Polybrominated Dibenzo-p-dioxins/dibenzofurans Research Articles

Br-to-Cl Transformation Guided the Formation of Polyhalogenated Dibenzo-p-dioxins/Dibenzofurans.

Polyhalogenated dibenzo-p-dioxins/dibenzofurans (PXDD/Fs) are commonly released into the environment as byproducts of combustion processes, accompanied by flue gases. Chlorinated (Cl) and brominated (Br) precursors play crucial roles in forming PXDD/Fs. However, the specific contributions of Cl-precursors and Br-precursors to PXDD/Fs formation have not been fully elucidated. Herein, we demonstrate that the formation of Br-precursors can increase the fraction of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) congeners substituted at specific positions, such as 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF, and 2,3,4,6,7,8-HxCDF. This is attributed to the electrophilic chlorination reaction of the Br-precursors, which includes the Br-to-Cl transformation pathway, following the principle of regioselectivity. The observed formation of polybrominated/chlorinated dibenzo-p-dioxins/benzofurans (PBCDD/Fs) from 1,2-dibromobenzene (1,2-DiBBz) as a Br precursor provides direct evidence supporting the proposed Br-to-Cl transformation. Quantum chemical calculations are employed to discuss the principle of regioselectivity in the Br-to-Cl transformation, clarifying the priority of the position for electrophilic chlorination. Additionally, the concentration of PCDD/Fs formed from 1,2-DiBBz is 1.6 μg/kg, comparable to that of polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) (2.4 μg/kg), highlighting the potential of brominated organic pollutants as precursors for PCDD/Fs formation. This study provides three potential pathways for PCDD/Fs formation from Br-precursors, establishing a theoretical foundation for elucidating the formation mechanism of PXDD/Fs in the coexistence of Cl and Br.

Co-incineration of medical waste in municipal solid waste incineration increased emission of chlorine/brominated organic pollutants

Co-incineration of medical waste (MW) in municipal solid waste incinerators (MSWIs) is a crucial disposal method for emergency disposal of MW and the management of MW in small and medium-sized towns. This study aims to analyze and compare the levels and distribution patterns of chlorine/brominated dioxins and their precursors in fly ash from MSWIs and medical waste incinerators (MWIs) while also focusing on identifying the new pollution concerns that may arise from the co-incineration of municipal solid waste (MSW) mixed with MW (MSW/MW). The concentration of chlorobenzene (CBzs), polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) in fly ash from co-incineration of MSW/MW are 887.4, 134.4 and 27.6 μg/kg, respectively, which are 5.1, 2.0 and 2.9 times higher than that from MSWIs. The levels of polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) are about three orders of magnitude lower than that of PCDD/Fs. For the fly ash from MSWIs, the predominant PCDD/Fs congener is OCDD, which prefers synthesis and adsorption on fine-grained fly ash. For fly ash from MWIs, the major PCDD/Fs congeners are 1, 2, 3, 4, 6,7, 8-HpCDF, and OCDF, which prefer synthesis and adsorption on coarse-grained fly ash. Correlation analysis exhibited that both 1,2,3-TriCBz and 1,2,4-TriCBz in fly ash have a markedly linear correlation with PCDD/Fs and PCBs, but PBDD/Fs shows a poor negative correlation with PCDD/Fs.

Persistent Halogenated Organic Pollutants in Deep-Water-Deposited Particulates from South China Sea.

POP data are limited in the marine environment; thus, this study aimed to investigate background persistent organic pollutant (POP) levels in oceanic deep-water-deposited particulates in the South China Sea (SCS). Six POPs, including polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (DL-PCBs), polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs), polychlorinated diphenyl ethers (PCDEs), and polybrominated biphenyls (PBBs), were investigated in eight pooled samples from the SCS from 20 September 2013 to 23 March 2014 and 15 April 2014 to 24 October 2014 at depths of 2000 m and 3500 m. PBDEs were the most predominant compounds, with the highest mean Σ14PBDE of 125 ± 114 ng/g dry weight (d.w.), followed by Σ17PCDD/F, Σ12PBDD/F, and Σ12DL-PCB (275 ± 1930, 253 ± 216, and 116 ± 166 pg/g d.w., respectively). Most PBDD/F, PBB, and PCDE congeners were below the detection limits. PCDDs had the highest toxic equivalency (TEQ), followed by PBDDs and DL-PCBs. Among the six POPs, PBDEs were the major components of the marine-deposited particles, regarding both concentrations and mass fluxes. Compared to 3500 m, PBDE levels were higher at a depth of 2000 m. PBDE mass fluxes were 20.9 and 14.2 ng/m2/day or 68.2 and 75.9 ng/m2/year at deep-water 2000 and 3500 m, respectively. This study first investigated POP levels in oceanic deep-water-deposited particles from existing global data.

