Plant uptake of atmospheric brominated flame retardants at an E-waste site in southern China

Brominated flame retardants (BFRs) were measured in eucalyptus leaves and pine needles as well as the leaf surface particles (LSPs) of the two species at an e-waste site in southern China in 2007-2008. The monthly concentrations of total BFRs in the eucalyptus leaves and pine needles were in range of 30.6-154 and 15.1-236 ng/g dry weight, respectively, and relatively higher concentrations were observed in winter and spring. Correlation analysis of BFR concentrations and comparison of PBDE compositions between the plants and LSPs, air (gaseous and particle-bound phases), and ambient variables were conducted. The results revealed that BFRs in the plants, especially for less brominated BFRs, showed positive relationships with BFRs in the LSPs and negative relationships with the gaseous BFRs and ambient temperature. The PBDE profiles in the plants were similar to the gaseous profile for low brominated BDEs (di- through hexa-BDEs) and to the LSP profiles for highly brominated BDEs (hepta- through deca-BDEs). Applying McLachlan's framework to our data suggests that the uptake of BFRs was controlled primarily by gaseous partitioning equilibrium for compounds with log octanol-air partition coefficients (K(OA)) < 12 and by particle-bound deposition for compounds with log K(OA) > 13. Different relationships between the plant/air partition coefficient (K(PA)) and K(OA), which depend on the uptake mechanisms, were observed for polybrominated diphenyl ethers (PBDEs). This paper adds to the current knowledge of the factors and mechanisms governing plant uptake of semivolatile organic compounds with relatively high K(OA) in the environment.     

Spatial distribution of polybrominated diphenyl ethers and polychlorinated dibenzo-p-dioxins and dibenzofurans in soil and combusted residue at Guiyu, an electronic waste recycling site in southeast China

Surface soils and combusted residue from a village located in southeast China, which has been intensely involved in the dismantling and "recycling" of computer parts (e-waste) for the past decade, were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Total PBDE concentrations were highest in combusted residue of plastic chips and cables collected from a residential area (33,000-97,400 ng/g, dry wt), in soils from an acid leaching site (2720-4250 ng/g, dry wt), and a printer roller dump site (593-2890 ng/g, dry wt). BDE-209 was the most dominant congener (35-82%) among the study sites indicating the prevalence of commercial Deca-BDE, however signature congeners from commercial Penta- and Octa-BDE were also found. PCDD/F concentrations were also highest in soil from the acid leaching site (12,500-89,800 pg/g, 203-1100 pg WHO-TEQ/g, dry wt) and in combusted residue (13,500-25,300 pg/g, 84.3-174 pg WHO-TEQ/g, dry wt) and were comparable to PCDD/F levels of some open dumping sites in Asian developing countries. Of the e-waste activities, acid leaching and open burning emitted the highest concentrations of PBDEs and PCDD/Fs. This study is among the very few studies dealing with the important issue of pollution generated from crude e-waste recycling. Our results showthatthe crude processing of e-waste has become one of the major contributors of PBDEs and PCDD/Fs to the terrestrial environment.     

Polybrominated diphenyl ethers vs alternate brominated flame retardants and Dechloranes from East Asia to the Arctic

Marine boundary layer air and seawater samples taken during a polar expedition cruise from East China Sea to the Arctic were analyzed in order to compare the occurrence, distribution, and fate of the banned polybrominated diphenyl ethers (PBDEs) with their brominated alternatives as well as the chlorinated Dechloranes. The sum of PBDEs (∑(10)PBDEs) in the atmosphere ranged from 0.07 to 8.1 pg m(-3) with BDE-209 being the dominating congener and from not detected (n.d.) to 0.6 pg L(-1) in seawater. Alternate brominated flame retardants (BFRs), especially hexabromobenzene (HBB), (2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), pentabromotoluene (PBT), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EHTBB), bis-(2-ethylhexyl)-tetrabromophthalate (TBPH), were detected in higher concentrations than PBDEs, even in the high Arctic (0.6 to 15.4 pg m(-3) for sum of alternate BFRs), indicating the change of PBDEs toward alternate BFRs in the environmental predominance. In addition, Dechlorane Plus (DP) as well as Dechlorane 602, 603, and 604 were detected both in the atmosphere and in seawater. The highest concentrations as well as the highest compound variability were observed in East Asian samples suggesting the Asian continent as source of these compounds in the marine environment. The air-seawater exchange indicates strong deposition, especially of alternate BFRs, as well as dry particle-bound deposition of BDE-209 into the ocean.     

