An intercalibration study on organobromine compounds: Results on polybrominated diphenylethers and related dioxin-like compounds

An intercalibration study on organobromine compounds has been conducted to evaluate the accuracy and reliability in the analysis of brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and their related compounds like polybrominated and monobromo-polychlorinated dibenzodioxins and -furans (PBDDs/DFs, MoBPCDDs/DFs). This paper reports the results for these compounds in 'Mixed Standard Solutions' and 'Air-Dried Sediment'. The relative standard deviations (RSDs) for PBDEs, PBDDs/DFs and MoBPCDDs/DFs in mixed standard solutions ranged from 9% to 24%, 4% to 20% and 8% to 27%, respectively. The results of this study are better than those reported in earlier international interlaboratory studies due to general improvement in analytical methods and an increasing number of available authentic standards, particularly for PBDEs. In the analysis for higher brominated compounds such as octabromodibenzodioxin, the participants were advised to optimize the calibration curves befitting the range of concentrations found in samples because variation of relative response factors was noted. The results for 'Air-Dried Sediment' were also reasonable with RSDs from 10% to 38% for PBDEs, 8% to 38% for PBDDs/DFs and 17% to 36% for MoBPCDDs/DFs. In the sediment sample, possible errors in the sample pretreatment and/or interference by other compounds/impurities were indicated. The concentrations of pentabromodiphenylether, BDE100, varied more than the other PBDE isomers due to its poor separation in some chromatographic conditions. In addition, interference by PBDEs was observed in the analysis for PBDFs. Potential degradation/secondary formulation of PBDEs and PBDFs during the Soxhlet extraction were suggested when copper powder was added into the sediment samples. Inspite of these observations, the results in this study are better than those reported in other interlaboratory studies due to the advice given to participants for improving the results. Compared with the results for PCDDs/DFs (5-23% RSDs) and Co-PCBs (6-24% RSDs), the RSDs for most of the organobromine compounds were high, indicating an immature QA/QC approach for the analysis of PBDEs and related compounds in comparison to common chlorinated dioxins.     

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

Large-scale fires and time trends of PCDDS/DFs in sediments

Drastic increases in PCDDs/DFs concentrations were identified in the uppermost layers of a sediment core sample taken from the coastal area of Kobe City. As large-scale fires caused by the Great Hanshin-Awaji earthquake were deemed to be a possible cause, we performed additional sampling of sediment cores and surface sediment samples, estimating the total amount of PCDDs/DFs released from fires and presuming the load to sediments by individual transport routes, such as air and water, using an air diffusion model to investigate the influence of fires. The total amount of PCDDs/DFs released from fires was estimated at 2000 g-total PCDDs/DFs, 22 g-TEQ. Increases in PCDDs/DFs generated in fires were principally transported through water rather than air. If 20% of the total PCDDs/DFs formed in fires had entered water, it would correspond to the entire increase of PCDDs/DFs concentration in sediment cores.     

Hazardous substances in indoor dust emitted from waste TV recycling facility

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

Leaching characteristics of PCDDs/DFs and dioxin-like PCBs from landfills containing municipal solid waste and incineration residues

To investigate the leaching characteristic of persistent organic pollutants (POPs), such as non-ortho and mono-ortho substituted chlorobiphebyls (dioxin-like PCBs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), in leachate from municipal solid waste (MSW) landfill sites containing incineration residues, raw leachate samples were collected twice from 12 selected MSW landfill sites. The samples were divided into their liquid and solid phases using GF/B (pore size 1.0 microm), and the concentrations of POPs then determined. The concentrations of PCDDs/DFs ranged from 0.65 to 5.88 pg-TEQ/l (average 2.86 pg-TEQ/l), and those of dioxin-like PCBs from 0.05 to 0.32 pg-TEQ/l (average 0.18 pg-TEQ/l). The major congeners of leached PCDDs/DFs and dioxin-like PCBs in liquid and solid phases were OCDD (about 60%), 2,3',4,4',5-PeCBs (about 30%), and 2,3,4,4',5-PeCBs (about 54%). The relationship between landfill age and the leaching concentration of PCDDs/DFs, and effects of dissolved organic carbon (DOC) on the leaching of PCDDs/DFs are also discussed. Finally, a leaching prediction model of PCDDs/DFs from MSW landfills has been suggested using parameters, such as hydrophobic neutral organic carbons, total dissolved solid, and the ratio of non-biodegradable wastes in landfill sites.     

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.     