Using In Vitro and Machine Learning Approaches to Determine Species-Specific Dioxin-like Potency and Congener-Specific Relative Sensitivity among Birds for Brominated Dioxin Analogues.

There is a paucity of experimental data regarding dioxin-like toxicity of polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and non-ortho polybrominated biphenyls (PBBs). In this study, avian aryl hydrocarbon receptor 1 (AHR1)-luciferase reporter gene assays were used to determine their species-specific dioxin-like potencies (DLPs) and congener-specific interspecies relative sensitivities in birds. The results suggested that DLPs of the brominated congeners for chicken-like (Ile324_Ser380) species did not always follow World Health Organization toxicity equivalency factors of their chlorinated analogues. For ring-necked pheasant-like (Ile324_Ala380) and Japanese quail-like (Val324_Ala380) species, the difference in DLP for several congeners was 1 or even 2 orders of magnitude. Moreover, molecular docking and molecular dynamics simulation were performed to explore the interactions between the brominated congeners and AHR1-ligand-binding domain (LBD). The molecular mechanics energy (EMM) between each congener and each individual amino acid (AA) residue in AHR1-LBD was calculated. These EMM values could finely characterize the final conformation of species-specific AHR1-LBD for each brominated congener. Based on this, mechanism-driven generalized linear models were successfully built using machine learning algorithms and the spline approximation method, and these models could qualitatively predict the complex relationships between AHR1 conformations and DLPs or avian interspecies relative sensitivity to brominated dioxin-like compounds (DLCs). In addition, several AAs conserved among birds were found to potentially interact with species-specific AAs, thereby inducing species-specific interactions between AHR1 and brominated DLCs. The present study provides a novel strategy to facilitate the development of mechanism-driven computational prediction models for supporting safety assessment of DLCs, as well as a basis for the ecotoxicological risk assessment of brominated congeners in birds.

Concentrations of organic contaminants in industrial and municipal bioresources recycled in agriculture in the UK

Many types of bioresource materials are beneficially recycled in agriculture for soil improvement and as alternative bedding materials for livestock, but they also potentially transfer contaminants into plant and animal foods. Representative types of industrial and municipal bioresources were selected to assess the extent of organic chemical contamination, including: (i) land applied materials: treated sewage sludge (biosolids), meat and bone meal ash (MBMA), poultry litter ash (PLA), paper sludge ash (PSA) and compost-like-output (CLO), and (ii) bedding materials: recycled waste wood (RWW), dried paper sludge (DPS), paper sludge ash (PSA) and shredded cardboard. The materials generally contained lower concentrations of polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (PCBs) relative to earlier reports, indicating the decline in environmental emissions of these established contaminants. However, concentrations of polycyclic aromatic hydrocarbons (PAHs) remain elevated in biosolids samples from urban catchments. Polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) were present in larger amounts in biosolids and CLO compared to their chlorinated counterparts and hence are of potentially greater significance in contemporary materials. The presence of non-ortho-polychlorinated biphenyls (PCBs) in DPS was probably due to non-legacy sources of PCBs in paper production. Flame retardent chemicals were one of the most significant and extensive groups of contaminants found in the bioresource materials. Decabromodiphenylether (deca-BDE) was the most abundant polybrominated diphenyl ether (PBDE) and may explain the formation and high concentrations of PBDD/Fs detected. Emerging flame retardant compounds, including: decabromodiphenylethane (DBDPE) and organophosphate flame retardants (OPFRs), were also detected in several of the materials. The profile of perfluoroalkyl substances (PFAS) depended on the type of waste category; perfluoroundecanoic acid (PFUnDA) was the most significant PFAS for DPS, whereas perfluorooctane sulfonate (PFOS) was dominant in biosolids and CLO. The concentrations of polychlorinated alkanes (PCAs) and di-2-ethylhexyl phthalate (DEHP) were generally much larger than the other contaminants measured, indicating that there are major anthropogenic sources of these potentially hazardous chemicals entering the environment. The study results suggest that continued vigilance is required to control emissions and sources of these contaminants to support the beneficial use of secondary bioresource materials.