Atmospheric deposition of halogenated flame retardants at urban, e-waste, and rural locations in southern China

Measurements of atmospheric deposition fluxes and temporal variation of halogenated flame retardants (HFRs) from 2007 to 2008 at urban, electronic waste (e-waste), and rural sites in southern China are presented. The deposition fluxes of total HFRs at the urban (99.3-1327 ng m(-2) day(-1)) and e-waste (79.1-1200 ng m(-2) day(-1)) sites were much higher than at the rural site (9.27-79.5 ng m(-2) day(-1)), demonstrating that e-waste recycling and industrial activities in southern China are two important sources of HFRs in the environment. The urban deposition profile was dominated by current-use HFRs (decabrominated diphenyl ether and decabromodiphenyl ethane), whereas the profile at the e-waste site reflects the past when significant amounts of PBDEs and Dechlorane Plus were used. Source apportionment estimated by principal component analyses with multiple linear regression analysis showed that deposition HFRs at the rural site were primarily contributed by the urban and e-waste sources (45% and 38%, respectively) compared to the contribution from local emission (17%). Our results suggest that the HFRs that are readily present in gas or sorbed onto fine particle phases have enhanced potential for long-range atmospheric transport.     

Brominated flame retardants in seawater and atmosphere of the Atlantic and the Southern Ocean

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

Brominated flame retardants and dechlorane plus in the marine atmosphere from Southeast Asia toward Antarctica

The occurrence, distribution, and temperature dependence in the marine atmosphere of several alternative brominated flame retardants (BFRs), Dechlorane Plus (DP) and polybrominated diphenyl ethers (PBDEs) were investigated during a sampling cruise from the East Indian Archipelago toward the Indian Ocean and further to the Southern Ocean. Elevated concentrations were observed over the East Indian Archipelago, especially of the non-PBDE BFR hexabromobenzene (HBB) with concentrations up to 26 pg m(-3) which were found to be related to continental air masses from the East Indian Archipelago. Other alternative BFRs- pentabromotoulene (PBT), pentabromobenzene (PBBz), and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE)-were elevated, too, with concentrations up to 2.8, 4.3, and 2.3 pg m(-3), respectively. DP was detected from 0.26 to 11 pg m(-3) and bis-(2-ethylhexyl)-tetrabromophthalate (TBPH) ranged from not detected (nd) to 2.8 pg m(-3), respectively. PBDEs ranged from nd to 6.6 pg m(-3) (Σ(10)PBDEs) with the highest individual concentrations for BDE-209. The approach of Clausius-Clapeyron (CC) plots indicates that HBB is dominated by long-range atmospheric transport at lower temperatures over the Indian and Southern Ocean, while volatilization processes and additional atmospheric emissions dominate at higher temperatures. In contrast, BDE-28 and -47 are dominated by long-range transport without fresh emissions over the entire cruise transect and temperature range, indicating limited fresh emissions of the meanwhile classic PBDEs.     