Brominated-chlorinated diphenyl ethers formed by thermolysis of polybrominated diphenyl ethers at low temperatures

Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants (BFRs) used mainly as additives in different kinds of plastic material. Various PBDEs are found in all environmental compartments as well as in tissue and blood serum of animals and humans due to their persistence and tendency to bioaccumulate. Emission of PBDEs into the environment can occur during recycling of PBDE-containing plastic material or during their uncontrolled or insufficient combustion as e.g. in accidental fires or landfill fires. Under these circumstances, PBDEs can also function as precursor molecules for the formation of polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). In this study, we qualitatively investigated the reaction of two PBDE congeners, 2,2′,4,4′-tetrabromo diphenyl ether (BDE 47) and 2,2′,4,4′,5,5′-hexabromo diphenyl ether (BDE 153), as well as hexabromobenzene (HBB), a flame retardant used in the past, when exposed to temperatures between 250 °C and 500 °C. The formed reaction products were analysed by high resolution gas chromatography–low resolution mass spectrometry (HRGC-LRMS). Among others brominated–chlorinated diphenyl ethers were formed by chlorodebromination of the PBDEs. In addition, thermolysis of BDE 47 and BDE 153 in the presence of tetrachloromethane as model substance for an organic chlorine source was studied. Thermal treatment of HBB resulted in the formation of brominated–chlorinated benzenes.     

Hydroxylated and methoxylated polybrominated diphenyl ethers and polybrominated dibenzo-p-dioxins in red alga and cyanobacteria living in the Baltic Sea

Hydroxylated polybrominated diphenyl ethers (OH-PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) are present in the ecosystem of the Baltic Sea. OH-PBDEs are known to be both natural products from marine environments and metabolites of the anthropogenic polybrominated diphenyl ethers (PBDEs), whereas, MeO-PBDEs appear to be solely natural in origin. Polybrominated dibenzo-p-dioxins (PBDDs) are by-products formed in connection with the combustion of brominated flame retardants (BFRs), but are also indicated as natural products in a red alga (Ceramium tenuicorne) and blue mussels living in the Baltic Sea. The aims of the present investigation were to quantify the OH-PBDEs and MeO-PBDEs present in C. tenuicorne; to verify the identities of PBDDs detected previously in this species of red alga and to investigate whether cyanobacteria living in this same region of the Baltic Sea contain OH-PBDEs, MeO-PBDEs and/or PBDDs. The red alga was confirmed to contain tribromodibenzo-p-dioxins (triBDDs), by accurate mass determination and additional PBDD congeners were also detected in this sample. This is the first time that PBDDs have been identified in a red alga. The SigmaOH-PBDEs and SigmaMeO-PBDEs concentrations, present in C. tenuicorne were 150 and 4.6 ng g(-1) dry weight, respectively. In the cyanobacteria 6 OH-PBDEs, 6 MeO-PBDEs and 4 PBDDs were detected by mass spectrometry (electron capture negative ionization (ECNI)). The PBDDs and OH-PBDEs and MeO-PBDEs detected in the red alga and cyanobacteria are most likely of natural origin.     

The study on biomass fraction estimate methodology of municipal solid waste incinerator in Korea

In Korea, the amount of greenhouse gases released due to waste materials was 14,800,000 t CO₂eq in 2012, which increased from 5,000,000 t CO₂eq in 2010. This included the amount released due to incineration, which has gradually increased since 2010. Incineration was found to be the biggest contributor to greenhouse gases, with 7,400,000 t CO₂eq released in 2012. Therefore, with regards to the trading of greenhouse gases emissions initiated in 2015 and the writing of the national inventory report, it is important to increase the reliability of the measurements related to the incineration of waste materials.

This research explored methods for estimating the biomass fraction at Korean MSW incinerator facilities and compared the biomass fractions obtained with the different biomass fraction estimation methods. The biomass fraction was estimated by the method using default values of fossil carbon fraction suggested by IPCC, the method using the solid waste composition, and the method using incinerator flue gas.

The highest biomass fractions in Korean municipal solid waste incinerator facilities were estimated by the IPCC Default method, followed by the MSW analysis method and the Flue gas analysis method. Therefore, the difference in the biomass fraction estimate was the greatest between the IPCC Default and the Flue gas analysis methods. The difference between the MSW analysis and the flue gas analysis methods was smaller than the difference with IPCC Default method. This suggested that the use of the IPCC default method cannot reflect the characteristics of Korean waste incinerator facilities and Korean MSW.