Ca2+ mediated mechanism of octa-brominated dioxin/furan formation via BDE-209 thermolysis: Introducing the Mayer bond order difference

Polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) that form during industrial thermal processes, such as the cement kiln co-processing of BDE-209, are highly toxic contaminants. Nevertheless, the formation mechanisms of octa-brominated dioxins/furans (OBDD/Fs), most PBDD/F congeners, and one precursor of the more toxic lower PBDD/Fs from BDE-209 have received little attention. In cement kiln co-processes, the Ca2+-mediated regulation of OBDD/F formation is still debated. In this study, simulation experiments revealed that the average brominating degree of PBDD/Fs was 7.8, indicating that OBDD/Fs are dominant congeners (93.6 % median). Density functional theory (DFT) calculations found a new transition state (TS1) with a lower energy barrier than that found in a previous study. Three major OBDD/F formation reactions suggested that the presence of Ca2+ was thermodynamically beneficial to the formation of OBDD/Fs. This promotion effect can be attributed to the transfer of electron density leading to a change in the Mayer bond order (MBO) among elements when Ca2+ was bound. Intriguingly, in the transition state structures of the Ca2+-bound and Ca2+-free systems, the MBO difference among the old and new bonds can reveal the difficulty of Ca2+-mediated OBDD/F formation reactions from BDE-209.

Occurrence of polybrominated dibenzo-p-dioxins, dibenzofurans (PBDD/Fs) and polybrominated diphenyl ethers (PBDEs) in pilot whales (Globicephala melas) caught around the Faroe Islands

Blubber from Faroese pilot whales (Globicephala melas) was analysed for brominated dioxins PBDD/Fs, with a subset also analysed for chlorinated dioxins, PCDD/Fs. The studied individuals were restricted to juvenile male whales sampled in the Faroe Islands during the period 1997–2013. Among the PBDD/Fs, the furans were predominant, although the relative abundance of various congeners differed between samples. Furans accounted for, on average, 79% of the ∑PBDD/Fs in the samples, with 1,2,3,4,6,7,8-HpBDF the most abundant congener, found in half of the analysed pilot whales. The concentration range for ∑PBDD/Fs among the samples was 0.080–71 pg/g l.w. (lipid weight), and the sum of toxic equivalents ranged from 0.0039 to 4.7 pg TEQ/g l.w. No relationship was found between PBDD/Fs and PCDD/Fs. In addition, 20 pilot whale samples from the period 2010–2013 were analysed for PBDEs. Several PBDE congeners were found in all of the sampled pilot whales, and at noticeably higher levels than PBDD/Fs and PCDD/Fs. The ∑PBDEs ranged from 140 to 1900 ng/g l.w., with BDE #47 the most abundant congener detected in the samples. Results from the present study were then compared with data from previous studies on pilot wales to investigate temporal trends between 1986 and 2013. The comparison indicated that PBDE concentrations in juvenile males have decreased from 1996 to the latest observations in 2013. No relationship between the concentration levels of PBDD/Fs and PBDEs in the sampled pilot whales could be identified, which indicates possible differences in the metabolism of, or exposure to, PBDEs and PBDD/Fs.

Occurrence, composition, source, and regional distribution of halogenated flame retardants and polybrominated dibenzo-p-dioxin/dibenzofuran in the soils of Guiyu, China

Guiyu, China, is well-known for the crude disposal of electronic waste (EW) and severe persistent organic pollutants (POPs). Therefore, in this study, the occurrence, composition, and source of polybrominated diphenyl ethers (PBDEs), 2,2′,4,4′,5,5’-hexabromobiphenyl (BB153), some novel brominated flame retardants (NBFRs), Dechlorane Plus (DP) and polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) in farmland soils covering Guiyu were studied. In EW disposal area soils, PBDEs were the most abundant FRs, with concentrations of 13–1014 ng g−1. The primary PBDE sources were technical Penta- and Deca-BDE mixtures in northern and southern Guiyu, respectively. The levels of BB153 were relatively low, possibly because it has been banned in the 1970s. The concentrations of hexabromobenzene (HBB) were 0.048–3.3 ng g−1, while pentabromoethylbenzene (PBEB) was almost not detected in the soils. Two alternatives to commercial PBDEs, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), were the primary NBFRs, with concentrations of 1.8–153 ng g−1 and 0.43–15 ng g−1, respectively. DP was another primary FR, with concentrations of 0.57–146 ng g−1. Moreover, syn-DP and anti-DP isomers were not stereoselectively decomposed during the EW disposal process and were therefore present in their original fractions in the soils. The levels of PBDD/Fs in EW disposal area soils were 2.5–17 pg TEQ g−1. 1,2,3,4,6,7,8-HpBDF and OBDF were the dominant congeners, mainly derived from processing, pyrolysis and combustion of BFRs. The regional distribution of pollutants was shown to be related to the disposal manner of EW, with their open thermal disposal tending to release more highly brominated compounds such as BDE209, DBDPE, and 1,2,3,4,6,7,8-HpBDF. Additionally, some riverbank sites were heavily polluted because of nearby point sources, downwind Simapu (SMP) town without EW disposal activity was also contaminated by these pollutants.

