Organophosphorus flame retardants in house dust from the Philippines: occurrence and assessment of human exposure

The use of organophosphorus flame retardants (PFRs) as flame retardants and plasticizers has increased due to the ban on common polybrominated diphenyl ether mixtures. However, only limited information on PFR contamination is available so far from Southeast Asia. In the present study, residual levels of PFRs in house dust and exposure through dust ingestion were investigated in the Philippines. House dust samples (n?=?37) were collected from Malate (residential area) and Payatas (municipal dumping area) in the Philippines and analyzed using ultra-high-performance liquid chromatography coupled with tandem mass spectrometry. Among the targeted seven PFRs, triphenyl phosphate (TPP) was the predominant compound. Median levels of ΣPFRs in Malate (530 ng/g) were two times higher (p?<?0.05) than in Payatas (240 ng/g). The estimated daily intake of PFRs in the Philippines (of areas studied) via house dust ingestion was below the guideline values. House dust may be an important contributor in the overall exposure of humans to TPP even when considering dietary sources. To our knowledge, this is a first report on PFR contamination in house dust from developing country. PFRs were ubiquitously detected in the home environments in the Philippines. Although estimated exposure levels through dust ingestion were below the guideline, it was suggested that toddlers are at higher risk. Therefore, further investigations to understand the behavior of PFRs in house and other microenvironments and overall exposure pathways for the country’s populace to PFRs are necessary.     

"Novel" brominated flame retardants in Belgian and UK indoor dust: implications for human exposure

Concentrations of several “novel” brominated flame retardants (NBFRs) are reported in indoor dust samples from Belgian houses (n = 39) and offices (n = 6) and from day-care centers and schools in the West Midlands of the UK (n = 36). Using a GC-ECNI/MS method, the following NBFRs were quantified: decabromodiphenyl ethane (DBDPE) (range <20-2470 ng g⁻¹), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) (range <0.5-1740 ng g⁻¹), tetrabromobisphenol A-bis(2,3-dibromopropylether) (TBBPA-DBPE) (range <20-9960 ng g⁻¹), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) (range <2-436 ng g⁻¹) and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) (range <2-6175 ng g⁻¹). Hexachlorocyclopentadienyl-dibromocyclooctane (HCDBCO), another NBFR, was below the detection limit of 2 ng g⁻¹ dust in all dust samples. No correlation was detected between concentrations of NBFRs and PBDEs. The ratio of TBB:TBPH in the dust samples ranged from 0.01 to 4.77 (average 0.42), compared to the ratio present in the commercial flame retardant product FM 550 (TBB:TBPH = 4:1). Furthermore, no correlation was detected between concentrations in dust of TBB and TBPH. This may suggest different sources of these NBFRs, or similar sources but compound-specific differences in their indoor fate and transport. Exposure via dust ingestion was estimated for both adults and toddlers under low-end (5th percentile), typical (median), and high-end (95th percentile concentrations) scenarios. These were calculated assuming 100% absorption of intake dust and using mean dust ingestion (adults = 20 mg d⁻¹; for toddlers = 50 mg d⁻¹) and high dust ingestion (adults = 50 mg d⁻¹; for toddlers = 200 mg d⁻¹). Typical exposure with high dust ingestion estimates for adults were 0.01, 0.2, 0.01, 0.02 and 0.08 ng kg⁻¹ bw d⁻¹ and for toddlers 0.05, 1.9, 0.08, 0.4 and 1.12 ng kg⁻¹ bw d⁻¹ for BTBPE, DBDPE, TBB, TBPH and TBBPA-DBPE, respectively. Our results showed that, similar to PBDEs, toddlers have higher exposure to NBFRs than adults. This study documents the presence of NBFRs in indoor environments, and emphasizes the need to evaluate the health implications of exposure to such chemicals.     

A nationwide survey of 20 legacy brominated flame retardants in indoor dust from China: continuing occurrence,national distribution,and implication for human exposure

Environmental Science and Pollution Research - Despite the restrictions on polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDDs), these chemicals are still ubiquitous...     