Polybrominated diphenyl ethers and polychlorinated dibenzo-p-dioxins and dibenzofurans in surface dust at an E-waste processing site in Southeast China

Surface dust collected from printed circuit board recycling workshop floors, roads, a schoolyard, and an outdoor food market in Guiyu, China, a village intensely involved in e-waste processing, were investigated for levels of polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). PBDE concentrations in dust from workshop-floors (14,800 ± 5130 ng/g) and on adjacent roads to the workshops (24,900 ± 31,600 ng/g) were highest among the study sites whereas PCDD/F concentrations were highest at the schoolyard (1316 pg/g) and in a workshop (1264 pg/g). Analyses of <2 mm and <53 μm dust particle sizes did not show any significant differences in PBDE concentrations. The cytotoxicity was investigated using two bioassays: 7-ethoxyresorufin O-deethylase (EROD-TEQ) and MTT. EROD-TEQ values ranged from 260 to 432 pg/g, with the highest in dust collected from a street lined with workshops. Using the MTT assay, cytoxicity of dust from the plastic chips drying district in Guiyu was higher than dust from the other sites investigated. This study showed that the primitive recycling of e-waste introduced toxic pollutants into the environment which are potentially harmful to the health of e-waste workers and local residents, especially children, and warrants an urgent investigation into POPs related health impacts.     

Tris(2,3-dibromopropyl) isocyanurate, hexabromocyclododecanes, and polybrominated diphenyl ethers in mollusks from Chinese Bohai Sea

A novel brominated flame retardant (BFR), tris(2,3-dibromopropyl) isocyanurate (TBC), as well as hexabromocyclododecanes (HBCDs) and polybrominated diphenyl ethers (PBDEs), were analyzed in 11 species of mollusks collected from nine coastal cities around the Chinese Bohai Sea in 2009 and 2010. The detection frequencies were 100%, 99%, and 77% for PBDEs, HBCDs, and TBC, respectively. Concentrations of ∑HBCDs ranged from below detection limit (nd) to 28.8 ng g(-1) on a dry weight (dw) basis, followed by ∑(12)PBDE (0.01-20.4 ng g(-1) dw) and TBC (nd-12.1 ng g(-1) dw). Statistically significant linear correlations were found among the three BFRs. Positive correlations were found between BFRs concentrations and lipid content in mollusks. The concentrations tend to decrease with increasing trophic levels of the mollusks, implying trophic dilution rather than biomagnifications of the BFRs in the aquatic food chains of the sampling area. Among the 11 mollusks species, Mytilus edulis showed higher bioaccumulation capability than others and was therefore considered to be an appropriate bioindicator of contamination by the BFRs in the Chinese Bohai Sea, in agreement with its previous selection for the biomonitoring of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). A dramatic decrease in PBDE concentrations in mollusks of the area was found for the time period from 2003 to 2010, with a half-life of only 2.3 ± 1.7 years, reflecting a rapid response of mollusks to the change in pollution of the marine environment.     

Hair as an indicator of endogenous tissue levels of brominated flame retardants in mammals

Few data are available on brominated flame retardants (BFRs) in terrestrial mammalian wildlife. Moreover, the use of hair in nondestructive monitoring of BFRs in mammals or humans has not been investigated. In the present study, concentrations of polybrominated diphenyl ethers (PBDEs) and brominated biphenyl 153 (BB 153) were analyzed in tissues of the European hedgehog Erinaceus europaeus. Road kills and carcasses from wildlife rescue centers were used to investigate relationships between concentrations of BFRs in hair and internal tissues, BFR tissue distribution (hair, liver, kidney, muscle, and adipose tissue), and PBDE congener tissue pattern dissimilarities. Liver concentrations of PBDEs and BB 153 were in the ranges 1-1178 and 0-2.5 ng/g of liver wet weight, respectively. PBDEs were predominant in adipose tissue and liver, while accumulation of BB 153 was tissue independent. The less persistent compound BDE 99 was more dominant in hair than in internal tissues. We observed positive relationships between BFR levels in hair and internal tissues for sum PBDEs and BDE 47 (0.37 < r < 0.78). The present study demonstrated that hair is a suitable indicator of PBDE exposure in terrestrial mammals which can be used in nondestructive monitoring schemes.     

