Phosphorus flame retardants: properties, production, environmental occurrence, toxicity and analysis

Since the ban on some brominated flame retardants (BFRs), phosphorus flame retardants (PFRs), which were responsible for 20% of the flame retardant (FR) consumption in 2006 in Europe, are often proposed as alternatives for BFRs. PFRs can be divided in three main groups, inorganic, organic and halogen containing PFRs. Most of the PFRs have a mechanism of action in the solid phase of burning materials (char formation), but some may also be active in the gas phase. Some PFRs are reactive FRs, which means they are chemically bound to a polymer, whereas others are additive and mixed into the polymer. The focus of this report is limited to the PFRs mentioned in the literature as potential substitutes for BFRs. The physico-chemical properties, applications and production volumes of PFRs are given. Non-halogenated PFRs are often used as plasticisers as well. Limited information is available on the occurrence of PFRs in the environment. For triphenyl phosphate (TPhP), tricresylphosphate (TCP), tris(2-chloroethyl)phosphate (TCEP), tris(chloropropyl)phosphate (TCPP), tris(1,3-dichloro-2-propyl)phosphate (TDCPP), and tetrekis(2-chlorethyl)dichloroisopentyldiphosphate (V6) a number of studies have been performed on their occurrence in air, water and sediment, but limited data were found on their occurrence in biota. Concentrations found for these PFRs in air were up to 47 μg m(-3), in sediment levels up to 24 mg kg(-1) were found, and in surface water concentrations up to 379 ng L(-1). In all these matrices TCPP was dominant. Concentrations found in dust were up to 67 mg kg(-1), with TDCPP being the dominant PFR. PFR concentrations reported were often higher than polybrominated diphenylether (PBDE) concentrations, and the human exposure due to PFR concentrations in indoor air appears to be higher than exposure due to PBDE concentrations in indoor air. Only the Cl-containing PFRs are carcinogenic. Other negative human health effects were found for Cl-containing PFRs as well as for TCP, which suggest that those PFRs would not be suitable alternatives for BFRs. TPhP, diphenylcresylphosphate (DCP) and TCP would not be suitable alternatives either, because they are considered to be toxic to (aquatic) organisms. Diethylphosphinic acid is, just like TCEP, considered to be very persistent. From an environmental perspective, resorcinol-bis(diphenylphosphate) (RDP), bisphenol-A diphenyl phosphate (BADP) and melamine polyphosphate, may be suitable good substitutes for BFRs. Information on PFR analysis in air, water and sediment is limited to TCEP, TCPP, TPhP, TCP and some other organophosphate esters. For air sampling passive samplers have been used as well as solid phase extraction (SPE) membranes, SPE cartridges, and solid phase micro-extraction (SPME). For extraction of PFRs from water SPE is recommended, because this method gives good recoveries (67-105%) and acceptable relative standard deviations (RSDs) (<20%), and offers the option of on-line coupling with a detection system. For the extraction of PFRs from sediment microwave-assisted extraction (MAE) is recommended. The recoveries (78-105%) and RSDs (3-8%) are good and the method is faster and requires less solvent compared to other methods. For the final instrumental analysis of PFRs, gas chromatography-flame photometric detection (GC-FPD), GC-nitrogen-phosphorus detection (NPD), GC-atomic emission detection (AED), GC-mass spectrometry (MS) as well as liquid chromatography (LC)-MS/MS and GC-Inductively-coupled plasma-MS (ICP-MS) are used. GC-ICP-MS is a promising method, because it provides much less complex chromatograms while offering the same recoveries and limits of detection (LOD) (instrumental LOD is 5-10 ng mL(-1)) compared to GC-NPD and GC-MS, which are frequently used methods for PFR analysis. GC-MS offers a higher selectivity than GC-NPD and the possibility of using isotopically labeled compounds for quantification.     