Organophosphate flame retardants and plasticizers in indoor air

Analytical methods were developed for a broad range of organophosphate flame retardants and plasticizers in indoor air. Screening was performed of various indoor environments at 12 locations in and around Zurich, Switzerland. Method recoveries ranged from 62% for triphenyl phosphate to 100% for tris(2-ethylhexyl) phosphate. Tris(2-chloro-isopropyl) phosphate was found in the highest concentration (260 ng/m(3)) mainly in cars and furniture stores. Tris(2-ethylhexyl) phosphate and triphenyl phosphate, both up to 3.4 ng/m(3), were also detected in quantifiable concentrations at several sites. Tris(1,3-dichloroisopropyl) phosphate, tricresyl phosphate and tri(2-butoxyethyl) phosphate were below the limit of quantification in all samples. The results of the risk assessment indicate that the observed concentrations are below the predicted threshold for human health effects.     

Legacy and emerging flame retardants in indoor and outdoor dust from Indo-Gangetic Region (Patna) of India: implication for source apportionment and health risk exposure

Environmental Science and Pollution Research - The fate of legacy and emerging flame retardants are poorly reported in developing countries, including India. Also, the positive matrix factorization...     

Brominated flame retardants in dust from UK cars--within-vehicle spatial variability, evidence for degradation and exposure implications

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.     

Analysis of brominated flame retardants in house dust

The main objective of this study was to create a robust analytical method to analyse the flame retardants decabromodiphenylether (BDE-209), hexabromocyclododecane (HBCD), and tetrabromobisphenol-A (TBBPA) in house dust in order to estimate the degree of contamination of indoor environment. A liquid chromatography method equipped with a UV-detector and electro spray-tandem mass spectrometry was used to achieve this result. Applying an external calibration for BDE-209, an internal calibration for TBBPA, and a standard addition method for HBCD low limits of quantification were obtained. The analytical procedure was carried out under exclusion of UV-light as the target compounds potentially degrade when being exposed to UV-light. Empirical data were obtained in addition to the dust samples to estimate potential influences of apartment characteristics. A weak correlation between the number of electric devices and TBBPA was found.     

Analysis of brominated flame retardants in house dust

The main objective of this study was to create a robust analytical method to analyse the flame retardants decabromodiphenylether (BDE-209), hexabromocyclododecane (HBCD), and tetrabromobisphenol-A (TBBPA) in house dust in order to estimate the degree of contamination of indoor environment. A liquid chromatography method equipped with a UV-detector and electro spray-tandem mass spectrometry was used to achieve this result. Applying an external calibration for BDE-209, an internal calibration for TBBPA, and a standard addition method for HBCD low limits of quantification were obtained. The analytical procedure was carried out under exclusion of UV-light as the target compounds potentially degrade when being exposed to UV-light. Empirical data were obtained in addition to the dust samples to estimate potential influences of apartment characteristics. A weak correlation between the number of electric devices and TBBPA was found.     

Transfer of brominated flame retardants from components into dust inside television cabinets

Television (TV) set components are highly flame resistant, with their added brominated compounds such as polybrominated diphenyl ethers (PBDEs). These compounds might be released indoors via dust, which presents a potential exposure pathway for humans in the home environment. In this study, we collected dust from inside TV sets and TV set component samples (parts of housing front cabinets, rear cabinets and circuit boards) of five sets used in Japan. We measured BFRs (i.e., PBDEs, tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs)) and polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/DFs). Analytical results of the TV components showed that the concentrations of PBDEs, TBBPA and PBDFs (48,000mug/g, 19,000mug/g and 9600ng/g as mean values, respectively) were all highest in the rear cabinets. The SigmaPBDD concentrations (460ng/g as a mean value) detected were highest in the circuit board samples. The respective SigmaPBDE and SigmaPBDF concentrations in the dust samples were 67-500mug/g (mean 300mug/g) and 180-650ng/g (mean 410ng/g). Such concentrations were 2-3 orders of magnitude higher than those previously reported for house dust samples, which suggests that the brominated compounds are transferred from TV components into dust. Comparison of congener patterns of the brominated compounds in the dust identified the components as the source of these BFRs.     