Unintentional production of persistent chlorinated and brominated organic pollutants during iron ore sintering processes

Iron ore sintering (SNT) processes are major sources of unintentionally produced chlorinated persistent organic pollutants (POPs), including polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs). However, few studies of emissions of brominated POPs, such as polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) and polybrominated diphenyl ethers (PBDEs), during SNT have been performed. Stack gas and fly ash samples from six typical SNT plants in China were collected and analyzed to determine the concentrations and profiles of PCDD/Fs, PCBs, PCNs, PBDD/Fs, and PBDEs, as well as any correlations among these compounds. The PCDD/F, PCB, PCN, PBDD/F, and PBDE emission factors were 2.47, 0.61, 552, 0.32, and 107μgt−1, respectively (109, 4.07, 10.4, 4.41 and 0.02ng toxic equivalents t−1, respectively). PCBs were the most abundant compounds by mass, while PCNs were the next most abundant, contributing 51% and 42% to the total POP concentration, respectively. However, PCDD/Fs were the dominant contributors to the chlorinated and brominated POP toxic equivalent concentrations, contributing 89% to the total toxic equivalent concentration. The PCDD/F and other chlorinated and brominated POP concentrations were positively correlated, indicating that chlorinated and brominated POP emissions could be synergistically decreased using the best available technologies/best environmental practices already developed for PCDD/Fs.

Characterization and inventory of PBDD/F emissions from deca-BDE, polyethylene (PE) and metal blends during the pyrolysis process

The thermal treatment of waste electrical and electronic equipment (WEEE) is regarded as the largest potential contributor to the environmental release of polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs). Herein, the pyrolysis of decabromodiphenyl ether (deca-BDE), polyethylene (PE) and metal blends was conducted to investigate the emission characteristics of PBDD/Fs at different thermal treatment conditions. The total yield of polybrominated dibenzo-p-dioxins (PBDDs) was less than that of polybrominated dibenzofurans (PBDFs) during the pyrolysis of the PE matrix and metal blends. 2,3,7,8-TBDF and 1,2,3,7,8-PBDF were the dominant congeners emitted from the pyrolysis. Temperature, presence of oxygen and type of added metal were the critical influencing factors for the PBDD/F formation rates and speciation in the pyrolysis process.

Simultaneous separation of chlorinated/brominated dioxins, polychlorinated biphenyls, polybrominated diphenyl ethers and their methoxylated derivatives from hydroxylated analogues on molecularly imprinted polymers prior to gas/liquid chromatography and mass spectrometry

Polychlorinated dibenzo-p-dioxins/furans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) are important contaminants in the environment. In recent years also polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs) have been reported as emerging environmental stressors. It has been suggested that hydroxylated polybrominated biphenyl ethers (OH-BDEs) are important – may be even the most important – precursors of brominated dioxins/furans. The aim of this study was to develop a robust, time-saving analytical procedure to collectively separate in animal tissues such compounds prior to determination of individual substances with a gas/liquid chromatograph coupled to an ion trap/time-of-flight mass spectrometer (GC/IT-MS or UPLC/TOF-MS). Two OH-CB/BDE separation methods including alkaline extraction and molecularly imprinted polymers (MIP) were compared. Performance of both methods was validated: absolute recovery values were in the 47–90% range depending on the compound, while recovery relative standard deviation was below 20% in most cases. Levels of the studied compounds have been assessed in some real life samples.

