non-PBDE Brominated Flame Retardants Research Articles

Exposure and health risk assessment of secondary contaminants closely related to brominated flame retardants (BFRs): Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) in human milk in shanghai

Polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs), as the secondary environmental pollutants of the widely used brominated flame retardants (BFRs), possess the similar physicochemical and toxic properties as polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). However, studies on human body exposure to them are extremely limited. In this study, forty human milk samples collected in Shanghai were measured for 13 PBDD/F congeners using gas chromatography-high resolution mass spectrometry (GC-HRMS), to investigate their exposure level and characteristics, potential source and corresponding health risks to breastfed infants. The results showed no PBDDs but three PBDF congeners including 2,3,7,8-TBDF, 1,2,3,4,6,7,8-HpBDF and OBDF (mean concentration (detection rates) are 3.2 pg/g (72.5%), 9.5 pg/g (100%) and 28 pg/g (67.5%), respectively) were detected. The average toxic equivalent quantity (TEQ, 0.42 pg/g lw) presented the highest concentration level compared to other regions reported. The contribution of PBDFs to the total TEQ of PBDD/Fs and PCDD/Fs is 6.8%. The correlation between PBDD/Fs and age or dietary habits was not observed, which normally existed in their chlorinated analogues-PCDD/Fs. Significant correlations were observed between PBDFs and highly brominated polybrominated diphenyl ethers (PBDEs) (especially for BDE 183 and BDE 209). The correlation between PCDD/Fs and PBDFs was not observed except 2,3,7,8-TBDF. The high PBDFs exposure in Shanghai may originate from the emission of PBDEs and/or non-PBDE BFRs in environment, according to the consistency of the environmental data previously reported. The average estimated dietary intakes (EDI) for breastfed infants is 2.0 pg TEQ/kg·bw/day (0.13–13 pg TEQ/kg·bw/day), within the range of the tolerable daily intake (TDI) for TCDD (1–4 pg TEQ/kg·bw/day) suggested by the World Health Organization (WHO). However, given the high toxicity of PBDD/Fs, the potential health risks of these pollutants for breastfed infants should be of concern.

Halogenated organic contaminants of concern in urban-influenced waters of Lake Ontario, Canada: Passive sampling with targeted and non-targeted screening

Passive samplers are useful tools for monitoring hydrophobic, persistent, and potentially bioaccumulative contaminants in the environment. In this study, low density polyethylene passive samplers were deployed in urban-influenced and background nearshore freshwaters of northwestern Lake Ontario and analyzed for a broad range of both legacy halogenated organic contaminants (HOCs) and halogenated flame retardants (HFRs). Non-targeted analysis was conducted for screening additional halogenated substances. For most compounds, concentrations were greatest in the industrialized Hamilton Harbour and more generally at sites that have stronger influences of wastewater effluent discharges and stormwater run-off through rivers and creeks. Polychlorinated biphenyls (PCBs) remain the dominant class of HOCs in water, with dissolved-phase concentrations ranging from 10 to 4100 pg/L (ΣPCBs), followed by polybrominated diphenylethers (ΣPBDEs; 14–960 pg/L) and the organochlorine pesticides (OCPs; 22–290 pg/L). Several non-PBDE brominated flame retardants (nBFRs) and chlorinated Dechlorane-related compounds were detected, with hexabromocyclododecanes (ΣHBCDD; sum of 3 diastereoisomers) the most abundant (1.0–21 pg/L). Non-targeted screening of samples by high resolution mass spectrometry using Kendrick mass defect plots for data analysis indicated that several other halogenated compounds were present in waters at relatively high abundances compared to the flame retardants, based on semi-quantitative estimates. These included methyl-triclosan, four halogenated anisoles (2,4,6-tribromoanisole, dimethyl-trichloroanisole, pentachloroanisole, and pentachlorothioanisole), and pentachloro-aniline. Dissolved-phase methyl-triclosan was estimated to contribute up to approximately 40% of the summed target HOC concentrations. Polyethylene passive samplers provided an excellent medium for both non-targeted screening of HOCs not currently included in monitoring programs and tracking brominated and chlorinated chemicals slated for reductions in uses and emissions through international (Stockholm Convention) and binational (Great Lakes) agreements.