Implications: Incineration is one of most effective methods for disposal of municipal solid waste (MSW). This paper investigates the applicability of using biomass content to estimate the amount of CO₂ released, and compares the biomass contents determined by different methods in order to establish a method for estimating biomass in the MSW incinerator facilities of Korea. After analyzing the biomass contents of the collected solid waste samples and the flue gas samples, the results were compared with the Intergovernmental Panel on Climate Change (IPCC) method, and it seems that to calculate the biomass fraction it is better to use the flue gas analysis method than the IPCC method. It is valuable to design and operate a real new incineration power plant, especially for the estimation of greenhouse gas emissions.     

Analysis of flame retarded polymers and recycling materials

Recycling activities on polymeric materials are increasing and becoming more and more important in recent years. For polymers containing no flame retardants, suitable recycling strategies already exist. In order to investigate the recyclability of flame retarded polymers that contain brominated flame retardants, a number of samples were analysed as received from a recycling company. Following the identification and sorting of the samples according to type of polymers and flame retardants, material recycling was tested for the flame retarded polymers identified to occur most frequently. The reactivity of the flame retardants during the recycling procedure was studied by analysing for brominated dioxins and furans. The results demonstrate that flame retarded polymers can be recycled under certain experimental conditions.     

Soil contamination by brominated flame retardants in open waste dumping sites in Asian developing countries

In Asian developing countries, large amounts of municipal wastes are dumped into open dumping sites each day without adequate management. This practice may cause several adverse environmental consequences and increase health risks to local communities. These dumping sites are contaminated with many chemicals including brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs).BFRs may be released into the environment through production processes and through the disposal of plastics and electronic wastes that contain them.The purpose of this study was to elucidate the status of BFR pollution in municipal waste dumping sites in Asian developing countries. Soil samples were collected from six open waste dumping sites and five reference sites in Cambodia, India, Indonesia, Malaysia, and Vietnam from 1999 to 2007. The results suggest that PBDEs are the dominant contaminants in the dumping sites in Asian developing countries, whereas HBCD contamination remains low. Concentrations of PBDEs and HBCDs ranged from ND to 180 μg/kg dry wt and ND to 1.4 μg/kg dry wt, respectively, in the reference sites and from 0.20 to 430 μg/kg dry wt and ND to 2.5 μg/kg dry wt, respectively, in the dumping sites. Contamination levels of PBDEs in Asian municipal dumping sites were comparable with those reported from electronic waste dismantling areas in Pearl River delta, China.     

Behavior of PCNs, PCDDs, PCDFs, and dioxin-like PCBs in the thermal destruction of wastes containing PCNs

In the first known study to characterize the emissions of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (dl-PCBs) from the thermal treatment of wastes containing PCNs, the formation and decomposition behavior of these pollutants was investigated both at laboratory scale and at plant scale. Exhaust gas measurements from laboratory-scale combustion of rubber belts containing PCNs (FB belts) were used as the basis for calculations predicting that the incremental dioxin toxic equivalency (TEQ) emissions from municipal solid waste (MSW) incinerators would be less than 0.1 ng/m3 N. In order to directly examine co-incineration of FB belts with MSW and to address potential differences between the laboratory experiment and full-scale MSW incinerators, experiments were conducted using a larger scale thermal treatment test facility with sampling and analysis at several points in the thermal treatment process. Congener specific analysis of PCNs clearly showed that both destruction and synthesis simultaneously occurred during combustion in the kiln. Most of the PCNs were destroyed by secondary combustion, and almost all PCNs were removed after flue gas treatment. Almost all PCDDs/DFs were synthesized as by-products of kiln combustion, most of them were destroyed by the secondary combustion, and almost all dioxins (PCDDs/DFs and dl-PCBs) were removed after flue gas treatment. The TEQ emission levels were less than 0.1 ng/m3 N for all plant-scale tests, and differences in TEQ emission levels were very small. Adding wastes containing PCNs to MSW will not influence thermal treatment emissions to the environment from modern solid waste incinerators.     

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(10)BDE, BDE-209) was detected in relatively high concentrations compared to other PBDE congeners in most samples. Similar results, in which D(10)BDE 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.     

Levels and distribution of polybrominated diphenyl ethers in humans and environmental compartments: a comprehensive review of the last five years of research

Environmental Science and Pollution Research - Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs), present in the environment, animals, and humans. Their...     