Exposure of electronics dismantling workers to polybrominated diphenyl ethers, polychlorinated biphenyls, and organochlorine pesticides in South China

In P.R. China, electronic waste (e-waste) from across the world is dismantled and discarded. Concentrations of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs) were measured in serum from residents of an e-waste dismantling region (Guiyu, South China), where 80% of families work in e-waste recycling, and compared to a matching cohort from a nearby region where the fishing industry dominates (Haojiang). Serum concentrations of PBDEs and OCPs, but not PCBs, were significantly different in the two regions: the median sigmaPBDE concentration was 3 times higher in Guiyu than Haojiang, whereas the opposite was true for dichloro-diphenyl-trichloroethane (DDT). PBDEs typically accounted for 46% of the total organohalogen chemicals in samples from Guiyu, but 8.7% in Haojiang. The median BDE-209 concentration in Guiyu was 50-200 times higher than previously reported in occupationally exposed populations. The highest BDE-209 concentration was 3100 ng/g lipid, the highest yet reported in humans. Serum PBDE concentrations did not correlate with PCBs or OCPs, whereas PCBs and OCPs showed positive correlations, suggesting that sources of PBDEs to humans are different from PCBs and OCPs. The levels of PBDEs in individuals from Haojiang are possibly related to the recycling activity at Guiyu, through atmospheric transport.     

Dechlorane Plus in human hair from an e-waste recycling area in South China: comparison with dust

Dechlorane Plus (DP) and a dechlorination product, 1,6,7,8,9,14,15,16,17,17,18-octadeca-7,15-diene (anti-Cl(11)-DP), were measured in human hair and indoor dust collected from an e-waste recycling area and two control areas (rural and urban) in South China. DP was detected in hair and dust samples at concentrations ranging from 0.02-58.32 ng/g and 2.78-4197 ng/g, respectively. anti-Cl(11)-DP, mainly detected in human hair and dust samples from the e-waste recycling area, ranged from nd (nondetected) to 0.23 ng/g in hair and from nd to 20.22 ng/g in dust. Average values of anti-DP fractional abundance (f(anti) ratio) in hair of e-waste dismantling workers (0.55 ± 0.11) and dust from e-waste recycling workshops (0.54 ± 0.15) were significantly lower than those in other groups (0.62-0.76 means for hair and 0.66-0.76 means for dust). Significantly positive correlation between DP concentrations in dust and hair and similarity in f(anti) ratios between hair and dust suggest that ingestion of dust comprise one of the major routes for DP exposure. Significantly positive relationships were also observed between anti-Cl(11)-DP and anti-DP for both hair and dust samples with similar regression line slopes. The ratios of anti-Cl(11)-DP to anti-DP between hair and dust show no significant difference. These results suggest that anti-Cl(11)-DP in the human body is likely accumulated from the environmental matrix and not formed from biotransformation of the parent DP.     

Body loadings and health risk assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans at an intensive electronic waste recycling site in China

This study is one of the very few investigating the dioxin body burden of a group of child-bearing-aged women at an electronic waste (e-waste) recycling site (Taizhou, Zhejiang Province) (24 +/- 2.83 years of age, 40% were primiparae) and a reference site (Lin'an city, Zhejiang Province, about 245 km away from Taizhou) (24 +/- 2.35 years of age, 100% were primiparae) in China. Five sets of samples (each set consisted of human milk, placenta, and hair) were collected from each site. Body burdens of people from the e-waste processing site (human milk, 21.02 +/- 13.81 pg WHO-TEQ1998/g fat (World Health Organization toxic equivalency 1998); placenta, 31.15 +/- 15.67 pg WHO-TEQ1998/g fat; hair, 33.82 +/- 17.74 pg WHO-TEQ1998/g dry wt) showed significantly higher levels of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/ Fs) than those from the reference site (human milk, 9.35 +/- 7.39 pg WHO-TEQ1998/g fat; placenta, 11.91 +/- 7.05 pg WHO-TEQ1998/g fat; hair, 5.59 +/- 4.36 pg WHO-TEQ1998/g dry wt) and were comparatively higher than other studies. The difference between the two sites was due to e-waste recycling operations, for example, open burning, which led to high background levels. Moreover, mothers from the e-waste recycling site consumed more foods of animal origin. The estimated daily intake of PCDD/Fs within 6 months by breastfed infants from the e-waste processing site was 2 times higher than that from the reference site. Both values exceeded the WHO tolerable daily intake for adults by at least 25 and 11 times, respectively. Our results implicated that e-waste recycling operations cause prominent PCDD/F levels in the environment and in humans. The elevated body burden may have health implications for the next generation.     

