Homologue Composition of Technical Chlorinated Paraffins Used in Several Countries over the Last 50 Years─SCCPs Are Still Out There.

Chlorinated paraffins (CPs) are widely produced chemicals, with certain CP subgroups facing global restrictions due to their environmental dispersion, persistence, bioaccumulation, and toxicity. To evaluate the effectiveness of these international restrictions, we assessed the homologue group contribution and the mass fraction of short-chain CPs (SCCPs: C10-C13), medium-chain CPs (MCCPs: C14-C17), and long-chain CPs (LCCPs: ≥C18) in 36 technical CP mixtures used worldwide over the last 50 years. Using low-resolution mass spectrometry (LC-ESI-MS/MS), we quantified 74 CP homologue groups (C10Cl4-C20Cl10). Additionally, high-resolution mass spectrometry (LC-ESI-QTOF-MS) screening was employed to identify unresolved CP contents, covering 375 CP homologue groups (C6Cl4-C30Cl30). Overall, 1 sample was mainly composed of

Short- and medium-chain chlorinated paraffins in polyvinyl chloride consumer goods available in the Japanese market.

Chlorinated paraffins (CPs), including short-chain CPs (SCCPs) and medium-chain CPs (MCCPs), are hazardous chemical additives widely applied as plasticizers and flame retardants in polymers, mainly in polyvinyl chloride (PVC). In 2017, SCCPs were listed under the Stockholm Convention on Persistent Organic Pollutants (POPs). MCCPs were proposed for listing as POPs in 2021. SCCPs are also restricted under the Basel Convention, with two tentative low POP content (LPC) limits (100 and 10,000 mg kg-1) for SCCPs in waste. As a signatory Party of both conventions, Japan must ensure their implementation and manage SCCP wastes in environmentally sound ways. Therefore, we aimed to assess the occurrence of SCCPs and MCCPs in PVC consumer goods (n = 87) available in the Japanese market. CPs were detected in 48% of the samples. Regarding positive samples, children's products and toys (1.3-120,000 mg kg-1) were more impacted by SCCPs whereas electrical and electronic cables (1.2-59,000 mg kg-1) and house interior products (3.5-550 mg kg-1) were more impacted by MCCPs. Fourteen and four samples exceeded the LPC limit of 100 and 10,000 mg kg-1 for SCCPs, respectively. Most products were impacted by CP contents (<1 % w/w) considerably below those reported as intentional CP uses in PVC. However, 11 samples with total CP contents ranging from 1.3% to 15 % (w/w) might have been impacted by intentional CP use as secondary plasticizer in PVC. Most of the impacted consumer goods available in the Japanese market were manufactured overseas, highlighting that only restricting POPs nationally is not enough for thorough implementation of the Basel and Stockholm Conventions. Therefore, imported PVC consumer goods, PVC waste and PVC recycling streams need to be monitored as relevant potential sources of SCCPs worldwide, even where the national industry strictly follows the restriction of such chemicals.

Enhancing Scientific Support for the Stockholm Convention's Implementation: An Analysis of Policy Needs for Scientific Evidence.

The Stockholm Convention is key to addressing the global threats of persistent organic pollutants (POPs) to humanity and the environment. It has been successful in identifying new POPs, but its national implementation remains challenging, particularly by low- and middle-income Parties. Concerted action is needed to assist Parties in implementing the Convention's obligations. This analysis aims to identify and recommend research and scientific support needed for timely implementation of the Convention. We aim this analysis at scientists and experts from a variety of natural and social sciences and from all sectors (academia, civil society, industry, and government institutions), as well as research funding agencies. Further, we provide practical guidance to scientists and experts to promote the visibility and accessibility of their work for the Convention's implementation, followed by recommendations for sustaining scientific support to the Convention. This study is the first of a series on analyzing policy needs for scientific evidence under global governance on chemicals and waste.

Inventory approach for short-chain chlorinated paraffins for the Stockholm Convention implementation in Brazil.