Worker exposure to flame retardants in manufacturing, construction and service industries

Workers in several industries are occupationally exposed to flame retardants. This study characterizes flame retardant exposure for nine industries through air and hand wipe measures for 105 workers. Specifically, we analyzed 24 analytes from three chemical classes: organophosphate flame retardants (OFRs), polybrominated diphenyl ethers (PBDEs), and non-PBDE brominated flame retardants (NPBFRs). The industries were: carpet installation, chemical manufacturing, foam manufacturing, electronic scrap, gymnastics, rigid board installation, nail salons, roofing, and spray polyurethane foam. Workers wore personal air samplers for two entire workdays and provided hand wipe samples before and after the second work day. Bulk products were also analyzed. The air, hand wipe and bulk samples were evaluated for relevant flame retardants. Spray polyurethane foam workers’ tris(1-chloro-2-propyl) phosphate air (geometric mean = 48,500 ng/m3) and hand wipe (geometric mean = 83,500 ng per sample) concentrations had the highest mean industry concentration of any flame retardant analyzed in this study, followed by triphenyl phosphate air concentration and tris(1,3-dichloro-2-propyl) phosphate hand wipe concentration from chemical manufacturers. Overall, OFR air and hand wipe concentrations were higher and more prevalent than PBDEs or non-PBDE brominated flame retardants. Some industries including spray polyurethane foam application, chemical manufacturing, foam manufacturing, nail salons, roofing, and rigid polyiso board installation had high potential for both air and hand exposure to OFRs. Carpet installers, electronic scrap workers, and gymnastic workers had exposures to all three classes of flame retardants including PBDEs, which were phased out of production in 2013. Air and dermal exposures to OFRs are prevalent in many industries and are replacing PBDEs in some industries.

Occurrence and source apportionment of atmospheric halogenated flame retardants in Lhasa City in the Tibetan Plateau, China

Active air samples were collected in Lhasa, one of the highest cities in the world (3650m above sea level) located in the Tibetan Plateau, and were analyzed for 38 halogenated flame retardants (HFRs), including polybrominated diphenyl ethers (PBDEs), non-PBDE brominated flame retardants (NBFRs) and dechlorane plus (DPs). The median concentrations of PBDEs, NBFRs and DPs were 40, 23 and 0.21pg/m3, respectively. Correlation analysis indicated the common source and/or similar environmental behavior for several HFRs. The Clausius–Clapeyron equation was applied to diagnose the sources of lower molecular weight HFRs (LMW-HFRs), which suggested that the gaseous LMW-HFRs at Lhasa were more controlled by regional or long-range atmospheric transport rather than the temperature-driven evaporation from local contaminated surfaces. Finally, the potential source contribution function model was applied to assess the influences of air parcels on the atmospheric concentrations of HFRs in Lhasa, which suggested that the sources of higher molecular weight HFRs (HMW-HFRs) were mostly originated from local emissions, while the others were originated from long-range atmospheric transport.

Dietary exposure assessment of Chinese population to tetrabromobisphenol-A, hexabromocyclododecane and decabrominated diphenyl ether: Results of the 5th Chinese Total Diet Study

Based on the 5th Chinese Total Diet Study (TDS) carried out in 2011, the dietary exposure of Chinese population to three currently used brominated flame retardants (BFRs), tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD) and decabrominated diphenyl ether (BDE-209), was estimated and the related health risks were assessed. Levels of the three BFRs were determined in 80 composite samples from four animal-origin food groups. The average levels of BFRs in various food groups ranged from 0.671 to 5.76 ng/g lipid weight (lw). The levels of TBBPA were lower than those of HBCD but higher than those of BDE-209. Moreover, average contamination levels of TBBPA and HBCD in TDS 2011 were found to be 3 to 30 times higher than those observed in TDS 2007 in the four food groups, indicating an increase in TBBPA and HBCD in the environment during 2007–2011. The average estimated daily intakes (EDIs) of TBBPA, HBCD and BDE-209 via food consumption for a “standard Chinese man” were 1.34, 1.51 and 0.96 ng/kg bw/day, respectively. Meat and meat products were found to be the major contributor to the daily dietary intake because the consumption of meat and meat products were significantly higher than that of other food groups in China. In comparison, the levels and EDIs of BFRs in this study were found to be higher than those in most studies worldwide. However, the large margin of exposure (MOE), with at least 1.1 × 105 calculated following the European Food Safety Authority (EFSA) approach, indicates that the estimated dietary exposure to these three BFRs is unlikely to raise significant health concerns. In addition, a comparison between the contamination levels of TBBPA, HBCD, BDE-209 and some novel BFRs in food samples from TDS 2011 indicated an obvious shift in the industrial production and usage pattern between PBDE and non-PBDE BFRs in China.