Polybromodiphenyl ethers and decabromodiphenyl ethane in aquatic sediments from southern and eastern arkansas, United States

South-central Arkansas (AR) is home to major manufacturing facilities for brominated flame retardant chemicals (BFRs) in the U.S. Unintended release during production may have caused accumulation of the BFRs in the local environment. In this work, sediment cores were collected from six water bodies in AR, including three located close to the BFR manufacturing facilities in El Dorado and Magnolia, to investigate past and recent deposition histories. A total of 49 polybromodiphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE) were detected, with concentrations as high as 57?000 and 2400 ng/g dry weight for decabromodiphenyl ether (BDE209) and DBDPE, respectively. Log-log regression of BDE209 and DBDPE surface concentrations versus distance to known BFR manufacturing facilities fit the Gaussian Plume Dispersion model, and showed that, if the distance is shortened by half, concentrations of BDE209 and DBDPE would increase by 5-fold. The spatial distribution and temporal trend of the contamination indicate that the manufacturing of PBDEs and DBDPE is the primary source for these compounds in the environment of southern Arkansas. Interestingly, the occurrence of debromination of PBDEs in the sediments of a previously used wastewater sludge retention pond in Magnolia is indicated by the presence of congeners that had not been detected in any commercial PBDE mixtures and by increased fractions of lower brominated congeners relative to higher brominated congeners. Two unknown brominated compounds were detected in the sediments, and identified as nonabromodiphenyl ethanes.     

Riverine inputs of polybrominated diphenyl ethers from the Pearl River Delta (China) to the coastal ocean

Riverine runoff is an important mode to transport anthropogenic pollutants from terrestrial sources to oceans. Polybrominated diphenyl ethers (PBDEs) were measured in riverine runoff samples from the eight major outlets within the Pearl River Delta (PRD), China, an economically fast developing region housing a vast number of electronics manufacturing and assembling plants. The sigma 17PBDEs (sum of 17 BDE congeners, i.e., BDE-28, -47, -66, -85, -99, -100, -138, -153, -154, -183, -196, -197, -203, -206, -207, -208, and -209) concentrations varied from 344 to 68,000 pg/L, with those of BDE-209, BDE-47, and BDE-99 being 335-65200, 3-143, and <1-200 pg/L, respectively. These levels were in the high end of the global PBDEs concentrations in the aquatic environments. The monthly inputs of sigma 17PBDEs ranged from 0.21 to 215 kg at individual outlets, and the annual input of sigma 17PBDEs from all the outlets was estimated at 2140 kg/year. Of the target BDE congeners, BDE-209 was the most predominant component with an annual input of 1960 kg/year, followed by BDE-47 (13.3 kg/year) and BDE-99 (11.7 kg/year). An extrapolation of the past use of PBDEs in the region concluded that 23 metric tons of sigma 17PBDEs have been discharged into the coastal ocean from the PRD in the last 20 years. The amount of PBDEs imported to China in the form of e-waste was estimated at 35000 metric tons/year, higher than the annual domestic production of brominated fire retardants (approximately 10000 metric tons/year) and the annual riverine input of total PBDEs from the PRD, suggesting that the majority of PBDEs inventory has been accumulated from importation of e-wastes. Because of the continuous importation of e-wastes and strong demand for brominated fire retardants, the impact of PBDEs on China's and the world's environments is expected to persist for many years to come.     