Chlorinated paraffins (CPs) are chemicals with multipurpose applications. Their global production has increased despite their adverse impacts on the environment and human health. In 2017, short-chain chlorinated paraffins (SCCPs) were listed as persistent organic pollutants (POPs) in the Stockholm Convention. Yet, specific exemptions were granted for their applications despite the recycling prohibition for products containing SCCPs. Therefore, we aimed to produce the first Brazilian inventory of SCCPs following its respective guidance to evaluate the applicability of the SCCP inventory guidance and to provide technical insights regarding SCCPs in the update of the Brazilian National Implementation Plan (NIP). Moreover, we performed a review of SCCP occurrence in Brazil to fulfil data gaps in the inventory development. We identified and consulted nationwide stakeholders and assessed foreign trade data of CPs and products that might contain CPs in relevant amounts. The Brazilian production of CPs was discontinued in 1994. However, CPs are still imported and used in the country. CPs have been mostly applied as plasticizers, flame retardants and lubricants in Brazil. The import of products containing CPs also pose a significant route of CP entrance into Brazil. Thus, the current end-of-life management of CP-containing products is a bottleneck towards the Convention implementation. The guidance application was feasible and useful despite the low engagement of stakeholders. To assess foreign trade of CPs and CP-containing products, we recommend the use of more specific tracking codes. Besides, the review of SCCP occurrence is not a demanded part for an inventory but was a useful complementation.

Recycling plastics containing decabromodiphenyl ether into new consumer products including children's toys purchased in Japan and seventeen other countries.

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 black-colored 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.

Simultaneous determination of polybrominated diphenyl ethers and hexabromocyclododecane in plastic waste by short-column gas-chromatography-quadrupole mass spectrometry and electron capture detector.

To avoid recycling plastic waste containing polybrominated diphenyl ethers (PBDEs) or hexabromocyclododecane (HBCD), which are listed in the Stockholm Convention on Persistent Organic Pollutants (POPs), a simple method to determine their contents at the time of waste disposal is needed. Herein, we developed a rapid analytical method using a gas chromatograph coupled with quadrupole mass spectrometry or electron capture detection to simultaneously detect PBDEs and HBCD in plastic waste. PBDEs and HBCD were ultrasonically extracted from plastic samples using toluene. The dissolved polymer matrix was then removed using n-hexane and 44% H2SO4-impregnated silica gel before analysis of the extract. A run time of less than 10 min was achieved using a custom, short GC column (5 m). The detection limits of the method were below the upper threshold of the low POP content limits defined by the Basel Convention (<1000 mg kg-1 for both PBDEs and HBCD). The accuracy of the method was confirmed by analyzing seven polymer reference materials. The determined PBDE and HBCD concentrations in most of these reference materials were within 30% of the certified values; the coefficients of variation in triplicate analysis were also within 30%. The concentrations of PBDEs and HBCD in actual plastic waste measured by this method were comparable with those obtained by more sophisticated and expensive methods, such as GC-high-resolution MS for PBDEs and liquid chromatography-tandem mass spectrometry for HBCD. Hence, the method developed herein is a less expensive alternative for identifying PBDE- and HBCD-containing wastes.

Short- and Medium-Chain Chlorinated Paraffins in Polyvinylchloride and Rubber Consumer Products and Toys Purchased on the Belgian Market.

This study investigates the presence of Stockholm Convention listed short-chain chlorinated paraffins (SCCPs) and their replacement medium-chain chlorinated paraffins (MCCPs) counterparts in polyvinyl chloride and rubber consumer products and toys purchased on the Belgian market in 2019. SCCPs were detected in 27/28 samples at concentrations ranging from

Liquid chromatography-electrospray ionization-tandem mass spectrometry for the determination of short-chain chlorinated paraffins in mixed plastic wastes.

Wastes containing short-chain chlorinated paraffins (SCCPs) at concentrations above the Basel Convention low persistent organic pollutant content (LPC) values must be destroyed or irreversibly transformed in an environmentally-sound manner. Here, we developed a novel liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MSMS) method for determining the concentrations of SCCPs in mixed plastic wastes. Major SCCP homologues were identified with good separation and peak width by using a low-hydrophobicity cyano-propyl column and a mobile phase consisting of water and methanol containing ammonium acetate. Precursor ion peaks corresponding to the formation of stable SCCP homologue-adducts were observed, followed by two intense product ion peaks corresponding to separation of the adduct into acetate and the homologue. The formulation of a novel calibration standard with known SCCP homologue percentage composition supported the development of our novel mass spectrometric technique. The results obtained with the LC-ESI-MSMS system were quantitatively and qualitatively comparable with those obtained with a high-resolution mass spectrometry (HRMS) coupled to gas chromatography (GC) system. Homologue concentrations determined by LC-ESI-MSMS were significantly correlated with those determined by GC-HRMS in samples of commercial chlorinated paraffin mixture and mixed plastic waste, respectively. As a complementary technique to the highly accurate, but less versatile GC-HRMS approaches, the SCCP analysis by LC-ESI-MSMS is a practical way to identify mixed plastic wastes containing SCCPs at concentrations higher than the Basel Convention's LPC value.