Multi-year air monitoring of legacy and current-use brominated flame retardants in an urban center in northeastern China

The occurrence and temporal trends of polybrominated diphenyl ethers (PBDEs) and non-PBDE brominated flame retardants (NBFRs) were investigated in an urban atmosphere of Northeast China in consecutive six years (2008–2013). Among all chemicals, BDE-209, l,2,5,6,9,10-hexabromocyclododecane (HBCD), and decabromodiphenylethane (DBDPE) were the three most dominant compounds. During the period, the levels of pentabromodiphenyl ethers in the gas-phase and octabromodiphenyl ethers in the particle-phase significantly decreased, while the levels of BDE-209 and NBFRs increased in either the gas-phase or particle-phase. Ambient temperature was the most significant variable that influenced the gas-phase and particle-phase concentrations of BFRs, followed by wind speed and relative humidity. A stronger temperature dependence of the atmospheric concentrations was found for lower mass BFRs. Gas-particle partitioning studies suggested PBDEs in the urban atmosphere of Northeast China were at steady-state. Steady-state equation can also well describe the partitioning behavior for NBFRs, suggesting that the atmospheric partitioning behaviors of NBFRs were similar to those of PBDEs.

New non-PBDE brominated flame retardants in sediment and plant samples from Jiaozhou Bay wetland

Seven non-polybrominated diphenyl ethers (non-PBDE) (TBB, TBX, PBT, PBEB, HBB, DBHCTD and BB153) were analyzed in sediment and plant samples which were collected from Xiaojianxi landfill to Dagu river estuary in Jiaozhou Bay wetland. The species of non-PBDE were different in sediment and plant samples with the concentration of 0.41–9.66ngg−1 and 0.15–1.2ngg−1, respectively. DBHCTD was the main non-PBDE compared with other target compounds and its concentration was 1.21–9.66ngg−1dw. Generally, the concentration of non-PBDE in sediment showed a decreasing tendency while discrete decline in plant has been revealed. Furthermore, DBHCTD, HBB, as well as other BFRs, might have a common BFRs degradation or similar accumulation potential in sediment, as their Pearson relationship p<0.05. Generally, the content of non-PBDE in Jiaozhou Bay wetland was higher than other published research. Therefore, more attention should be paid to non-PBDE on account of their persisting impact on human health and environment.

Occurrence of legacy and emerging halogenated organic contaminants in marine shellfish along French coasts

Current contamination levels of selected legacy, currently-used and emerging halogenated contaminants were monitored in marine shellfish along French coastlines. The studied contaminants included polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenylethane (DBDPE), hexabromobenzene (HBB), 2,2′,4,4′,5,5′-hexabromobiphenyl (BB-153) and perfluorinated compounds (PFCs).BDE-47, BDE-209, BTBPE, HBB and α-HBCDD were detected in 100% of the analyzed samples, whereas BB-153, DBDPE and PFOS were detected at frequencies of 97%, 90% and 55%, respectively. Concentrations were in the pgg−1ww range and varied as follows: PFOS>BDE-47∼α-HBCDD>BDE-209>BTBPE∼DBDPE>HBB∼BB-153. Overall, non-PBDE Brominated Flame Retardants (BFRs) revealed concentrations between 3 and 59 times lower than those of PBDEs.PBDE pattern was dominated by BDE-47, followed by BDE-99>BDE-100>BDE-49>BDE-209>BDE-154; these 6 congeners represented 94% of the summed ten PBDEs. PFC pattern determination revealed PFOS as the predominant PFC in samples from the English Channel and Atlantic, whereas perfluorocarboxylic acids (PFCAs) prevailed in Mediterranean samples. Temporal trend investigations on archived samples from the Mediterranean coast collected between 1981 and 2012 showed a prevalence of PFOS until 1998; PFCAs subsequently increased and became more abundant than PFOS. High levels of PFCAs were observed until 2008, followed by a decrease and stabilization in 2010–2012. Amongst PFCAs, perfluorotridecanoic acid (PFTrDA) and perfluoroundecanoic acid (PFUnA) were predominant and exhibited similar time trends, suggesting similar sources at the investigated site, home to major industrial activity.

