Emerging and legacy flame retardants in indoor dust from East China.

To understand human exposure to dust-associated flame retardants in the biggest metropolitan area (city of Shanghai) of East China, our study determined a suite of legacy and emerging flame retardants in dust from dwellings, cars, and university computer labs. The results exhibited a consistent dominance of organophosphate flame retardants (OPFRs) over polybrominated diphenyl ethers (PBDEs) and other alternative flame retardants (AFRs) regardless of microenvironments. In addition to OPFRs, some alternative flame retardants, such as decabromodiphenyl ethane (DBDPE), 2-ethylhexyltetrabromobenzoate (EH-TBB), bis(2-ethylhexyl)-3,4,5,6-tetrabromobenzoate (BEH-TEBP), and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), were also frequently detected. Among them, DBDPE exhibited concentrations comparable to those of PBDEs. Comparison with international studies indicated that concentrations of ∑PBDEs (0.2-12.3 μg/g dry weight or dw) and ∑OPFRs (3.8-165.5 μg/g dw) from Shanghai dwellings (bedroom and living room) were generally in the middle of concentration ranges reported worldwide, whereas elevated DBDPE concentrations (0.1-9.5 μg/g dw) was observed compared with most other countries or regions. OPFR compositions in house dust from this study also differed from those from many other countries. This suggested inter-regional differences in market demands on the quantities and types of flame retardants. Human intake estimation suggested elevated exposure for toddlers when compared with adults, although the daily intake estimations of individual flame retardants were generally 2-4 orders of magnitude lower than the reference doses. The findings from this preliminary study developed a baseline for future evaluation of the sources and fate of emerging flame retardants and related human exposure risks in East China.

Peng C ，Tan H ，Guo Y ，Wu Y ，Chen D ... -  《-》

Occurrence and human exposure to brominated and organophosphorus flame retardants via indoor dust in a Brazilian city.

Indoor dust is considered an important human exposure route to flame retardants (FRs), which has arised concern due the toxic properties of some of these substances. In this study, ten organophosphorus flame retardants (OPFRs), eight polybrominated diphenyl ethers (PBDEs) and four new brominated flame retardants (NBFRs) were determined in indoor dust from different places in Araraquara-SP (Brazil). The sampled places included houses, apartments, offices, primary schools and cars. The analysis of the sample extracts was performed by gas chromatography coupled to mass spectrometry and two ionization techniques were used (electron ionization - EI; electron capture negative ionization - ECNI). OPFRs were the most abundant compounds and tris(2-butoxyethyl) phosphate (TBOEP), tris(phenyl) phosphate (TPHP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP) and tris(2-chloroisopropyl) phosphate (TCIPP) were present at the highest concentrations. Among the brominated FRs, the most ubiquitous compounds were BDE-209, bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP) and decabromodiphenyl ethane (DBDPE). Statistical analysis revealed that there were differences among dust typologies for TBOEP, TDCIPP, ethylhexyl diphenyl phosphate (EHDPHP), BDE-209, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EH-TBB), BEH-TEBP and DBDPE, which were attributed to different construction materials in each particular environment and to the age of the buildings. The highest levels of brominated FRs were observed in offices, TBOEP was at high concentration in primary schools, and TDCIPP was at high concentration in cars. A preliminary risk assessment revealed that toddlers were exposed to TBOEP levels higher than the reference dose when considering the worst case scenario. The results obtained in this study showed for the first time that although Brazil does not regulate the use of FRs, these substances are present in indoor dust at levels similar to the observed in countries that have strict fire safety standards, and that humans are exposed to complex mixtures of these contaminants via indoor dust.

Cristale J ，Aragão Belé TG ，Lacorte S ，Rodrigues de Marchi MR ... -  《-》

Measurement of legacy and emerging flame retardants in indoor dust from a rural village (Kopawa) in Nepal: Implication for source apportionment and health risk assessment.

Under the Stockholm Convention, signatory countries are obliged to direct source inventories, find current sources, and provide ecological monitoring evidence to guarantee that the encompassing levels of persistent organic pollutants (POPs) are declining. However, such monitoring of different types of POPs are to a great degree constrained in most developing countries including Nepal and are primarily confined to suspected source area/ densely populated regions. In this study, 9 polybrominated diphenyl ethers (PBDEs), 2 dechlorane plus (DPs), 6 novel brominated flame retardants (NBFRs) and 8 organophosphate ester flame retardants (OPFRs) were investigated in indoor dust from a rural area (Kopawa) in Nepal in order to evaluate their occurrence/level, profile, spatial distribution and their sources. Additionally, health risk exposure was estimated to anticipate the possible health risk to the local population. The results showed that OPFRs was the most abundant FR measured in the dust. The concentration of ∑8OPFRs was about 2, 3 and 4 orders of magnitude higher than the ∑6NBFRs, ∑9PBDEs, and ∑2DPs, respectively. Tris (methylphenyl) phosphate (TMPP) and Tris (2-ethylhexyl) phosphate (TEHP) were the most abundant OPFRs analyzed in the dust; while decabromodiphenyl ethane (DBDPE) exceeded among NBFRs. Likewise, 2,2',3,3',4,4',5,5',6,6'-decabromodiphenylether (BDE-209) was the most identified chemical among PBDEs. The total organic carbon (TOC) content in dust was significantly and positively connected with octa-BDEs (Rho = 0.615, p < 0.01), BTBPE (Rho = 0.733, p < 0.01), TPHP (Rho = 0.621, p < 0.01), TEHP (Rho = 0.560, p < 0.01) and TMPPs (Rho = 0.550, p < 0.01), while black carbon (BC) was either weakly related or not related, suggesting little or no impact of BC in the distribution of FRs. Principal component analysis indicated the contribution from commercial penta-, octa- and deca-BDEs formulation, the adhesive substance, food packaging and paints, and degradation of BDE-209 as the essential sources of FRs. Health risk exposure estimates showed that dermal absorption via dust as the primary route of FRs intake. The estimated daily exposure of PBDEs, NBFRs and OPFRs were 2-10 orders of magnitude lower than their corresponding reference dose (RfD), suggesting insignificant risk. However, other routes such as inhalation and dietary intake might still be significant in the case of Kopawa which should be tested in future.