Validity of using a relative potency factor approach for the risk management of dioxin-like polychlorinated naphthalenes.

Here, we characterized the dioxin-like activities of 42 polychlorinated naphthalenes (PCNs) and 6 technical Halowax formulations by using the DR-CALUX (dioxin-responsive chemically activated luciferase expression) assay with rat hepatoma luciferase-expressing H4IIE cells. Of the 42 PCNs examined, 31 showed dioxin-like activities, for which the mass-based REP-EC5TCDD (potency relative to that of 2,3,7,8-tetrachlorodibenzo-p-dioxin based on the 5% effective concentration determined from the dose-response curve for 2,3,7,8-TCDD) ranged from 0.00000012 to 0.0051, indicating that some of the PCNs (e.g., 1,2,3,6,7,8-HxCN and 1,2,3,4,6,7-HxCN) had dioxin-like activities that were equal to or higher than the WHO-TEFs and the mass-based REP-EC5TCDD reported for dioxins such as octachlorodibenzo-p-dioxin, octachlorodibenzofuran, 3,3',4,4'-tetrachlorobiphenyl (PCB-77), 3,4,4',5-tetrachlorobiphenyl (PCB-81), and 3,3',4,4',5,5'-hexachlorobiphenyl (PCB-169). For PeCNs to OCN with high dioxin-like activities, REPs determined in previous studies were comparable to the REP values obtained in the present study. The TCDD-EQs (2,3,7,8-TCDD equivalents) obtained experimentally for the Halowax formulations decreased in the order HW1051 (37 mg/kg) > HW1014 (30 mg/kg) > HW1013 (5.6 mg/kg) > HW1099 (2.9 mg/kg) > HW1001 (0.60 mg/kg) > HW1031 (<0.10 mg/kg) and were comparable to the theoretical TCDD-EQs calculated by multiplying the concentration and REP of each PCN. In addition, the theoretical TCDD-EQs for PCNs in emission gases produced by thermal processes were below the Japanese emission standard of 0.1-10 ng WHO-toxicity equivalent (TEQ)/m3N, and 3 to 4 orders of magnitude lower than the corresponding WHO-TEQ. Based on a comparison of theoretical and experimental TCDD-EQs, we found that our REP-based approach was suitable for the risk management of industrially produced and unintentionally generated dioxin-like PCNs. This approach will be particularly useful for the risk management of unintentionally generated PCNs in emission gases because the contribution of dioxin-like PCNs to the whole dioxin-like toxicity of emission gases can be elucidated.

Time series of hexabromocyclododecane transfers from flame-retarded curtains to attached dust.

While the production and new use of hexabromocyclododecane (HBCD) mostly ceased after being listed as a persistent organic pollutant under the Stockholm Convention in 2013, its emission from treated products in use to indoor environments still deserves attention. To examine the transfer of HBCD diastereomers to dust on the surface of flame-retarded curtains and to better characterize the potential of treated fabrics to be sources of HBCD in dust, we carried out a series of 196-day experiments using two types of curtains and attached dusts. Concurrently, the physicochemical properties (vapor pressure, water solubility, and octanol-water partition coefficient) of the HBCD diastereomers were measured. HBCD diastereomers migrated from curtains to dust with half-saturation times of about 20-50 days. By day 196, mean HBCD concentrations in dust had reached 13-290 µg/g, depending on the types of curtains and dusts. The composition of HBCD, dominated by γ-HBCD in the curtains, was dominated by α-HBCD in the post-experiment dusts, probably because of the higher vapor pressure of α-HBCD compared to γ-HBCD. The initial HBCD contents of the two curtains were comparable, but the concentrations and profiles of HBCD diastereomers in the post-experiment dusts differed markedly, probably because differences between the texture and/or surface finishing of the treated fabrics affected HBCD transfer to the attached dust.

Destruction behavior of short- and medium-chain chlorinated paraffins in solid waste at a pilot-scale incinerator.

