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Polybrominated diphenyl ethers (PBDEs) are flame retardants widely used to manufacture several commercial plastic products. The major homologue in commercial PBDE mixtures are listed in the Stockholm Convention on Persistent Organic Pollutants and are scheduled for global elimination. Hence, to understand more about unintentional contamination of plastic recycling stream by restricted PBDEs, we examined 540 small plastic consumer products (1139 components after dismantling), including children's toys, purchased in 18 countries (mainly Japan) between 2015 and 2019. Handheld X-ray fluorescence analysis revealed that 219 plastic components (19% of the total samples) contained bromine at a concentration of >30 mg kg- 1. Chemical analysis of these bromine-positive components revealed that 109 pieces (9.6% of the total), mainly those made of blackcolored plastic, contained PBDEs at concentrations ranging between 35 and 10,000 mg kg- 1, with the maximum contribution from decabromodiphenyl ether (decaBDE). These PBDE concentrations were insufficient to impart flame retardancy, suggesting that the recycled plastic used to manufacture these consumer products probably originated from electronic waste, the manufacture of which was the primary use of commercial decaBDE mixtures. PBDEs were also found in secondary raw plastic materials and their final products obtained in India in 2019, demonstrating that plastics containing decaBDE end up in products where they serve no functional purpose. To contribute to the circular economy, the recycling of plastic waste in end-of-life products should be promoted. However, urgent action is needed to prevent plastic additives of concern, including PBDEs, from entering new products used in daily lives, particularly those used by children.

The concentrations of organic flame retardants (FRs) and dioxin-like activities in dust collected from five countries were investigated. The correlations between the concentrations of the different groups of FRs and dioxin-like activities were examined. Chlorinated paraffins (CPs, C 9 to C 31 ) were found in the highest concentration (median ∑CP 700 μg/g, range 280–4750 μg/g), followed by organophosphate esters (median ∑ 13 OPEs 56 μg/g, range 21–110 μg/g), halogenated flame retardants (median ∑ 17 HFRs 3.3 μg/g, range 0.87–14 μg/g) and polybrominated diphenyl ethers (median ∑ 17 PBDEs 2.8 μg/g, range 0.46–11 μg/g). There were no significant differences in concentrations of the FRs among the countries but differences in PBDE and CP congener profiles were found. BDE209 predominated in dust from Australia, the UK, Sweden and China, ranging from 50 to 70% of total PBDEs. The lowest percentage of BDE209 was found in the dust from Canada, representing only 20% of total PBDEs. For CPs in dust from Sweden, the long-chain CPs (especially C 18 congeners) predominated, while for other countries, medium-chain CPs (especially C 14 congeners) predominated. The dioxin-activities of the dusts ranged from 58 to 590 pg CALUX-TEQ/g, and had a median of 200 pg CALUX-TEQ/g. There were significant positive correlations between concentrations of PBDEs and CPs with dioxin-like activities. The dioxin-like activity may be due to the presence of polychlorinated or polybrominated dioxin/furans (PBDD/DFs) or polychlorinated naphthalenes (PCNs) in the dust. The PBDD/DFs are known impurities and degradation product of the penta-BDE mixture, and PCNs are known impurities of CPs which exhibit dioxin-like activities.

We investigated the concentrations of polybrominated diphenyl ethers (PBDEs) and alternative flame retardants (FRs) in environmental samples collected in January 2012, 2013, and 2014 from an electronic waste-processing area in northern Vietnam. During the study period, PBDE and alternative FR concentrations in soils around the electronic waste-processing workshops ranged from 37 to 9200 ng g −1 dry weight (dw) and from 35 to 24,000 ng g −1 dw; the concentrations in soils around the open-burning sites ranged from 1.6 to 62 ng g −1 dw and from −1 dw; and the concentrations in river sediments around the workshops ranged from 100 to 3800 ng g −1 dw and from 23 to 6800 ng g −1 dw, respectively. Over the course of study period, we observed significant decreases in concentrations of PBDEs and significant increases in concentrations of alternative FRs, particularly Dechlorane Plus isomers and oligomeric organophosphorus FRs ( o -PFRs) in both soils and sediments around the workshops. We also report information on concentrations and environmental emissions of o -PFRs and their low-molecular-weight impurities in the same soils and sediments. The detection of o -PFR impurities around the workshops and the open-burning sites highlights an enhanced breakdown of o -PFRs probably due to weathering during open storage and high temperature attained during the burning of electronic wastes.