Yadav IC ，Devi NL ，Singh VK ，Li J ，Zhang G ... -  《-》

Concentrations of legacy and novel brominated flame retardants in indoor dust in Melbourne, Australia: An assessment of human exposure.

Polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFR) have been used in a range of polymers to inhibit the spread of fires but also have a propensity to migrate out of consumer materials and contaminate indoor dust. In this study, a total of 57 dust samples were collected from 12 homes, eight offices and eight vehicles in Melbourne, Australia and analysed for eight PBDEs (-28, -47, -99, -100, -153, -154, -183 and -209) and seven NBFRs (PBT, PBEB, HBB, EH-TBB, BEH-TEBP, BTBPE and DBDPE) to determine human exposure risks from dust ingestion. Samples were analysed using selective pressurized liquid extraction (S-PLE) and gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Legacy and replacement flame retardants were detected in all samples with overall ∑PBDE concentrations ranging from 120 to 1700,000 ng/g (median 2100 ng/g) and ∑NBFRs ranging from 1.1 to 10,000 ng/g (median 1800 ng/g). BDE-209 and DBDPE were the dominant compounds in dust samples, followed by congeners associated with commercial Penta-BDE formulations (-47, -99, -100, -153 and -154) and then EH-TBB of the FireMaster 550 and BZ-54 products. ∑Penta-BDE concentrations were elevated in office samples compared with homes and vehicles, while EH-TBB and BDE-209 measured higher concentrations in vehicles compared with their respective levels in homes and offices. Risk assessment estimates revealed the majority of exposure to occur in the home for both adults and toddlers in the City of Melbourne. Generally, body weight adjusted exposure to PBDEs and NBFRs was predicted to be 1 to 2 orders of magnitude higher for toddlers than adults. Estimated rates of BDE-47, -99, -153 and -209 ingestion were each 2 orders of magnitude or more below the USEPA's prescribed oral reference dose values (RfDs) for typical exposure scenarios. However, exposure rates for BDE-47 and -99 reached as high as 52 and 95% of RfDs, respectively, for adults and 4.4 and 7.4%, respectively, for toddlers in high exposure scenarios. This study provides the first wide-ranging survey of NBFRs in indoor dust from homes, offices and vehicles in Australia and offers further evidence of human exposure to legacy and novel brominated flame retardants via dust ingestion.

McGrath TJ ，Morrison PD ，Ball AS ，Clarke BO ... -  《-》

A review on organophosphate flame retardants in indoor dust from China: Implications for human exposure.

To investigate the status of organophosphate flame retardants (OPFRs) in indoor dust in China, published scientific studies were systematically collected and analyzed. The analysis revealed large variations among microenvironments, including offices (median: 14.59 μg/g) and e-waste workshops (median: 13.36 μg/g), with high levels of OPFRs contamination. Chlorinated organophosphate ester flame retardants (Cl-OPFRs) were the dominant OPFRs (52-75%) in most indoor dust samples; however, in e-waste workshops, aryl- and alkyl-OPFRs were the most abundant. As an alternative flame retardant to polybrominated diphenyl ethers (PBDEs), OPFRs concentrations have increased in recent years in indoor environments in China. Urban sources are of greatest concern: Shanghai (mean: 13.54 μg/g), Guangzhou (mean: 10.76 μg/g), and Beijing (mean: 9.37 μg/g) have high ΣOPFRs contamination levels in indoor dust. Compared to other countries, the OPFRs concentrations in indoor dust in all studied microenvironments from China (median: 8.81 μg/g) were low. The estimated daily intakes of ΣOPFRs by dust ingestion for adults and children were 2.12 and 11.06 ng/kg/body weight/day (average), respectively. Human exposure to OPFRs through the accidental intake of indoor dust does not pose a direct health risk to the Chinese population. However, indoor dust ingestion is an important route for human exposure to OPFRs.

Chen Y ，Liu Q ，Ma J ，Yang S ，Wu Y ，An Y ... -  《-》