Incineration experiments with solid wastes containing approximately 3% (w/w) short-chain chlorinated paraffins (SCCPs) that have recently been listed as persistent organic pollutants (POPs) and medium-chain chlorinated paraffins (MCCPs) were conducted using a pilot-scale incinerator to investigate the efficiency of their destruction as well as the unintentional formation of POPs and their destruction behaviors during controlled incineration. A series of experiments demonstrated that SCCPs and MCCPs in solid wastes were progressively destroyed and removed during rotary kiln combustion and downstream flue gas treatments. Destruction efficiencies of SCCPs and MCCPs exceeding 99.9999% were confirmed. SCCPs in bottom and fly ash samples were present at levels below their quantification limits (0.021 and 0.31 mg/kg), and MCCPs in the bottom and fly ash samples were likewise present at concentrations below their quantification limits (0.034 and 0.50 mg/kg). Total concentrations of toxicity equivalency quantities (TEQs) for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) in emission gas samples collected at the bag filter exit and final exit were 0.083-0.30 and 8.7 × 10-7 to 1.3 × 10-4 ng-TEQ/m3N, respectively, and those in bottom and fly ash samples were 0.12-0.47 and 9.0 × 10-3 to 0.14 ng-TEQ/g, respectively. The results obtained in this study suggest that controlled incineration of solid wastes under the current regulations for incinerators in Japan and the countries with regulations and monitoring to minimize emissions of PCDDs/DFs and dl-PCBs is one of the best available technologies for the environmentally sound management of wastes containing SCCPs and MCCPs.

Concentrations of POPs based wood preservatives in waste timber from demolished buildings and its recycled products in Japan.

One of the major proportions of recycled persistent organic pollutants (POPs)-containing waste is timber originating from old buildings, utility poles, and cross-arms because POPs-based treatments were once a common means of preserving wood. In 2016 and 2017, we conducted the first survey in Japan on the residue concentrations of chlordanes (CHLs), pentachlorophenol (PCP), pentachloroanisole (PCA), and polychloronaphthalenes (PCNs) in waste timber (n = 55) and its recycled products (woodchip, n = 42; particle board, n = 3). In the recycled products, the highest concentrations detected were 0.86 mg kg-1 CHLs, 3.0 mg kg-1 PCP, 1.1 mg kg-1 PCA, and 2.6 mg kg-1 PCNs, which were one to two orders lower than the low POP content (LPC) limits for the environmentally sound management of wastes defined under the Basel Convention (50, 100, and 10 mg kg-1, respectively). In the waste timber, which included bearers and columns from demolished buildings, the highest concentrations were 15 mg kg-1 CHLs, 0.20 mg kg-1 PCP, and 0.036 mg kg-1 PCNs, no higher than about 30% of the LPC limit. The concentration of CHLs in timber bearer was significantly higher than those in timber column (p < 0.05). Although none of the waste timber or recycled products had concentrations exceeding the LPC limits, one means of ensuring low POP concentrations in recycled products is separating timber bearer from timber column when demolishing wooden buildings, according to the results in Japan. The timber column can be used to produce recycled products and the remaining timber can be used for heat utilization and power generation.

Direct contact between dust and HBCD-treated fabrics is an important pathway of source-to-dust transfer.

Hexabromocyclododecanes (HBCDs) are a class of brominated flame retardant that have found extensive application in consumer products used widely in indoor environments. Although uncertainty remains about the human health impacts of HBCDs, ingestion of HBCD-contaminated indoor dust has been shown to be a particularly significant exposure pathway for young children. Despite this, understanding of the mechanisms via which HBCD transfer from products to indoor dust remains incomplete. In this study, an in-house test chamber was used to investigate transfer of HBCDs from a treated textile sample to indoor dust via direct textile:dust contact. Results were compared with previous data using the same test chamber to examine other pathways via which HBCDs transfer from products to dust, and highlighted HBCD transfer via direct source:dust contact as being particularly important. This novel finding was corroborated by complementary experiments that examined HBCD transfer via direct contact, from other treated textiles to three major components of indoor dust: artificial indoor dust, soil particles, and cotton linters.

Leaching behaviour of hexabromocyclododecane from treated curtains.

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 ß- 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.

Comprehensive characterisation of flame retardants in textile furnishings by ambient high resolution mass spectrometry, gas chromatography-mass spectrometry and environmental forensic microscopy.

The presence and levels of flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs) and organophosphate flame retardants (PFRs), was determined in textile home furnishings, such as carpets and curtains from stores in Belgium. A comprehensive characterisation of FRs in textile was done by ambient high resolution mass spectrometry (qualitative screening), gas chromatography-mass spectrometry (GC-MS) (quantitation), and environmental forensic microscopy (surface distribution). Ambient ionisation coupled to a time-of-flight (TOF) high resolution mass spectrometer (direct probe-TOF-MS) was investigated for the rapid screening of FRs. Direct probe-TOF-MS proved to be useful for a first screening step of textiles to detect FRs below the levels required to impart flame retardancy and to reduce, in this way, the number of samples for further quantitative analysis. Samples were analysed by GC-MS to confirm the results obtained by ambient mass spectrometry and to obtain quantitative information. The levels of PBDEs and PFRs were typically too low to impart flame retardancy. Only high levels of BDE-209 (11-18% by weight) were discovered and investigated in localised hotspots by employing forensic microscopy techniques. Most of the samples were made of polymeric materials known to be inherently flame retarded to some extent, so it is likely that other alternative and halogen-free FR treatments/solutions are preferred for the textiles on the Belgian market.