Sources, emissions, and fate of polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto, Canada

Indoor air concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) measured in 20 locations in Toronto ranged 0.008-16 ng·m(-3) (median 0.071 ng·m(-3)) and 0.8-130.5 ng·m(-3) (median 8.5 ng·m(-3)), respectively. PBDE and PCB air concentrations in homes tended to be lower than that in offices. Principal component analysis of congener profiles suggested that electrical equipment was the main source of PBDEs in locations with higher concentrations, whereas PUF furniture and carpets were likely sources to locations with lower concentrations. PCB profiles in indoor air were similar to Aroclors 1248, 1232, and 1242 and some exterior building sealant profiles. Individual PBDE and PCB congener concentrations in air were positively correlated with colocated dust concentrations, but total PBDE and total PCB concentrations in these two media were not correlated. Equilibrium partitioning between air and dust was further examined using log-transformed dust/air concentration ratios for which lower brominated PBDEs and all PCBs were correlated with K(OA). This was not the case for higher brominated BDEs for which the measured ratios fell below those based on K(OA) suggesting the air-dust partitioning process could be kinetically limited. Total emissions of PBDEs and PCBs to one intensively studied office were estimated at 87-550 ng·h(-1) and 280-5870 ng·h(-1), respectively, using the Multimedia Indoor Model of Zhang et al. Depending on the air exchange rate, up to 90% of total losses from the office could be to outdoors by means of ventilation. These results support the hypotheses that dominant sources of PBDEs differ according to location and that indoor concentrations and hence emissions contribute to outdoor concentrations due to higher indoor than outdoor concentrations along with estimates of losses via ventilation.     

Brominated flame retardants in waste electrical and electronic equipment: substance flows in a recycling plant

Brominated flame retardants (BFRs) are synthetic additives mainly used in electrical and electronic appliances and in construction materials. The properties of some BFRs are typical for persistent organic pollutants, and certain BFRs, in particular some polybrominated diphenyl ether (PBDE) congeners and hexabromocyclododecane (HBCD), are suspected to cause adverse health effects. Global consumption of the most demanded BFRs, i.e., penta-, octa-, and decaBDE, tetrabromobisphenol A (TBBPA), and HBCD, has doubled in the 1990s. Only limited and rather uncertain data are available regarding the occurrence of BFRs in consumer goods and waste fractions as well as regarding emissions during use and disposal. The knowledge of anthropogenic substance flows and stocks is essential for early recognition of environmental impacts and effective chemicals management. In this paper, actual levels of penta-, octa-, and decaBDE, TBBPA, and HBCD in waste electrical and electronic equipment (WEEE) as a major carrier of BFRs are presented. These BFRs have been determined in products of a modern Swiss recycling plant applying gas chromatography/electron capture detection and gas chromatography/mass spectrometry analysis. A substance flow analysis (SFA) technique has been used to characterize the flows of target substances in the recycling process from the bulk WEEE input into the output products. Average concentrations in small size WEEE, representing the relevant electric and electronic appliances in WEEE, sampled in 2003 amounted to 34 mg/kg for pentaBDE, 530 mg/kg for octaBDE, 510 mg/kg for decaBDE, 1420 mg/kg for TBBPA (as an additive), 17 mg/kg for HBCD, 5500 mg/kg for bromine, and 1700 mg/kg for antimony. In comparison to data that have been calculated by SFA for Switzerland from literature for the 1990s, these measured concentrations in small size WEEE were 7 times higher for pentaBDE, unexpectedly about 50% lower for decaBDE, and agreed fairly well for TBBPA (as an additive) and octaBDE. Roughly 60% of the total bromine input determined by SFA based on X-ray fluorescence analysis of the output materials of the recycling plant cannot be assigned to the selected BFRs. This is an indication for the presence of other brominated substances as substitutes for PBDEs in electrical and electronic equipment. The presence of BFRs, in particular PBDEs in the low grams per kilogram concentration range, in the fine dust fraction recovered in the off-gas purification system of the recycling plant reveals a high potential for BFR emissions from WEEE management and point out the importance for environmentally sound recycling and disposal technologies for BFR-containing residues.     