Polybrominated diphenyl ethers in house dust in Singapore

The use of polybrominated diphenyl ethers (PBDEs) as flame retardants in Singapore is not strictly regulated; therefore these compounds can be readily found in furniture, electronic devices, and building materials. This study was the first of its kind to be conducted in Singapore to measure concentrations of PBDEs in house dust. Samples were collected from 31 homes in various locations across the island-state of Singapore, and a total eight PBDEs congeners were measured. PBDEs were detected in all 31 dust samples and the number of BDE congener detected per home ranged between 3 and 8. The most abundant BDE congeners found were BDE 47, 99 and 209, with a median value of 20 ng g(-1) dust, 24 ng g(-1) dust and 1000 ng g(-1) dust, respectively. BDE 209 contributed 88% to the median of all the congeners, and BDE 47 and 99 contributed 1.8% and 3.5%, respectively. Different congener profiles were observed between this and studies conducted elsewhere, which is consistent with the use of different commercial PBDE around the world. No significant correlations between PBDE dust levels and residential characteristics (number of TVs and computers, floor area or flooring material) were observed. The daily intake of PBDEs via the inhalation pathway was estimated. House dust may be regarded as the most important exposure route of PBDEs for children.     

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.     

Organohalogen compounds in human breast milk from mothers living in Payatas and Malate, the Philippines: Levels, accumulation kinetics and infant health risk

Human breast milk samples (n = 33) from primipara and multipara mothers from Payatas a waste dump site, and Malate a reference site in the Phillipines were collected in 2004 and analyzed for eight organohalogen compounds, viz., PCBs, DDTs, CHLs, HCHs, HCB, TCPMe, PBDEs and HBCDs. DDTs and PCBs were predominant in all the samples. Overall mean concentrations of PBDEs found in our study were higher (7.5 ng/g lipid wt.) than those reported for Japan and many other Asian countries. Primipara mothers had significantly higher levels of DDTs, CHLs and HCHs than multipara mothers, but not PBDEs and HBCDs. A few individuals accumulated CHLs close to or even higher than the tolerable daily intake guidelines proposed by Health Canada.     

Occupational exposure to synthetic musks in barbershops,compared with the common exposure in the dormitories and households

Synthetic musks (SMs) have been widely used as fragrance ingredients in personal care and sanitary commodities. Due to their high volatility and particle-binding affinity, the indoor dust is a major reservoir of SMs, and dust ingestion could be an important exposure way to special populations, such as hairdressers. In spite of the known toxicity of SMs, there is no information regarding the occurrence of SMs in barbershop dusts and the exposure of hairdressers through indoor dust ingestion. In the present study, the levels of two nitro musks and five polycyclic musks were measured from indoor dust samples collected from barbershops, and some other indoor dust samples were also collected from dormitories, bathhouses and households for comparison. The concentrations of ∑SMs in barbershop dusts were 10–100 times higher than those from the other three indoor microenvironments. Polycyclic musks accounted for 89.4% of ∑SMs on average in all samples, of which two compounds, HHCB and AHTN jointly dominated 97.9% of polycyclic musks. The levels of HHCB and AHTN varied from 12.2 to 8.39 × 10⁵ and from 13.2 to 3.49 × 10⁵ ng g⁻¹, respectively. The daily intakes (DIs) of ∑SMs through house dust ingestion were estimated using the model of high dust ingestion and worst-case exposure (P95), and the corresponding exposure rates were 2791, 135 and 727 ng d⁻¹ for the hairdressers, general population and toddlers. SMs were also detected in blood samples collected from the hairdressers and normal adults (n = 50 and 10, respectively). There was no significant difference between these two groups. Despite the absence of higher SM concentrations in hairdresser’s blood, we should not overlook the potential occupational health risks due to their high SMs ingestion rate.     

"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.     

Geographical distribution of polybrominated diphenyl ethers (PBDEs) and organochlorines in small cetaceans from Asian waters

Polybrominated diphenyl ethers (PBDEs) are one of the flame retardants widely used in plastics, textiles, electronic appliances, and electrical household appliances. In this study, PBDEs and organochlorine compounds (OCs) were determined in the archived samples from the Environmental Specimen Bank for Global Monitoring (es-BANK) at Ehime University. The blubber of cetaceans found stranded along the coasts of Japan, Hong Kong, the Philippines and India during the period from 1990 to 2001 were employed for chemical analysis to understand the present status of contamination and the specific accumulation of PBDEs. PBDEs were detected in all the cetacean samples analyzed, and concentrations were one or two orders of magnitude lower than for PCBs and DDTs. Concentrations of PBDEs ranged from a low value of 6.0 ng/g lipid wt. in spinner dolphin (Stenella longirostris) from India to a high value of 6000 ng/g lipid wt. in Indo-Pacific humpback dolphin (Sousa chinensis) from Hong Kong. No difference in PBDE levels between coastal and offshore species from Japan was observed, implying the existence of pollution sources in this region other than Japan. Highest concentrations of PBDEs were found in animals from Hong Kong, followed by Japan, and much lower levels from the Philippines and India, suggesting that developing nations may also have pollution sources of PBDEs. Geographical distribution of PBDEs in Asian waters was different from PCBs but similar to DDTs.     