Legacy and alternative halogenated flame retardants in Lake Geneva fish

Environmental Science and Pollution Research - Legacy (i.e., polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD)) and alternative halogenated flame retardants (HFRs) were...     

Levels and sources of brominated flame retardants in human hair from urban, e-waste, and rural areas in South China

Human hair and indoor dust from urban, e-waste, and rural areas in south China were collected and analyzed for brominated flame retardants (BFRs). BFRs concentrations in hair from occupational e-waste recycling workers were higher than those from non-occupational exposed residents in other sampling areas. Polybrominated diphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE) are two major BFRs in hair samples. The PBDE congener profiles in hair from the e-waste area are different from those from urban and rural areas with relatively higher contribution of lower brominated congeners. DBDPE, instead of BDE209, has become the major BFR in non-e-waste recycling areas. Significant correlations were found between hair level and dust level for DBDPE and BTBPE but not for PBDEs. The different PBDE congener profiles between dust and hair may suggest that exogenous exposure to the PBDE adsorbed on dust is not a major source of hair PBDEs.     

Occurrence and fate of four novel brominated flame retardants in wastewater treatment plants

Four novel brominated flame retardants (NBFRs), i.e., decabromodiphenylethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB) were studied in 377 liquid samples and 288 solid samples collected from 20 wastewater treatment plants. Lagoon, primary, secondary, and advanced treatment processes were included, in order to investigate NBFR occurrence and the effects of WWTP operational conditions on NBFR removal. Median influent and effluent levels were 14 to 3,700 and 1.0 to 180 pg/L respectively, with DBDPE being the highest in both. Overall median removal efficiencies for DBDPE, BTBPE, HBB, and PBEB across all process types were 81 to 93, 76 to 98, 61 to 97, and 54 to 97 %, respectively with advanced treatment processes obtaining the best removals. NBFRs removal was related to retention time, surface loading rate, and biomass concentration. Median NBFR levels in treated biosolids were 80 to 32,000 pg/g, influenced by solids treatment processes.     

Arsenic and lead in the indoor residential settings of different socio-economic status; assessment of human health risk via dust exposure

Environmental Science and Pollution Research - In the present study, occurrence of arsenic (As) and lead (Pb) is reported in rural and urban household dust (floor and AC filter dust) of the Kingdom...     

水体中27种有机磷阻燃剂(OPFRs)的检测及风险评价

有机磷阻燃剂(organophosphorus flame retardants,OPFRs)具有致畸、致癌、致突变风险以及神经毒性作用。为了更好地研究其存在水平和健康风险,建立了固相萃取与高效液相色谱-串联质谱仪和气相色谱-质谱联用仪检测水体中27种OPFRs的分析方法,并对OPFRs进行了健康风险评价。20种OPFRs采用MCX固相萃取柱预处理和LC-MS/MS进行检测,以甲醇和含10 mmol·L⁻¹的甲酸水溶液作为流动相进行梯度洗脱,7种OPFRs采用HLB串联Envi-18固相萃取柱进行预处理并利用GC-MS进行检测。检测结果表明,27种OPFRs的检出限为0.02~2.53 ng·L⁻¹;定量限为0.06~8.43 ng·L⁻¹;回收率为65.82%~108.48%。2021年4月份,采集北京市潮白河地表水和地下水8个水样并检测其OPFRs。实测结果表明：除磷酸三(2-异丙基苯)酯、磷酸异癸基二苯酯、磷酸叔丁基苯二苯酯、磷酸二苄酯外,其余23种OPFRs均有不同程度检出,质量浓度为0~973.17 ng·L⁻¹;磷酸三(2-乙基己基)酯、磷酸三乙酯、磷酸三丙酯、磷酸三异丙酯含量相对较高,分别高达973.17、459.90、315.47、298.41 ng·L⁻¹。采用USEPA模型对水样中的OPFRs进行了健康风险评价, 13种OPFRs的非致癌风险值为0~6.17×10⁻⁴,4种OPFRs致癌风险值为1.37×10⁻⁹~1.07×10⁻⁷;在高暴露条件下,OPFRs的非致癌风险值为1.61×10⁻⁵~6.17×10⁻⁴,致癌风险值为1.00×10⁻⁸~1.07×10⁻⁷,均低于风险阈值。上述结果说明,水体中OPFRs产生的健康风险处于较低水平。此次采集的潮白河地表水和地下水水中OPFRs的致癌风险和非致癌风险均处于较低水平。本研究结果可为地表水和地下水水体中OPFRs的检测及风险评价提供参考。     