Determination of brominated flame retardants and brominated dioxins in fish collected from three regions of Japan

The concentrations of brominated dioxins which are polybrominated dibenzo-p-dioxins/polybrominated dibenzofurans (PBDD/DFs) and mono-bromo polychlorinated dibenzo-p-dioxins/dibenzofurans, polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA) were investigated in a total of 45 fish samples collected from three regions in Japan. In the brominated dioxins, 1,2,3,4,6,7,8-heptabromodibenzofuran (HpBDF) was the most abundant congener, and it was found in seven fish samples at 0.10-25.6 pg/g wet weight (ww). The highest concentration of 1,2,3,4,6,7,8-HpBDF was found in the pike eel. Regarding other congeners, 2,3,7,8-tetrabromodibenzo-p-dioxin was detected in the sea bream at 0.02 pg/g ww, and 2,3,7,8-tetrabromodibenzofuran was detected in the conger eel at 0.03 pg/g ww. 3-Bromo-2,7,8-trichlorodibenzofuran was detected in the Sardinella zunasi and the conger eel at 0.01 pg/g ww and 0.02 pg/g ww, respectively. Using toxic equivalency factors of chlorinated dioxins, we calculated the PBDD/DFs concentrations of these fish samples at 0.001-0.256 pg TEQ/g ww. PBDEs were detected in all of the fish samples. The concentrations of total PBDEs were 0.01-2.88 ng/g ww. The seerfish and the yellowtail containd PBDEs in high concentrations. The most dominant congener in most of the fish was 2,2',4,4'-tetrabromo diphenyl ether. TBBPA was detected in 29 fish samples at 0.01-0.11 ng/g ww. The mean level of TBBPA was about one-tenth or less of the total level of PBDEs. A good correlation was obtained between total PBDEs and fat content. On the other hand, no correlation was obtained between TBBPA and fat content. The daily intakes from fish were estimated to be 0.58 ng/kg body weight (bw)/day for total PBDEs, 0.03 ng/kg bw/day for TBBPA, and 0.01 pg TEQ/kg bw/day for brominated dioxins in the case assuming that the average bw of a Japanese adult person is 50 kg and that the average fish consumption is 82 g/day. For PBDEs, the provisionally calculated value was much less than the lowest observed adverse effect level value (1 mg/kg bw/day). For brominated dioxins, the daily intake was at a very low level compared with the Japanese daily intake of polychlorinated dioxins from fish. Even if the value of PBDD/DFs is added to the amount of chlorinated dioxin exposure, it was estimated that it is less than the tolerable daily intake (4 pg TEQ/kg bw/day) in Japan.     

PBDEs in the atmosphere of three locations in western Europe

Atmospheric concentrations of PBDEs (108 samples in total) were measured at 2 rural/semirural sites in England and 1 remote site on the west coast of Ireland in the years 2001 and 2000, respectively. Detailed analysis of the factors affecting concentrations is performed. The United Kingdom (UK) has been a major producer and user of PBDEs. Concentrations of sigmaPBDEs at Mace Head (MH), Ireland ranged between 0.22 and 5.0 pg m(-3) with a mean of 2.6 pg m(-3) and were controlled primarily by advection. sigmaPBDEs concentrations at Hazelrigg (HR), northwest England, ranged between 2.8 and 37 pg m(-3) with a mean of 12 pg m(-3) and at Chilton (CH), southwest England between 3.4 and 33 pg m(-3) with a mean of 11 pg m(-3). The average mixture of PBDEs in air was similar to that of commercial penta-BDE products. Movement of air over local/regional sources influenced concentrations of PBDEs at all sites, particularly at MH. At the two English sites during the summer, concentrations of PBDEs were strongly influenced bytemperature, indicating that air-surface exchange processes play an important role. Advection became more influential during winter, particularly at CH, where a different congener profile was observed in some samples as ambient air temperatures decreased and PBDE concentrations increased. It is hypothesized that this was due to increased emissions from diffuse combustion sources.     