Concentrations and accumulation profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans in aquatic tissues, and ambient air from South Korea

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/DFs), including 2378-substituted isomers were present in samples of shellfish and fish, and ambient air collected from Masan Bay, and Masan City, South Korea. Total concentrations of PCDDs/DFs in mussel and clam were 750 pg g(-1), lipid weight (lw), and 3418 pg g(-1), lw, respectively. Total concentrations of PCDDs/DFs in mullet, gizzard and flounder were 52, 82, and 122 pg g(-1), lw, respectively. Shellfish tissues contained a greater number of PCDD/DF isomers, contributing greater total concentrations of PCDDs/DFs compared to fish collected from the same locations. The predominance of 2378-substituted PCDDs/DFs in fish is represented in greater total concentrations of 2378-TeCDD equivalents (TEQs), whereas there was very limited occurrence of 2378-substituted isomers in shellfish. TEQ concentrations in samples of mussel and clam were 0.97 and 12 pg g(-1), lw, respectively. Total TEQs in mullet, gizzard and flounder were 12, 22 and 18 pg g(-1), lw, respectively. In fish 2378-substituted PCDDs accounted for 100% of the total concentrations of PCDDs, and 2378-substituted PCDFs accounted from 59% to 73% of the total PCDFs. The 2378-substituted isomers accounted for only 3% of the total PCDDs/DFs in shellfish. Ambient air collected from two sites contained a wide range of isomers of tetra- through heptachlorinated PCDDs/DFs. Even though the total concentration of PCDDs/DFs in ambient air (12.8 pgm(-3)) collected from an industrial area was 2-fold greater than that in air samples (6.3 pgm(-3)) collected from an urban/rural area, total TEQs (0.07 and 0.08 pgm(-3)) there was no statistical difference between the two samples.     

Leaching of brominated flame retardants in leachate from landfills in Japan

Leachate samples were taken from seven different landfills and concentrations of brominated flame retardants (BFRs), i.e. polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA), were quantified. Leaching characteristics of BFRs, especially factors affecting leachability, were clarified to obtain basic information regarding the release of BFRs into the environment. The results obtained for observed levels of the sum of PBDE-47, -99 and -100 were n.d.--4000 pg/l for the raw leachate and n.d. for the treated one, respectively, and those of TBBPA were n.d.--620,000 pg/l for the raw leachate and n.d.--11,000 pg/l for the treated one, respectively. Three sites that not only had crushed material from bulk wastes such as waste electric and electronic equipment, but also were under operation or within a year since closure, indicated a higher concentration of BFRs than the other sites. In particular extremely high concentration of PBDEs was observed at a site with a large amount of organics. Considering the leaching characteristics of BFRs, there exists the possibility that leachability of PBDEs is influenced by the presence of dissolved humic matter (DHM) in the leachate. The high removal efficiency for BFRs in the leachate treatment process was also confirmed.     

Atmospheric deposition of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in urban and suburban areas of Korea

Bulk atmospheric samples (wet and dry) were collected monthly throughout a year at urban and suburban areas of Korea to assess the deposition flux and seasonal variations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The PCDDs/DFs deposition fluxes ranged from 1.0 to 3.7 ng TEQ/m²/year in the urban area and from 0.5 to 4.6 ng TEQ/m²/year in the suburban area. The deposition fluxes of PCDDs/DFs in this study were comparable to or lower than those previously reported at different locations. The atmospheric deposition fluxes of particles and PCDDs/DFs in winter tended to be higher than those in summer. However, monthly variations between particle and PCDDs/DFs deposition fluxes were small, and the correlation coefficients between the deposition fluxes of air particles and each homologue group of PCDDs/DFs varied according to the degree of chlorination of the homologue group. The deposition velocity of PCDDs/DFs in the urban area was estimated at 0.04 cm/s, which is a lower value than those found in other studies. The two most likely factors affecting the monthly variation of deposition fluxes are the ambient temperature and the amount of precipitation. In particular, the ambient temperature had an influence on the lower chlorinated homologues of PCDDs/DFs while precipitation had an influence on the higher chlorinated PCDDs/DFs. The PCDDs/DFs profiles in atmospheric deposition bulk samples showed a similar pattern at the urban and suburban sites. The possibility of the loading of PCDDs/DFs by Asian dust events could be partly confirmed by investigation of homologue profiles.     

Levels and sources of brominated flame retardants in human hair from urban, e-waste, and rural areas in South China

Human hair and indoor dust from urban, e-waste, and rural areas in south China were collected and analyzed for brominated flame retardants (BFRs). BFRs concentrations in hair from occupational e-waste recycling workers were higher than those from non-occupational exposed residents in other sampling areas. Polybrominated diphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE) are two major BFRs in hair samples. The PBDE congener profiles in hair from the e-waste area are different from those from urban and rural areas with relatively higher contribution of lower brominated congeners. DBDPE, instead of BDE209, has become the major BFR in non-e-waste recycling areas. Significant correlations were found between hair level and dust level for DBDPE and BTBPE but not for PBDEs. The different PBDE congener profiles between dust and hair may suggest that exogenous exposure to the PBDE adsorbed on dust is not a major source of hair PBDEs.     