Brominated flame retardants and phenolic endocrine disrupters in Finnish human adipose tissue

Brominated flame retardants and phenolic compounds, of which several have been shown to exhibit endocrine disrupting effects, were screened in extracts of Finnish human adipose tissue samples. The samples were collected during autopsy from 39 subjects, of which 23 were males and 16 females. The samples were homogenised and extracted, and then cleaned-up by preparative gel permeation chromatography. The phenolic compounds were determined in silylated extracts. A total of 21 individual compounds were analysed in the extracts by gas chromatography-mass spectrometry (HRGC-LRMS) in the selected ion monitoring mode. The most commonly occurring compounds were 4-octylphenol diethoxylate, 4,4'-dihydroxybiphenyl, and 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), but also some other alkylphenols, pentabromophenol, and 2,2',4,4',5-penta- and 2,2',4,4',5,5'-hexabromodiphenyl ether could be detected in 1-6 samples. The concentrations were ranging from trace amounts to 71 ng/g of lipid weight. The mean concentration of BDE-47 was 1.20 ng/g lipids, however, in 15 of the samples the concentration was below the detection limit. Compared to other European studies the average concentration of BDE-47 obtained in this study is at the lower end of the reported concentrations.     

Leaching of brominated flame retardants in leachate from landfills in Japan

Leachate samples were taken from seven different landfills and concentrations of brominated flame retardants (BFRs), i.e. polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA), were quantified. Leaching characteristics of BFRs, especially factors affecting leachability, were clarified to obtain basic information regarding the release of BFRs into the environment. The results obtained for observed levels of the sum of PBDE-47, -99 and -100 were n.d.--4000 pg/l for the raw leachate and n.d. for the treated one, respectively, and those of TBBPA were n.d.--620,000 pg/l for the raw leachate and n.d.--11,000 pg/l for the treated one, respectively. Three sites that not only had crushed material from bulk wastes such as waste electric and electronic equipment, but also were under operation or within a year since closure, indicated a higher concentration of BFRs than the other sites. In particular extremely high concentration of PBDEs was observed at a site with a large amount of organics. Considering the leaching characteristics of BFRs, there exists the possibility that leachability of PBDEs is influenced by the presence of dissolved humic matter (DHM) in the leachate. The high removal efficiency for BFRs in the leachate treatment process was also confirmed.     

Polybrominated dibenzodioxins and -furans from the pyrolysis of some flame retardants

Purified 2,4,6-Tribromophenol, Pentabromophenol, Tetrabromobisphenol A and Tetrabromophthalic anhydride were pyrolyzed at 700°C, 800°C and 900°C. DBrDD, T3BrDD, T4BrDD (up to 89.6%), PBrDD, DBrDF, T3BrDF, and PBrDF were formed from 2,4,6-tribromophenol. From pentabromophenol PBrDD, H6BrDD, H7BrDD, OBrDD, PBrDF, H6BrDF, H7BrDF and OBrDF were formed. The burning of tetrabromobisphenol A gave MBrDD, DBrDD, T3BrDD, T4BrDD, MBrDF, DBrDF, T3BrDF and T4BrDF. In the residues of thermal reactions from tetrabromophthalic anhydride no PBrDD/PBrDF could be found. In all these studies the maximum of PBrDD/PBrDF-formation was at 800°C. The absence of PBrDD(PBrDF from the pyrolysate of tetrabromophthalic anhydride may guide the development of new brominated flame retardants, since certain structural features may suppress the formation of PBrDD/PBrDF.     