Energy Recovery and Emissions of PBDD/Fs and PBDEs from Co-combustion of Woodchip and Wastewater Sludge in an Industrial Boiler

The emissions of polybrominated dibenzo-pdioxins,dibenzofurans (PBDD/Fs), and polybrominated diphenyl ethers (PBDEs) from trial combustion of 10 wt % dried industrial wastewater-treatment sludge (IWTS) and 90 wt % woodchip in an industrial boiler were investigated and compared to that from woodchip combustion. The PBDD/F toxic equivalent (TEQ) andPBDE emissions increased from 0.121 pg TEQ Nm−3 and 2260 pgNm−3, respectively, of the woodchip combustion to 0.211 pg TEQNm−3 and 4200 pg Nm−3, respectively, of the trial combustion.PBDD/F and PBDE congener profiles of inputs and outputs of the same type of combustion were similar; they also show similarity between woodchip and trial combustions, revealing that the destruction pathway was little affected by the introduction of the IWTS. The fates of PBDD/Fs and PBDEs show that the indigenous pollutants in the feed were effectively depleted (>93.5%). The dominant releasing route of PBDD/F and PBDE shifted from the stack flue gas of woodchip combustion to the ashes of trial combustion. This study demonstrates that co-combustion not only handles the fast growing sludge stream but also yields a saving of 26.3% in the fuel cost and treatment fees of sludge and ashes.

Occurrence of Brominated Persistent Organic Pollutants (PBDD/DFs, PXDD/DFs, and PBDEs) in Baltic Wild Salmon (Salmo salar) and Correlation with PCDD/DFs and PCBs

The contamination profiles of polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), diphenyl ethers (PBDEs), and mixed monobromo/chloro dibenzo-p-dioxins (PXDDs) and dibenzofurans (PXDFs) were determined in the tissue of Baltic wild salmon and compared with those of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs). Out of the analyzed PXDD/DFs, only the 3-B-2,7,8-triCDF was detected (in the concentration range of 0.039-0.075 pg g(-1) fresh weight (f.w.)). The toxic equivalents (TEQs) for analyzed PBDD/DFs (0.074-0.142 pg TEQ g(-1) f.w.) were found to contribute on average 2.1% to the total PCDD/DF-PBDD/DF-TEQ. The total concentrations of 27 PBDE congeners were in the range of 1.3-5.6 ng g(-1) f.w., with an average of 3.3 ng g(-1) f.w. The levels of PCDD/DFs and PCBs were found to be in the range of 4.53-14.6 pg WHO(2005)-PCDD/DF-PCB-TEQ g(-1) f.w., and concentrations of these compounds in most of the analyzed samples were above the maximum levels specified in Commission Regulation (EU) No. 1259/2011. Good correlation was observed between WHO(2005)-PCDD/DF-TEQ and WHO(2005)-PCB-TEQ (r(2) = 0.98), and these parameters were well correlated with the total sum of PBDE concentrations (r(2) = 0.91 and r(2) = 0.94, respectively). The results suggest that the consumption of Baltic wild salmon has no crucial impact on the average POP intake for typical Latvians.

Polybrominated Dibenzo-p-Dioxins, Dibenzofurans, and Biphenyls: Inclusion in the Toxicity Equivalency Factor Concept for Dioxin-Like Compounds

In 2011, a joint World Health Organization (WHO) and United Nations Environment Programme (UNEP) expert consultation took place, during which the possible inclusion of brominated analogues of the dioxin-like compounds in the WHO Toxicity Equivalency Factor (TEF) scheme was evaluated. The expert panel concluded that polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), and some dioxin-like biphenyls (dl-PBBs) may contribute significantly in daily human background exposure to the total dioxin toxic equivalencies (TEQs). These compounds are also commonly found in the aquatic environment. Available data for fish toxicity were evaluated for possible inclusion in the WHO-UNEP TEF scheme (van den Berg et al., 1998). Because of the limited database, it was decided not to derive specific WHO-UNEP TEFs for fish, but for ecotoxicological risk assessment, the use of specific relative effect potencies (REPs) from fish embryo assays is recommended. Based on the limited mammalian REP database for these brominated compounds, it was concluded that sufficient differentiation from the present TEF values of the chlorinated analogues (van den Berg et al., 2006) was not possible. However, the REPs for PBDDs, PBDFs, and non-ortho dl-PBBs in mammals closely follow those of the chlorinated analogues, at least within one order of magnitude. Therefore, the use of similar interim TEF values for brominated and chlorinated congeners for human risk assessment is recommended, pending more detailed information in the future.