Estimation of physicochemical properties of 52 non-PBDE brominated flame retardants and evaluation of their overall persistence and long-range transport potential

Non-PBDE (polybromodiphenyl ether) brominated flame retardants (BFRs) used as alternatives to PBDEs should be evaluated in terms of their environmental contamination potential. We first used two well-known estimation tools, EPI Suite and SPARC, to estimate the physicochemical properties of 52 non-PBDE BFRs. We assessed the dependence of the properties on the molecular weight and chemical structure of the compounds. The accuracy of the estimates was evaluated by comparing results with previous experimental data. In the case of EPI Suite, we have recommended an appropriate calculation method for the air–water partition coefficient. Half-lives in each environmental medium were also estimated with EPI Suite. Based on the estimated properties and half-lives, the overall persistence (Pov) and long-range transport potential (LRTP) of the BFRs were calculated using the Organization for Economic Cooperation and Development Pov and LRTP Screening Tool. We selected some POP-like chemicals from among the non-PBDE BFRs on the basis of their Pov and LRTP. From a Monte Carlo analysis of the calculated results for the selected BFRs, we suggest physicochemical properties to be measured in the future.

Fathead minnow (Pimephales promelas Rafinesque) exposure to three novel brominated flame retardants in outdoor mesocosms: bioaccumulation and biotransformation

The phaseout of polybrominated diphenyl ethers (PBDEs) has prompted the search for appropriate substitutes. These substitutes, referred to as novel brominated flame retardants (NBFRs), are poorly characterized in terms of their persistence, bioaccumulation, and toxicity. The authors assessed the bioaccumulation potential of 3 non-PBDE brominated flame retardants: 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), tetrabromobisphenol A bis(2,3-dibromopropylether) (TBBPA-BDBPE), and BZ-54, a mixture of bis(2-ethylhexyl)tetrabromophthalate) (BEH-TEBP) and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB). Replicate outdoor aquatic mesocosms were treated individually at concentrations designed to give a maximum load of 500 ng/g of flame retardant in the upper 5 cm of the sediment. Caged fathead minnows (Pimephales promelas, 24 fish per replicate) were introduced to each mesocosm and acclimated for 10 d prior to exposure. The exposure period was 42 d, followed by 28 d of depuration after transfer to a control mesocosm, during which physical, reproductive, and biochemical end points were examined. Tissue samples were taken to measure the accumulation, depuration, and biotransformation of NBFRs. Fathead minnows were observed to accumulate, after growth adjustment, BTBPE (16-4203 ng/g lipid) and TBBPA-BDBPE (>1000 ng/g lipid) but with a lack of consistent accumulation observed for EH-TBB and BEH-TEBP. However, limited biologically meaningful or consistent responses were observed in the monitored physical, reproductive, and biochemical parameters. Fathead minnows from each treatment exhibited several brominated transformation products. The authors conclude that these NBFRs have the potential to be bioaccumulative and persistent in vivo and, therefore, warrant further study of physiological effects linked to chronic, sublethal responses.