Reduction in Residential Chromium Following Site Remediation

ABSTRACT

The purpose of this study was to determine the influence of chromate production waste site remediation on residential Cr concentrations in house dust. Twenty-three homes in Jersey City, NJ, were identified as having had high (>500 u,g/gm, median 739 u,g/gm), medium (100-400 u,g/gm, median 245 u,g/gm), or low (<100 u,g/gm, median 48 u,g/ gm) Cr in house dust during a study conducted in 19921993 prior to site remediation. House dust samples were collected on four visits from each home between November 1996 and February 1998, extracted with HNO₃, and analyzed for Cr with an inductively coupled plasma-mass spectrometer. Homes that had low Cr concentrations in 1992-1993 continued to have low Cr concentrations (median 1 u,g/g). In contrast, substantial declines in Cr concentrations were found in the house dust collected from homes located near the remediated waste sites: previously high-level homes had a median of 50 u,g/g and mid-level homes had a median of 34 u,g/g. Site remediation had a beneficial effect on household loadings of Cr, since no differences in post-remediation house dust Cr concentrations were found among the three groups.     

Screening of organophosphorus compounds and their distribution in various indoor environments

Twelve organophosphorus compounds (OPs), which are used for diverse purposes (e.g. as plasticizers and flame retardants), were analysed in settled house dust from 15 indoor environments and in wipe test samples from computer screens and covers. Seven of the substances analysed dominated Swedish imports of OPs in 1999, six of these are also listed as EU High Production Volume Chemicals. Eight of the substances were found in all samples. Tris(2-butoxyethyl)phosphate was the most abundant in most of the samples, with levels ranging from 0.014 to 5.3 g/kg followed by tris(2-chloroethyl)phosphate, tris(chloropropyl)phosphate and tris(1,3-dichloropropyl)phosphate. In wipe test samples from computers, triphenyl phosphate proved to be the main component of the OPs analysed (4.0 microg/m2). Potential sources of these compounds include, inter alia, floor polish, polyvinylchloride floor coverings, upholstery and plastic products. The distribution patterns of the OPs differed between the sites and generally reflected the building materials and consumer products used in their vicinity.     

Reduction in residential chromium following site remediation

The purpose of this study was to determine the influence of chromate production waste site remediation on residential Cr concentrations in house dust. Twenty-three homes in Jersey City, NJ, were identified as having had high (> 500 micrograms/gm, median 739 micrograms/gm), medium (100-400 micrograms/gm, median 245 micrograms/gm), or low (< 100 micrograms/gm, median 48 micrograms/gm) Cr in house dust during a study conducted in 1992-1993 prior to site remediation. House dust samples were collected on four visits from each home between November 1996 and February 1998, extracted with HNO3, and analyzed for Cr with an inductively coupled plasma-mass spectrometer. Homes that had low Cr concentrations in 1992-1993 continued to have low Cr concentrations (median 1 microgram/g). In contrast, substantial declines in Cr concentrations were found in the house dust collected from homes located near the remediated waste sites: previously high-level homes had a median of 50 micrograms/g and mid-level homes had a median of 34 micrograms/g. Site remediation had a beneficial effect on household loadings of Cr, since no differences in post-remediation house dust Cr concentrations were found among the three groups.     