Exposure assessment of organophosphorus and organobromine flame retardants via indoor dust from elementary schools and domestic houses.

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.

Destruction behavior of hexabromocyclododecanes during incineration of solid waste containing expanded and extruded polystyrene insulation foams.

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-, ß-, 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 (<0.2 ng g(-1)) in the bottom and fly ash samples. From the obtained results, it was calculated that HBCDs were sufficiently destroyed in the whole incineration process with destruction efficiencies of more than 99.9999 for both of EPS and XPS cases. For PBDD/DFs, the levels detected in the bottom and fly ash samples were very low (0.028 ng g(-1) at maximum). In the case of XPS-added experiment, 2,3,7,8-TeBDD and 2,3,7,8-TeBDF were determined in the flue gas at levels (0.05-0.07 ng mN(-3)) slightly over the detection limits in the environmental emission gas samples, suggesting HBCDs in XPS are possibly a precursor of detected PBDD/DFs. Operational care should be taken when the ratio of HBCD-containing polystyrene is increased in the input wastes just to make sure of formation prevention and emission control of PBDD/DFs. The concentrations and congener patterns of PCDD/DFs and dl-PCBs in the samples during the three experiments were not affected by an addition of HBCDs.

Leaching of brominated flame retardants from mixed wastes in lysimeters under conditions simulating landfills in developing countries.

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.

Emission behavior of hexabromocyclododecanes and polybrominated diphenyl ethers from flame-retardant-treated textiles.

To evaluate the emission behavior of hexabromocyclododecanes (HBCDs) and polybrominated diphenyl ethers (PBDEs) added to textile products as flame retardants, we used a small stainless steel container (7 cm i.d. × 5.5 cm height, ca. 210 cm(3)) to conduct emission tests on three upholstery textile samples at temperatures of 20, 40, 60, and 80 °C. The textile samples, which were intended for use in curtain manufacture and had been treated with either technical HBCD or technical DecaBDE, emitted HBCDs and PBDEs, including BDE 209, even at room temperature (20 °C), and the emission rates increased with increasing test temperature. These results indicate that flame-retardant-treated upholstery textiles have the potential to be major sources of brominated flame retardant contamination in indoor air and dust. The HBCD diastereomer emission profiles at the test temperatures of 20 and 40 °C were similar to the profiles of the original textile samples; in contrast, at the higher test temperatures, the proportion of α-HBCD was larger (up to 70% of the total HBCD emission) than in the original samples. At the higher test temperatures, the proportions of di- to hexa-BDEs in the emissions were clearly larger than in the original sample, suggesting that the textile products treated with technical DecaBDE could be a source of environmentally relevant PBDE congeners such as BDE 47, 99, and 100. The emission rates of HBCDs from the textiles were two orders of magnitude higher than those of PBDEs, suggesting that HBCDs volatilize more easily from textile products to the indoor environment than PBDEs.

Photolysis of brominated flame retardants in textiles exposed to natural sunlight.

Photolytic transformation profiles of technical hexabromocyclododecane (HBCD) and technical decabromodiphenyl ether (DecaBDE) in flame-retarded textiles exposed to natural sunlight were compared. Textiles that contained approximately 4% HBCDs by weight showed no substantial loss of any of the HBCD diastereomers during the entire exposure period (371 days), indicating that they were resistant to sunlight, that is, that debromination and isomerization of HBCD diastereomers did not occur under the experimental conditions. Exposure of a textile treated with technical DecaBDE resulted in the formation of polybrominated dibenzofurans (PBDFs) as products of photodecomposition of polybrominated diphenyl ethers present in the technical DecaBDE. After 329 days of exposure, the total PBDF concentration reached a maximum of 27 000 ng g(-1), which was approximately 10 times the initial concentration. During the experiment, di- to hexa-BDF congener concentrations increased continuously. Although the concentrations of PBDFs in the textiles were 4­5 orders of magnitude lower than the concentrations of polybrominated diphenyl ethers, it is important to note that PBDFs were formed as a result of sunlight exposure during normal use of products treated with technical DecaBDE.