Sediment record and atmospheric deposition of brominated flame retardants and organochlorine compounds in Lake Thun, Switzerland: lessons from the past and evaluation of the present

Chronology of brominated fame retardants (BFRs), a class of currentlywidely used chemicals, was compared to the respective historical profiles of legacy organochlorine compounds in three dated sediment cores from a prealpine lake (Lake Thun, Switzerland). Concentrations of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) started to increase in the 1980s-1990s. In the more recent sediment layers, PBDEs still had steady or increasing concentrations, whereas for HBCDs one sediment core revealed a decreasing trend. In contrast to the contemporary BFRs, concentrations of legacy organochlorines, such as polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and dichlorodiphenyl trichloroethane (DDT), peaked in deeper sediment layers deposited some decades ago. Measurements of atmospheric deposition and evaluation of wastewater discharges pointtoward deposition on the lake surface as a relevant input pathway and wastewater as a minor source of POPs in Lake Thun. The effect of the environmental awareness and the regulations taken in the 1970s to reduce environmental pollution of organochlorines is well reflected in the analyzed sediment cores. The sediment burden closely follows estimated time trends of consumption and emission of PCBs and DDT. The current residues in sediment of BFRs are still lower than the historical peak levels of organochlorines. However, current atmospheric deposition of BFRs is similar to deposition of PCBs. Considering the high amount of BFRs presently stocked in the anthroposphere in flame proofed materials, further measures to reduce emissions during BFRs life cycle are recommended to prevent high environmental pollution as it occurred for the organochlorine compounds.     

Hexabromocyclododecanes in surface soils from E-waste recycling areas and industrial areas in South China: concentrations, diastereoisomer- and enantiomer-specific profiles, and inventory

Hexabromocyclododecanes (HBCDs) are raising concern because of their potential persistence, bioaccumulation, and toxicity. In this study, we investigated the concentrations, diastereoisomer- and enantiomer-specific profiles, and mass inventories of HBCDs in 90 surface soils from two e-waste recycling areas (Qingyuan, Guiyu) and from industrial areas in South China. The mean concentrations of total HBCDs in the surface soils ranged from 0.22 to 0.79 and from 0.31 to 9.99 ng/g dw for two surrounding e-waste recycling sites and industrial areas, respectively. The highest total HBCD concentration (284 ng/g dw) was found at the e-waste recycling site in Qingyuan, while total HBCD levels fell dramatically with increasing distance from the recycling site, suggesting that the e-waste recycling activities were an important source of HBCDs. The diastereoisomer profiles in 75 of the 90 soil samples differed from those of the commercial products. The mean enantiomeric fraction values for α-, β-, and γ-HBCDs in soils ranged from 0.503(0.010) to 0.507(0.003), 0.494(0.003) to 0.506(0.009), and 0.502(0.003) to 0.511(0.006), respectively, suggesting that there was no stereoselective transformation of the three diastereoisomers. The mass inventories of HBCDs gave preliminarily estimates of 3.42 kg and 1.84 tonnes for the e-waste recycling areas and industrial areas, respectively. It is notable that the diasteroisomer and enantiomer profiles of this study failed to distinguish definitely that the isomeric transformation occurred during the product processing or in the environmental matrix. Further laboratory studies on abiotic and biotic transformation are needed to clarify this issue.