Measurement of Vapor Pressures of Selected PBDEs, Hexabromobenzene, and 1,2-Bis(2,4,6-tribromophenoxy)ethane at Elevated Temperatures

Vapor pressures (pi) of selected brominated flame retardants (BFRs), such as three polybrominated diphenyl ethers, PBDEs, 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), 2,2′,4,4′,5-pentabromodiphenyl ether (BDE-99), and 2,2′,4,4′,5,5′-hexabromodiphenyl ether (BDE-153), and two non-PBDE BFRs, hexabromobenzene (HBB) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) in the temperature range of (313 to 423) K, were measured by the gas saturation method. The standard uncertainties of temperature and vapor pressure measurements were estimated to be within ± 0.08 K and typically ca. ± 3.9 %, respectively. The temperature dependence of pi, namely, enthalpy of sublimation (ΔsubH), was determined by fitting the experimental data with the Clausius–Clapeyron equation. From the equation and our previous works on water solubility, pi and Henry’s law constant at 298 K for those BFRs were predicted. On the basis of these results, the environmental partitioning characteristics were also discussed.

Occurrence of PBDEs and other alternative brominated flame retardants in sludge from wastewater treatment plants in Korea

Studies on the occurrence of polybrominated diphenyl ethers (PBDEs) and other alternative brominated flame retardants in the environment are scarce. In this study, PBDEs and non-PBDE brominated flame retardants (NBFRs), including decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), were measured in sludge collected from three types of wastewater treatment plants (WWTPs) in Korea. Total concentrations of PBDEs (∑PBDE) in sludge ranged from 298 to 48,000 (mean: 3240) ng/g dry weight. Among 10 NBFRs analyzed, DBDPE and BTBPE were the only ones detected in sludge samples. Concentrations of DBDPE and BTBPE ranged from <LOQ to 3100 (mean: 237) ng/g dry weight and from <LOQ to 21.0 (mean: 1.57) ng/g dry weight, respectively. Concentrations of PBDEs and DBDPE determined in sludge were higher than those reported in other countries. The highest concentrations of ∑PBDE and DBDPE were found in sludge samples originated from industrial-WWTPs (I-WWTPs), suggesting that industrial activities are a major source of these contaminants. Non-parametric multidimensional scaling ordination showed that congener profiles of PBDEs in sludge are dependent on the types of WWTPs. Almost all sludge samples contained a low ratio (mean: 0.18) of DBDPE/BDE 209, indicating an on-going contamination by PBDEs in Korea. However, the high ratios (>1) of DBDPE/BDE 209 were found in sludge from I-WWTPs, reflecting a shift in the usage pattern of BFRs by the Korean industry. The nationwide annual emission fluxes of ∑PBDE, DBDPE and BTBPE via WWTPs to the environment were estimated to be 7400, 480, and 3.7kg/year, respectively. This is the first study on the occurrence of alternative brominated flame retardants in sludge from Korea.

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.

Classic and novel brominated flame retardants (BFRs) in common sole ( Solea solea L.) from main nursery zones along the French coasts

Brominated flame retardants (BFRs) were investigated in juvenile common sole from nursery zones situated along the French coast in 2007, 2008 and 2009. Extensive identification was performed with regard to PBDEs, novel BFRs 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), and other non-PBDE BFRs, namely, hexabromobenzene (HBB) and 2,2′,4,4′,5,5′-hexabromobiphenyl (BB-153). Polybrominated diphenyl ether (PBDE) concentrations (Σ 14 congeners) ranged from 0.01 ng/g to 0.16 ng/g wet weight (ww) in muscle, and 0.07 ng/g to 2.8 ng/g ww in liver. Concentrations were in the lower range of those reported in the literature in other European locations. Lower PBDE concentrations, condition indices and lipid contents were observed in the Seine estuary in 2009, possibly in relation to a lower water flow. The PBDE patterns and ratios we observed suggested that juvenile sole have a relative high metabolic degradation capacity. Non-PBDE BFRs were detected at lower levels than PBDEs, i.e., within the < method detection limit – 0.005 ng/g ww range in muscle, and < method detection limit – 0.2 ng/g ww range in liver. The data obtained is of particular interest for the future monitoring of these compounds in the environment.