Post-combustion syntheses of PCDD/F and PBDD/F from halogen-rich fuel is suppressed by a pebble heater technology

GOAL, SCOPE AND BACKGROUND: Changes in German and European legislation shifted processing of polymer-rich shredding residues (SR) from landfill to thermal treatment. However, when waste of electric and electronic equipment (WEEE) is the source of SR, thermal treatment is complicated by halogens as well as the presence of polybrominated dioxins and furans (PBDD/F) and brominated flame retardants (BFR). Hence, WEEE requires high temperature incineration with sufficient residence times. Post-combustion synthesis of polyhalogenated dioxins and furans (PXDD/F) is dominant in the temperature range between 250-450 degrees C. Thus, a very rapid gas cooling from 450 degrees to 250 degrees C is important for proper raw gas treatment. The pebble heater technology developed by ATZ Entwicklungszentrum (Sulzbach-Rosenberg, Germany) might serve as an alternative to the state-of-the-art quench cooling. It is based on the application of a pebble bed of natural bulk material, which the exhaust gases flows through radially. It provides an excellent heat transfer and a temperature gradient in the range of 1,500-2,000 K/m. The paper presents data of a pilot application of the pebble heater technology for the treatment of raw gas derived from the incineration of polymeric materials from WEEE. METHODS: A liquid fuel was chosen in order to minimise technical modifications of the plant. It was analysed for halogens by x-ray fluorescence, for brominated flame retardants by HPLC-UV/MS and for PXDD/F by GC-HRMS. Combustion gases were rapidly cooled down to temperatures below 200 degrees C and emissions of PBDD/F and PCDD/ F were estimated without further off-gas treatment. PBDD/F emissions were computed as PCDD/F toxicity equivalents applying two different calculation approaches. RESULTS AND DISCUSSION: PCDD/F emissions accounted for 0.04 ng I-TEQ/Nm3 and are in compliance with European emission limits. Calculated PBDD/F toxicity equivalents exceeded the emission limit of 0.1 ng I-TEQ/Nm3 by factors of 75 and 208 depending on the calculation approach. A mass balance of PBDD/F and PCDD/F congeners revealed an efficient elimination of more than 95% in most cases. Lower reduction rates (76% for 2,3,7,8-TeBDF and 82% for 1,2,3,7,8-PeBDF) were attributed to incomplete combustion. An intended recovery of halogens by one-stage scrubbing downstream of the pebble heater was ineffective, recovering 28% of the applied chlorine and 9% of the bromine, only. CONCLUSIONS: Our pilot incineration test indicates that the pebble heater technology can effectively suppress a post-combustion synthesis of PCDD/F and PBDD/F, resulting in low PCDD/F emission levels without further off-gas treatment. The presented data state that WEEE is sensible to incomplete combustion, which will lead to increased PBDD/F emissions without increasing PCDD/F emission limits. This finding is especially relevant for small and low-technical incineration appliances, which have been reported to treat WEEE in developing countries and are considered to serve as a significant source of PXDD/F these days. RECOMMENDATIONS AND PERSPECTIVES: Monitoring of PCDD/F emissions only might considerably underestimate the total emission of dioxins and dioxin-like compounds. It is therefore an ineffective means for assessing resulting health risks, at least for those waste treatment plants which are considered to handle the increasing amounts of PBDD/ F-containing polymers from WEEE in future. Consequently, it is recommended to initiate a screening programme for PXDD/F emissions in large scale incineration facilities which are capable of treating WEEE shredder residues.     

Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants in air and seawater of the European Arctic

The spatial distribution of polybrominated diphenyl ethers (PBDEs) and several alternative non-PBDE, non-regulated brominated flame retardants (BFRs) in air and seawater and the air-seawater exchange was investigated in East Greenland Sea using high-volume air and water samples. Total PBDE concentrations (Ó₁₀PBDEs) ranged from 0.09 to 1.8 pg m⁻³ in the atmosphere and from 0.03 to 0.64 pg L⁻¹ in seawater. Two alternative BFRs, Hexabromobenzene (HBB) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), showed similar concentrations and spatial trends as PBDEs. The air-seawater gas exchange was dominated by deposition with fluxes up to −492 and −1044 pg m⁻² day⁻¹ for BDE-47 and DPTE, respectively. This study shows the first occurrence of HBB, DPTE and other alternative flame retardants (e.g., pentabromotoluene (PBT)) in the Arctic atmosphere and seawater indicating that they have a similar long-range atmospheric transport potential (LRAT) as the banned PBDEs.