A series of laboratory experiments were conducted, whereby two HBCDD treated polyester curtain samples were contacted with deionised Milli-Q water as leaching fluid and HBCDD determined in the resulting leachate. As well as single batch (no replenishment of leaching fluid), serial batch (draining of leachate and replenishment with fresh leaching fluid at various time intervals) experiments were conducted. In single batch experiments at 20 °C, ΣHBCDD concentrations increased only slightly with increasing contact time (6 h, 24 h, and 48 h). This is supported by serial batch tests at 20 °C in which leaching fluid was replaced after 6 h, 24 h, 48 h, 72 h, 96 h, and 168 h. Data from these experiments show that while concentrations of HBCDD in leachate after 24 h cumulative contact time exceed those at 6 h; concentrations in samples collected at subsequent contact times remained steady at ∼50% of those in the 24 h sample. Consistent with this, leaching is shown to be second order, whereby a period of initially intense dissolution of more labile HBCDD is followed by a slower stage corresponding to external diffusion of the soluble residue within the textile. In experiments conducted at 20 °C, α-HBCDD is preferentially leached compared to β- and γ-HBCDD. However, at higher temperatures, the relatively more hydrophobic diastereomers are proportionally more readily leached, i.e. raising the temperature from 20 °C to 80 °C increased concentrations of γ-HBCDD in the leachate by a factor of 28-33 while corresponding α-HBCDD concentrations only increased by a factor of 4.3-4.8.

To assess the exposure of flame retardants (FRs) for school-children, organophosphorus flame retardants and plasticizers (PFRs) and organobromine flame retardants (BFRs) were determined in the indoor dust samples collected from elementary schools and domestic houses in Japan in 2009 and 2010. PFRs were detected in all the dust samples analyzed and the highest concentration of total PFRs was thousand-fold higher than that of BFRs. Among the PFRs, tris(butoxyethyl)phosphate (TBOEP) showed the highest concentration with a median (med.) of 270,000 ng g(-1) dry weight (3700-5,500,000 ng g(-1) dry weight), followed by tris(methylphenyl)phosphate (TMPPs)>triphenyl phosphate (TPHP)=tris(1,3-dichloro-2-propyl)phosphate (TDCIPP)=tris(2-chloroisopropyl)phosphate (TCIPP)=tris(2chloroethyl)phosphate (TCEP)>ethylhexyl diphenyl phosphate (EHDPP). Significantly higher concentrations of TBOEP, tri-n-butyl phosphate (TNBP), TPHP, TMPPs, and total-PFRs were found in dust samples from elementary schools than from domestic houses. It might be due to that higher concentrations of TBOEP (as leveling agent) were detected from the floor polisher/wax products collected in those elementary schools. On the other hand, significantly higher concentrations of TCEP, TCIPPs, and total chloroalkyl-PFRs were found in domestic houses than in elementary schools. Exposure assessments of PFRs via indoor dust from elementary schools and domestic houses were conducted by calculating the hazard quotient (HQ). Among PFRs, HQs for TBOEP exceeded 1 (higher than reference dose: RfD) and its highest value was 1.9. To reduce the intake of TBOEP by school-children, it is recommended that the use of floor polisher/wax containing TBOEP be reduced in schools.

In developing countries, wastes are usually not separated before being disposed of in solid-waste landfills, most of which are open dumps without adequate measures to prevent environmental pollution. To understand the leaching behavior of brominated flame retardants (BFRs) from waste consumer products in landfills, we have been conducting a long-term landfill lysimeter experiment since 2006 under conditions designed to mimic three types of landfill conditions in developing countries: aerobic, semi-aerobic, and anaerobic. Pilot-scale lysimeters (60-cm i.d.) were filled with a 400-cm layer of mixed wastes consisting of 35 wt% food, 20 wt% paper, 20 wt% paper pulp, 13 wt% plastic, 10 wt% wood chips, 1 wt% glass, and 1 wt% metals, proportions that are typical of unsorted municipal solid waste in Asian developing countries. In the present study, we determined the concentrations of polybrominated diphenyl ethers, tetrabromobisphenol A, tribromophenols, and hexabromocyclododecanes in leachate samples collected from the lysimeters during the first 3.5 years of the experiment, to evaluate BFR elution behavior in early-stage landfills. Under all three conditions, BFR elution started at the beginning of the experiment. The BFR concentrations in the leachates from the aerobic lysimeter tended to be lower than those from the anaerobic lysimeter, suggesting that the presence of air inside landfills considerably reduces BFR elution to the surrounding environment. During the 3.5-year experiment, BFR outflow from the lysimeters was only 0.001–0.58% of the total BFRs in the loaded waste; that is, most of the BFRs in the waste remained in the lysimeters.