Polycyclic aromatic hydrocarbons in indoor and outdoor air in Turkey: Estimations of sources and exposure

The aim of the current study was to measure polycyclic aromatic hydrocarbons (PAHs) in eight indoor (In both kitchen and living room) air sampling locations using a passive sampling method for collection. Passive outdoor air samples were also collected from 3 of the same sampling locations as the indoor air sampling sites. Sampling was conducted in three seasons. The summer season, when windows are generally open, was between 18th July and 01st September, 2014; the autumn and winter seasons, when windows are mostly closed, was between 18^th October and 01^st December, 2014, and 01^st December, 2014, and 18^th January, 2015, respectively.

Average PAH concentrations in summer were 22 ± 21 ng/m³ and 17 ± 12 ng/m³ in the living room and kitchen, respectively, whereas living room and kitchen average PAH concentrations were 23 ± 16 ng/m³ and 20 ± 9 ng/m³, respectively, in autumn and 23 ± 13 ng/m³ and 23 ± 24 ng/m³, respectively, in winter. Outdoor air PAH concentrations in summer, autumn and winter were 7 ± 0.4 ng/m³, 22 ± 13 ng/m³ and 209 ± 33 ng/m³, respectively. An increase in outdoor PAH concentrations was measured in winter compared to the concentrations in summer and autumn, which paralleled the lower outdoor air temperature. However, PAH concentrations in the indoor environment vary according to the household characteristics and personal habits.     

Geographical distribution of non-PBDE-brominated flame retardants in mussels from Asian coastal waters

Hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), and decabromodiphenyl ethane (DBDPE) used as alternatives for polybrominated diphenyl ethers (PBDEs) are also persistent in the environment as PBDEs. Limited information on these non-PBDE brominated flame retardants (BFRs) is available; in particular, there are only few publications on environmental pollution by these contaminants in the coastal waters of Asia. In this regard, we investigated the contamination status of HBCDs, BTBPE, and DBDPE in the coastal waters of Asia using mussels as a bioindicator. Concentrations of HBCDs, BTBPE, and DBDPE were determined in green (Perna viridis) and blue mussels (Mytilus edulis) collected from the coastal areas in Cambodia, China (mainland), SAR China (Hong Kong), India, Indonesia, Japan, Malaysia, the Philippines, and Vietnam on 2003-2008. BTBPE and DBDPE were analyzed using GC-MS, whereas HBCDs were determined by LC-MS/MS. HBCDs, BTBPE, and DBDPE were found in mussels at levels ranging from <0.01 to 1,400, <0.1 to 13, and <0.3 to 22?ng/g lipid wt, respectively. Among the three HBCD diastereoisomers, α-HBCD was the dominant isomer followed by γ- and β-HBCDs. Concentrations of HBCDs and DBDPE in mussels from Japan and Korea were higher compared to those from the other Asian countries, indicating extensive usage of these non-PBDE BFRs in Japan and Korea. Higher levels of HBCDs and DBDPE than PBDEs were detected in some mussel samples from Japan. The results suggest that environmental pollution by non-PBDE BFRs, especially HBCDs in Japan, is ubiquitous. This study provides baseline information on the contamination status of these non-PBDE BFRs in the coastal waters of Asia.     

Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants in air and seawater of the European Arctic

The spatial distribution of polybrominated diphenyl ethers (PBDEs) and several alternative non-PBDE, non-regulated brominated flame retardants (BFRs) in air and seawater and the air-seawater exchange was investigated in East Greenland Sea using high-volume air and water samples. Total PBDE concentrations (Ó₁₀PBDEs) ranged from 0.09 to 1.8 pg m⁻³ in the atmosphere and from 0.03 to 0.64 pg L⁻¹ in seawater. Two alternative BFRs, Hexabromobenzene (HBB) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), showed similar concentrations and spatial trends as PBDEs. The air-seawater gas exchange was dominated by deposition with fluxes up to −492 and −1044 pg m⁻² day⁻¹ for BDE-47 and DPTE, respectively. This study shows the first occurrence of HBB, DPTE and other alternative flame retardants (e.g., pentabromotoluene (PBT)) in the Arctic atmosphere and seawater indicating that they have a similar long-range atmospheric transport potential (LRAT) as the banned PBDEs.