Polychlorinated biphenyls in vacuum dust and blood of residents in 20 Wisconsin households

Human exposure to PCBs is nearly universal in North America. While most exposure can be linked to consumption of contaminated fish, detection of PCBs in non-fish eating populations suggests that other routes of exposure including inhalation of PCB-laden particles or volatile congeners, ingestion of contaminated soil or dust, or dermal absorption following direct contact are also important. In an effort to assess the role of the residential environment as a source of exposure, vacuum dust was collected from the homes of 26 Wisconsin residents whose serum PCB levels had been measured approximately 2 years earlier. More than 60 congeners were detected in dust with all of the samples containing congeners 101, 110, 138 and 153. Total PCB levels ranged from 8.8 to 1186 ng g⁻¹ with levels being highest in vacuum dust from homes built between 1959 and 1970. Total PCB levels ranged from 0.05 to 8.34 μg L⁻¹ in serum collected from the adults living in these households, with congeners 138, 153 and 180 predominating. Hexa- and hepta-chlorinated biphenyls comprised 73% of the total residues detected in serum. However, most of the residues found in dust were lower chlorinated congeners with tetra- and penta-chlorinated biphenyls being dominant. Following log transformation, a positive association was found between serum and house dust PCB levels. This association was stronger among infrequent consumers of Great Lake fish, but of borderline statistical significance. This exploratory study suggests that house dust may be a significant source of exposure to PCBs and supports the need for further investigations.     

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.     

Occurrence of alternative flame retardants in indoor dust from New Zealand: indoor sources and human exposure assessment

Due to worldwide restrictions on polybrominated diphenyl ethers (PBDEs), the demand for alternative flame retardants (AFRs), such as organophosphate flame retardants (OPFRs), novel brominated FRs (NBFRs) and hexabromocyclododecanes (HBCDs), has recently increased. Little is known about human exposure to NBFRs and OPFRs and that their levels in dust have been scarcely evaluated worldwide. To increase the knowledge regarding these chemicals, we measured concentrations of five major NBFRs, ten OPFRs and three HBCD isomers in indoor dust from New Zealand homes. Dust samples were taken from living room floors (n=34) and from mattresses of the same houses (n=16). Concentrations (ngg(-1)) of NBFRs were: 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) (<2-175), decabromodiphenyl ethane (DBDPE) (<5-1430), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) (<2-2285) and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (TBPH) (<2-640). For OPFRs, concentrations (ngg(-1)) ranged between: tri-ethyl-phosphate (TEP) (<10-235), tri-n-butyl-phosphate (TnBP) (<20-7545), tris-(2-chloroethyl)-phosphate (TCEP) (<20-7605), tris-(1-chloro-2-propyl) phosphate (TCPP) (20-7615), tri-(2-butoxyethyl)-phosphate (TBEP) (50-27325), tris-(2,3-dichloropropyl)-phosphate (TDCPP) (20-16560), tri-phenyl-phosphate (TPhP) (20-35190), and tri-cresyl-phosphate (TCP) (<50-3760). HBCD concentrations fell in the range <2-4100ngg(-1). BTBPE, DBDPE, TBPH, TBEP, and TnBP showed significant positive correlation (p<0.05) between their concentrations in mattresses and the corresponding floor dust (n=16). These data were used to derive a range of plausible exposure scenarios. Although the estimated exposure is well below the corresponding reference doses (RfDs), caution is needed given the likely future increase in use of these FRs and the currently unknown contribution to human exposure by other pathways such as inhalation and diet.     

Hazardous substances in indoor dust emitted from waste TV recycling facility

Various hazardous substances contained in waste TV sets might be released into environment via dust during recycling activities. Two brominated flame retardants (BFRs), polybrominated diphenyl ethers (PBDEs), and tetrabromobisphenol A (TBBPA), and five kinds of heavy metals (Cu, Pb, Cd, Cr, and Ni) were detected in indoor dust collected from two workshops (TV dismantling workshop and subsequent recycling workshop). PBDEs concentrations in dust from waste wires recycling line (722,000 ng/g) were the highest among the studied sites, followed by those in manual dismantling–sorting line (117,000 ng/g), whereas TBBPA concentrations were the highest in manual dismantling–sorting line (557 ng/g) and printed circuit board (PCB) recycling line (428 ng/g). For heavy metals, Cu and Pb were the most enriched metals in all dust samples. The highest concentration of Pb (22,900 mg/kg) was found in TV dismantling workshop-floor dust. Meanwhile, Cu was the predominant metal in dust from the PCB recycling line, especially in dust collected from electrostatic separation area (42,700 mg/kg). Occupational exposure assessment results showed that workers were the most exposed to BDE-209 among the four PBDE congeners (BDE-47, BDE-99, BDE-153, and BDE-209) in both workshops. The hazard quotient (HQ) indicated that noncancerous effects were unlikely for both BFRs and heavy metals (HQ?<?1), and carcinogenic risks for Cd, Cr, and Ni (risk?<?10^?6) on workers in two workshops were relatively low.     