Brominated Flame Retardants in Seawater and Atmosphere of the Atlantic and the Southern Ocean

Seawater and air samples were collected aboard the FS Polarstern during the cruises ANT-XXV/1 + 2 in the Atlantic and Southern Ocean in 2008. The particulate and dissolved phase in water and particulate and gaseous phase in air were analyzed separately for nine polybrominated diphenyl ethers (PBDEs) and six non-PBDE brominated flame retardants (BFRs). Air concentrations of 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and hexabromobenzene (HBB) in the gaseous and particulate phase (median = 0.56 pg m(-3) for DPTE and 0.92 pg m(-3) for HBB) were comparable to ∑(9)PBDEs (1.0 pg m(-3)). Pentabromotoluene (PBT) was detectable in ∼30% of the gaseous phase samples, whereas concentration of 2,4,6-tribromophenyl allylether (ATE), hexachlorocyclopentenyl-dibromocyclooctane (HCDBCO) and 2-ethyl-1-hexyl 2,3,4,5-tetrabromobenzoate (EHTBB) were below their method detection limits. DPTE, and PBDEs were also found in seawater at low pg per liter levels. Elevated seawater concentrations of PBDEs and DPTE were measured in the English Channel and close to South African coast. Concentrations of DPTE, BDE-47, and BDE-99 in the atmosphere generally decreased from Europe toward the Southern Ocean, whereas no latitudinal trend was observed in seawater. Air-water exchange gradients suggested net deposition dominates for all selected substances. The medians of net deposition fluxes for the air-water gas exchange were 83, 21, 69, 20, and 781 pg m(-2) day(-1) for BDE-47, BDE-100, BDE-99, DPTE, and HBB, whereas medians of dry deposition fluxes were 2.0, 0.3, 1.2, 1.0, and 0.5 pg m(-2) day(-1) for BDE-47, BDE-100, BDE-99, DPTE, and HBB. Overall, these results highlight the important role of the long-range atmospheric transport of PBDE and non-PBDE BFRs to remote regions.

可搬型蛍光Ｘ線分析計による各種製品部材中ＲｏＨＳ指令対象物質のスクリーニング調査

The content of hazardous substances restricted by the European Union directive on the restriction of the use of certain hazardous substances in electrical and electronic equipment 2002/95/EC (RoHS directive) in various consumer products including electrical and electronic equipments (EEE), household products, recycled products etc. were analyzed by using a handheld X-ray fluorescence (XRF) analyzer. Among 358 products investigated, one third failed RoHS compliance for Br when assuming all Br derived from polybrominated biphenyls and/or polybrominated diphenyl ethers (PBDEs), and all passed the RoHS threshold for Hg levels. About half of EEE examined contained more than 0.1 wt% of Br with the maximum concentration of approximately 20 wt% in rear casing of a computer monitor, indicating some sort of brominated flame retardants (BFRs) were intentionally added. From the XRF analysis of chassis of televisions (TV) and personal computer (PC) monitors, it was revealed that the percentage of products which exceeded Br thresholds in liquid crystal display TVs and PC monitors were less than those in cathode-ray tube TVs and PC monitors, suggesting the shift of type of flame retardants used over time. As use of PBDEs was restricted by RoHS directive in 2006, the consumer-electronics makers started using alternative flame retardants including novel non-PBDE BFRs and phosphorus flame retardants as well.

Several current-use, non-PBDE brominated flame retardants are highly bioaccumulative: Evidence from field determined bioaccumulation factors

With the phaseout of brominated flame retardants (BFRs) polybrominated diphenyl ethers (PBDEs), some non-PBDE BFRs have prompted to be alternatives to the discontinued PBDEs. To assess the bioaccumulation potential of these chemicals, field bioaccumulation factors (BAFs) for several non-PBDE BFRs including hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB), were determined in the aquatic species from a natural pond in an electronic waste recycling site in South China. The log BAFs ranged 2.58–6.01, 3.24–5.58, 3.44–5.98, 2.85–5.98, 3.32–6.08, 2.04–4.77, 2.72–4.09 and 3.31–5.54 for α-HBCD, β-HBCD, γ-HBCD, ∑ HBCDs, BTBPE, PBT, PBEB, and HBB, respectively. The log BAF values for HBCD isomers, BTBPE, and HBB were greater than 3.7 (corresponding BAF value 5000) in most of the investigated species, demonstrating their highly bioaccumulative properties. α-, β-, and γ-HBCDs, BTBPE, and HBB appeared comparable or had even greater BAFs compared to PBDE congeners with similar K OW, suggesting that these BFRs may have a potentially high environmental risk. The BAFs for the given BFR compound were largely variable between species, due to the species-specific feeding ecology, trophic level, and metabolic capacity for these pollutants. Positive linear relationships between log BAF and log K OW ( r 2 = 0.59, p = 0.04), and molecular weight ( r 2 = 0.54, p = 0.06) of non-PBDE BFRs were observed in the species with low trophic level (Chinese mysterysnail), suggesting that the chemical's physicochemical properties also played key roles in the bioaccumulation processes.