This study analyzed polyhalogenated compounds (PHCs) such as brominated flame retardants (BFRs) in indoor air and dust samples from two modern homes in Japan. Concentrations of polychlorinated biphenyls (PCBs) and 2,4,6-tribromophenol (2,4,6-TBP) in exhaust and indoor air of two houses were detected at 10(2)-10(3)pgm(-3) order, which were well above those in outdoor air. For dust samples, the detected polybrominated diphenyl ether (PBDE) and polybrominated dibenzo-p-dioxins/furan concentrations resembled values found in our past study. Interestingly, compared to PBDE concentrations, two orders of magnitude higher concentration (13000 ng g(-1)) was observed for hexabromocyclododecanes (HBCDs) in a dust sample from one house. Based on the calculation of air/dust partition ratio values (Kad), low Kad values (log Kad

To establish a concise and rapid procedure to analyze hexabromocyclododecane (HBCD) diastereomers in flame-retarded textiles, three different methods of extraction-Soxhlet, ultrasonic, and soaking extractions with toluene and dichloromethane (DCM)-were compared. During Soxhlet extraction using toluene, the percent contribution of alpha-HBCD to total HBCDs increased slightly and that of gamma-HBCD decreased, indicating that gamma-HBCD was isomerized to some extent at the boiling point of toluene (110.6 degrees C). For ultrasonic extraction, the temperature of the water bath can easily increase over time during the procedure, which might lead to undesirable effects. Therefore, we considered soaking extraction with DCM to be the most facile procedure to analyze HBCD diastereomers in textiles. Using the method established in this study, commercially available textiles in Japan (n=10) were analyzed to understand the actual composition of HBCD contents and its diastereomer profiles. With the exception of one textile sample, HBCDs were detected in all the samples analyzed, with concentrations ranging from 22000 to 43000 mg kg(-1) (i.e. 2.2-4.3%). We found a higher proportion of the alpha-diastereomer in most textile products compared with that of commercial HBCD mixtures, indicating that gamma-HBCD isomerized to alpha-diastereomer by heating processes to incorporate the commercial formulation into treated materials or that the alpha-diastereomer preferentially absorbed onto textile materials during the manufacturing of flame-retarded consumer products.

Hexabromocyclododecanes (HBCDs) have been used for flame retardation mainly in expanded polystyrene (EPS) and extruded polystyrene (XPS) insulation foams. Controlled incineration experiments with solid wastes containing each of EPS and XPS were conducted using a pilot-scale incinerator to investigate the destruction behavior of HBCDs and their influence on the formation of polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/DFs). EPS and XPS materials were respectively blended with refuse derived fuel (RDF) as input wastes for incineration. Concentrations of HBCDs contained in the EPS- and XPS-added RDFs, were 140 and 1100 mg kg(-1), respectively. In which γ-HBCD was dominant (68% of the total HBCD content) in EPS-added RDF and α-HBCD accounted for 73% of the total HBCDs in XPS-added RDF. During the incineration experiments with EPS and XPS, primary and secondary combustion zones were maintained at temperatures of 840 °C and 900 °C. The residence times of waste in the primary combustion zone and flue gas in the secondary combustion zone was 30 min and three seconds, respectively. HBCDs were steadily degraded in the combustion chambers and α-, β-, and γ-HBCD behaved similarly. Concentration levels of the total HBCDs in the bag filter exit gas for the two experiments with EPS and XPS were 0.7 and 0.6ngmN(-3), respectively. HBCDs were also not detected (

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 (48,000 microg/g, 19,000 microg/g and 9600 ng/g as mean values, respectively) were all highest in the rear cabinets. The SigmaPBDD concentrations (460 ng/g as a mean value) detected were highest in the circuit board samples. The respective SigmaPBDE and SigmaPBDF concentrations in the dust samples were 67-500 microg/g (mean 300 microg/g) and 180-650 ng/g (mean 410 ng/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.