Perfluoroalkyl chemicals in vacuum cleaner dust from 39 Wisconsin homes

Perfluoroalkyl chemicals (PFCs) have been used as surfactants and stain repellants in a variety of consumer products for more than 50 years and there is growing concern regarding their persistence and toxicity. Human exposure to these chemicals is essentially universal in North America and researchers have linked them to a variety of health problems ranging from higher rates of cancer, to developmental and reproductive problems, and higher cholesterol levels. Major exposure pathways are food and water ingestion, dust ingestion via hand to mouth transfer. In an effort to assess residential exposure, the Wisconsin Department of Health Services tested vacuum cleaner contents from thirty-nine homes for 16 perflouroalkyl chemicals. PFOS, PFOA, PFHxS, PFHpA and PFNA were found in all of the vacuum dust samples and dust from eight homes contained all 16 PFCs included in our analysis. The most commonly detected compounds were perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate (PFHxS) and perfluorooctanoic acid (PFOA) which together made up 70% of the total PFC residues in dust from these homes. Summed PFC concentrations in these dust samples ranged from 70 to 2513 ng/g (median 280 ng/g). Our investigation suggests that these chemicals may be ubiquitous contaminants in US homes.     

Polybrominated diphenyl ethers in aircraft cabins--a source of human exposure?

Commercial aircrafts need a high degree of fire protection for passenger safety. Brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs), may be used for this purpose. Because PBDEs readily absorb to dust particles, aircraft crew and passengers may receive significant PBDEs exposure via inhalation. The aims of this work were to assess whether PBDEs could be found in aircraft cabin dust and whether serum levels of PBDEs increased in passengers after long-distance flights. Hence nine subjects on intercontinental flights collected cabin dust samples, as well as donated blood samples before departure and after return to Sweden. Two subjects who were domestic frequent flyers were also investigated. The levels of PBDEs in dust and serum were determined by GC/MS in electron capture negative ionization (ECNI) mode. Authentic reference substances were used for identification and quantitation. PBDEs were found in all aircraft dust samples at high concentrations, higher than in common household dust. Congener patterns indicated that the technical products PentaBDE, OctaBDE and DecaBDE were used in the aircrafts. Serum concentrations in the travellers were similar to those observed in Swedish residents in general. Post-travel serum levels of BDE-28, BDE-99, BDE-100, BDE-153, and BDE-154 were significantly higher (p<0.05) than concentrations prior to travel. The findings from this pilot study call for investigations of occupational exposures to PBDEs in cabin and cockpit crews.     

Microplastic pollution in deposited urban dust,Tehran metropolis,Iran

Environmental pollutants such as microplastics have become a major concern over the last few decades. We investigated the presence, characteristics, and potential health risks of microplastic dust ingestion. The plastic load of 88 to 605 microplastics per 30 g dry dust with a dominance of black and yellow granule microplastics ranging in size from 250 to 500 μm was determined in 10 street dust samples using a binocular microscope. Fluorescence microscopy was found to be ineffective for detecting and counting plastic debris. Scanning electron microscopy, however, was useful for accurate detection of microplastic particles of different sizes, colors, and shapes (e.g., fiber, spherule, hexagonal, irregular polyhedron). Trace amounts of Al, Na, Ca, Mg, and Si, detected using energy dispersive X-ray spectroscopy, revealed additives of plastic polymers or adsorbed debris on microplastic surfaces. As a first step to estimate the adverse health effects of microplastics in street dust, the frequency of microplastic ingestion per day/year via ingestion of street dust was calculated. Considering exposure during outdoor activities and workspaces with high abundant microplastics as acute exposure, a mean of 3223 and 1063 microplastic particles per year is ingested by children and adults, respectively. Consequently, street dust is a potentially important source of microplastic contamination in the urban environment and control measures are required.     

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.     

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.