCDs). HBCD diastereomers were detected in all samples with α-HBCD present in the highest proportion. TBBP-A, PBCDs, and TBCDs were detected in 35%, 42%, and 56% of the analyzed samples, respectively. Self-reported demographic, dietary and behavioral data were examined as predictors of HBCD levels. Levels of HBCD were significantly, positively associated with the number of stereo and video electronics in the home (17% increase/item; 95% Confidence Interval (CI) = 4-31%) and reduced in participants who regularly chose organic foods compared to those who did not (0.51, 95% CI = 0.32-0.82). These results suggest that lifestyle factors are related to body burdens of HBCD and that domestic electronics may be an important source of HBCD exposure in the indoor environment. [ABSTRACT FROM AUTHOR]

Current assessments of human exposure to flame retardants (FRs) via dust ingestion rely on measurements of FR concentrations in dust samples collected at specific points in time and space. Such exposure assessments are rendered further uncertain by the possibility of within-room and within-building spatial and temporal variability, differences in dust particle size fraction analysed, as well as differences in dust sampling approach. A meta-analysis of peer-reviewed data was undertaken to evaluate the impact of these factors on reported concentrations of brominated flame retardants (BFRs) and organophosphate esters (OPEs) in dust and subsequent human exposure estimates. Except for a few cases, concentrations of FRs in elevated surface dust (ESD) exceeded significantly those in floor dust (FD). The implications of this for exposure assessment are not entirely clear. However, they imply that analysing FD only will underestimate exposure for adults who likely rarely ingest floor dust, while analysing ESD only would overestimate exposure for toddlers who likely rarely ingest elevated surface dust. Considerable within-building spatial variability was observed with no specific trend between concentrations of either BFRs or OPEs in living rooms and bedrooms in the same homes, implying that exposure assessments based solely on sampling one room are uncertain. Substantial differences in FR concentrations were observed in different particle size fractions of dust. This is likely partly attributable to the presence of abraded polymer particles/fibres with high FR concentrations in larger particle size fractions. This has implications for exposure assessment as adherence to skin and subsequent FR uptake via ingestion and dermal sorption varies with particle size. Analysing dust samples obtained from a householder vacuum cleaner (HHVC) compared with researcher collected dust (RCD) will underestimate human exposure to the most of studied contaminants. This is likely due to the losses of volatile FRs from HHVC dust over the extended period such dust spends in the dust bag. Temporal variability in FR concentrations is apparent during month-to-month or seasonal monitoring, with such variability likely due more to changes in room contents rather than seasonal temperature variation. [Display omitted] • FR concentrations vary significantly between floor and elevated surface dust. • FR contamination of floor dust can vary significantly by within-room and within-building spatial variability. • The most suitable dust size fraction for exposure assessment is < 150 μm. [ABSTRACT FROM AUTHOR]