Trophodynamics of Hexabromocyclododecanes and Several Other Non-PBDE Brominated Flame Retardants in a Freshwater Food Web

Several currently used non-polybrominated diphenyl ether (PBDE) brominated flame retardants (BFRs), including hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), pentabromoethylbenzene (PBEB), and pentabromotoluene (PBT), are examined in the components of a freshwater food web from an electronic waste recycling site, South China. All these BFRs are detectable in the food web, with average concentrations of 13.9-868, 1.71-518, < 3.8-338, 197-3099, 3.98-25.6, and 1.20-3.60 ng/g lipid wt for HBCDs, BTBPE, DBDPE, HBB, PBEB, and PBT, respectively. Food web magnification is observed for (+)-alpha-, (-)-alpha-, (+/-)-alpha-, and total HBCDs, and HBB, with trophic magnification factors (TMFs) of 2.22, 2.18, 2.19, 1.82, and 1.46, respectively; whereas there is trophic dilution of BTBPE and PBT through the food web. The TMFs for (+)-alpha-, (-)-alpha-, and (+/-)-alpha-HBCDs are comparable to those of PBDEs detected previously in the same food web. Biota samples show a shift from gamma- toward alpha-HBCD compared with the suspended particles, sediment, and HBCD technical mixtures, with a significant increase of alpha-HBCD on ascending trophic levels. Except for alpha-HBCD in suspended particles and sediment, all the HBCD enantiomers detected are nonracemic in the environmental matrix. In biota, nonracemic residues of alpha-HBCD were observed in mud carp and crucian carp; beta-HBCD in prawn, mud carp, and crucian carp; and gamma-HBCD in water snake, with preferences for (+)-alpha-, (-)-beta-, and (+)-gamma-HBCDs.

Advances in the study of current-use non-PBDE brominated flame retardants and dechlorane plus in the environment and humans

The fate of the high production volume, currently in use, and not regulated non-polybrominated diphenyl ether (PBDE) flame retardants, such as tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD) and dechlorane plus (DP), and the alternative flame retardants of PBDE, such as BTBPE and DBDPE, in the environment has attracted increasing attention and aroused concern due to the increasing regulation and phasing-out of PBDEs. This paper reviews the distribution, bioaccumulation, human exposure and environmental behavior of those non-PBDE flame retardants in various environmental compartments. The data gaps and needs for future research are discussed.

Brominated flame retardants and organochlorine contaminants in winter flounder, harp and hooded seals, and North Atlantic right whales from the Northwest Atlantic Ocean

Various brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs) and current-use, non-PBDE BFRs, as well as organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs), were measured in winter flounder, harp and hooded seals, and North Atlantic right whales from the Eastern United States and Canada. The concentrations of PBDEs in winter flounder and right whales were similar in magnitude to the levels of PCBs, which was unlike the pattern observed in seals. In these marine mammals, the levels of PBDEs were orders of magnitude lower than the levels of OCs and PCBs detected. Evidence existed for the accumulation of methoxylated (MeO)-PBDEs of natural origin in seals and right whales. Current-use, non-PBDE BFRs (including hexabromocyclododecane, pentabromoethylbenzene, hexabromobenzene, and pentabromotoluene) were detected in winter flounder and marine mammals. Future research should focus on monitoring PBDEs, current-use, non-PBDE BFRs, and MeO-BDEs of natural origin in marine organisms from Massachusetts and Cape Cod Bays.