Polybrominated, polychlorinated and monobromo-polychlorinated dibenzo- p-dioxins/dibenzofurans and dioxin-like polychlorinated biphenyls in marine surface sediments from Hong Kong and Korea

In this study we investigated occurrences and distribution patterns of dioxin-related compounds (DRCs) such as polybrominated dibenzo- p-dioxins/dibenzofurans (PBDD/Fs), polychlorinated dibenzo- p-dioxins/dibenzofurans (PCDD/Fs), monobromo-polychlorinated dibenzo- p-dioxins/dibenzofurans (MoBPCDD/Fs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in marine surface sediments collected from the coastal waters of Hong Kong and Korea. In most sampling sites, concentrations of PCDDs were the highest, followed by DL-PCBs, PCDFs, PBDFs, PBDDs, MoBPCDDs and MoBPCDFs in this order. Levels of PBDD/Fs were generally 1–2 orders of magnitude lower than chlorinated analogues. Levels of PCDDs are higher than PCDFs in Hong Kong while levels of PBDFs are higher than PBDDs in Korea ( p < 0.05). Report of PBDD/Fs and MoBPCDD/Fs in sediments from East Asian countries is novel and original. Environmental levels of PBDD/Fs are supposed to start increasing in accordance with rising production, use and disposal of brominated flame retardants (BFRs) and recycling processes of e-waste in Asian developing countries.

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

Television (TV) set components are highly flame resistant, with their added brominated compounds such as polybrominated diphenyl ethers (PBDEs). These compounds might be released indoors via dust, which presents a potential exposure pathway for humans in the home environment. In this study, we collected dust from inside TV sets and TV set component samples (parts of housing front cabinets, rear cabinets and circuit boards) of five sets used in Japan. We measured BFRs (i.e., PBDEs, tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs)) and polybrominated dibenzo- p-dioxins/dibenzofurans (PBDD/DFs). Analytical results of the TV components showed that the concentrations of PBDEs, TBBPA and PBDFs (48,000 μg/g, 19,000 μg/g and 9600 ng/g as mean values, respectively) were all highest in the rear cabinets. The ΣPBDD concentrations (460 ng/g as a mean value) detected were highest in the circuit board samples. The respective ΣPBDE and ΣPBDF concentrations in the dust samples were 67–500 μg/g (mean 300 μg/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.

Determination of Polybrominated Diphenyl Ethers and Polybrominated Dibenzo-p-dioxins/Dibenzofurans in Marine Products

Polybrominated diphenyl ethers (PBDEs) have been widely used as flame retardants in plastics and textile coatings, and these compounds have been recognized as ubiquitous environmental contaminants. Furthermore, it is considered a serious problem that polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/DFs), having toxicities similar to those of chlorinated dioxins, are generated by the manufacture of brominated flame retardants (BFRs) such as PBDEs, and formed by the combustion of substances containing BFRs. Several congeners of PBDD/DFs and PBDEs have been detected in the adipose tissue of the Japanese. Although food is suspected as an exposure source, little information is available regarding the levels of these brominated compounds in food, as compared with information regarding dioxin or polychlorinated biphenyls. It is necessary to investigate the levels of these brominated organic compounds in various foods and to estimate their influence in the case of human exposure. We developed an efficient method of analyzing PBDEs and PBDD/DFs contents in food samples using accelerated solvent extraction and determined the concentrations in several marine products such as raw fish, processed foods, and seaweed purchased in Japan. A recovery test (n = 5) using the method and involving dried fish showed acceptable recoveries of 57.7-78.5% (RSD 5.4-15.9%) for PBDEs and 50.0-56.4% (RSD 1.5-7.9%) for PBDD/DFs. In the analysis of marine product samples, several congeners of PBDEs were detected in raw fish, processed fish, and seaweed; the highest concentration of sigmaPBDEs was detected in yellowtail (1161 pg/g whole basis), followed by mackerel (553.5 pg/g whole basis). The most dominant congener present in these marine samples was 2,2',4,4'-tetraBDE (#47).

Polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo- p-dioxins/dibenzofurans (PBDD/Fs) and monobromo-polychlorinated dibenzo- p-dioxins/dibenzofurans (MoBPXDD/Fs) in the atmosphere and bulk deposition in Kyoto, Japan

Polybrominated diphenyl ethers (PBDEs), polybrominated dibenzo- p-dioxins/dibenzofurans (PBDD/Fs) and monobromo-polychlorinated dibenzo- p-dioxins/dibenzofurans (MoBPXDD/Fs) in atmosphere, bulk atmospheric deposition and soil in Kyoto, which is an urban city in Japan, were measured. Decabromodiphenyl ether (D 10BDE, BDE-209) was detected in relatively high concentrations compared to other PBDE congeners in most samples. Similar results, in which D 10BDE was predominantly detected, were reported in other studies in Japan. However, these homologue profiles differ from those of studies conducted in North America. The partitioning of semivolatile organic compounds between atmospheric gas phase and particulate-associated phase is an important factor in their environmental behavior. In this study, atmospheric particulate phase fraction ( f P) of the brominated compounds increased with increasing bromine number, and f P was higher in samples collected in winter than in those collected in summer. Moreover, f P of PBDFs and MoBPXDFs was higher than that of PCDFs with the same halogen number. These results agree well with expectations from the vapor pressure of the brominated compounds and PCDD/Fs. Among the brominated compounds in the atmosphere, the level of MoBPXDD/Fs correlates positively with that of PCDD/Fs. This relationship has been previously observed in waste incineration samples. These results suggest that one of the sources of MoBPXDD/Fs in the atmosphere is incineration byproduct. The level of PBDD/Fs seems to correlate positively with that of PBDEs. This relationship suggest that the PBDD/Fs in the atmosphere relate to PBDEs, which is an impurity of PBDE products, or formed by the manufacture or combustion of plastics containing PBDEs.

Modified clean-up for PBDD, PBDF and PBDE with an active carbon column––its application to sediments

A clean-up method for polybrominated dibenzo- p-dioxins (PBDDs), dibenzofurans (PBDFs) and diphenyl ethers (PBDEs) was modified using combinations of multi-layered silica gel, Florisil and active carbon columns. By using active carbon column chromatography in the final procedure, PBDEs were well separated from PBDD/Fs in an elution test with reference standards. We report the application of this method to sediment samples taken from industrialized areas in Japan. These sediments contained PBDEs ranging in concentration from 13 to 2394 pg/g, dry wt. PBDEs did not interfere with the quantification of PBDD/Fs. In addition, PBDEs found in the PBDD/F fraction did not interfere with the identification of PBDFs using the HRGC/HRMS separation method. Some 2,3,7,8-tetra- to hexabrominated dioxins and furans were also detected in the sediment samples.

Polybrominated dibenzo-p-dioxins, dibenzofurans, and diphenyl ethers in Japanese human adipose tissue.

Human adipose samples collected in Tokyo, Japan in 1970 and 2000 were analyzed for the presence of polybrominated dibenzo-p-dioxins (PBDDs), dibenzofurans (PBDFs), and diphenyl ethers (PBDEs), and the concentrations in the two groups were compared. As far as we know, the concentrations of the PBDD/Fs in adipose tissue from the general Japanese population are reported for the first time. Three PBDD/F congeners were found in the following adipose tissues: 2,3,7,8-TeBDD, 2,3,7,8-TeBDF, and 2,3,4,7,8-PeBDF. The median concentrations (ranges) of three PBDD/Fs in 1970 and 2000 were 5.1 (3.4-8.3) and 3.4 (1.9-5.3) pg/g lipid wt (l.w.), respectively. For PBDEs, seven PBDE congeners were determined in the following samples: 2,4,4'-tribromodiphenyl ether (BDE-28), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), 2,2',4,4',6-pentabromodiphenyl ether (BDE-100), 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153), 2,2',4,4',5',6-hexabromodiphenyl ether (BDE-154), and 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183). Median concentrations (ranges) of PBDEs showed a significant increase from 29.2 (6.8-78.4) pg/g l.w. in 1970 to 1288 (466-2,753) pg/g l.w. in 2000. BDE-47, the major congener of PBDEs, was 56.2% and 35.6% of the total in 1970 and 2000, respectively, whereas the BDE-153 was < 1% and 29.7% of the total in 1970 and 2000, respectively. This may indicate that the source of PBDEs had changed during this period. Further analysis of archived human samples from 1970 to 2000 is needed to describe the details of the contamination trends of PBDD/Fs and PBDEs in the Japanese population. Furthermore, PBDD/F monitoring, particularly 2,3,7,8-TeBDD and 2,3,7,8-TeBDF, may give more toxicological information based on TeCDD toxic equivalents (TEQs).