溴系列阻燃剂现状及前景

1 市场需求与二恶英问题 1998年全球阻燃剂需求量为100～110万t/a,总销售额为22亿美元,欧洲占33％,美国30％,日本18％,除日本以外的亚洲地区19％。溴系列阻燃剂约占总需求量的39％。1998年美国、欧洲和日本的溴系列阻燃剂的消耗量分别为7.0万t/a,5.2万t/a和6.2万t/a,在本国阻燃剂消耗总量中的比例分别为16％,16％和37％。到2000年全球溴系列阻燃剂产量已突破30万     

Brominated flame retardants in serum from U.S. blood donors

Serum samples collected in 1988 from U.S. blood donors were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated and polybrominated biphenyls (PCBs and PBBs). The levels of the PBDEs are reported for the first time in serum from the U.S. population. The median concentrations and range of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47); 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153); 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183); and decabromodiphenyl ether (BDE-209) were 1.3 (<0.8-49); 0.54 (0.13-3.1); 0.24 (0.12-1.8); and <1 (<1-35) pmol/g lipid weight (l.w.), respectively. In addition we also measured detectable levels of nine additional PBDE congeners in many of the serum samples. The median concentrations and ranges of 2,2',4,4',5,5'-hexachloro- and hexabromobiphenyl (CB-153 and BB-153) were 190 (21-2600) and 19 (4.2-84) pmol/g l.w. The levels of PBDEs and CB-153 found in the U.S. samples were similar to background levels reported in the serum of Swedish hospital cleaners collected 10 years later, i.e., 1997. The BB-153 congener measured in the U.S. samples was not found in the Swedish samples. The difference in exposure to this congener could not be assessed in this study, although might be related to the 1973 BB-153 (FireMaster BP-6) animal and human contamination incident in the State of Michigan.     

PBCDD and PBCDF from incineration of waste-containing brominated flame retardants

Brominated organic flame retardants comprise a large, heterogeneous group of compounds that are useful but also potentially damaging to the environment. In this investigation, three common brominated flame retardants were co-combusted with an artificial municipal solid waste in a pilot-scale fluidized bed incinerator. Combustion conditions ensured degradation of the flame retardants, but stable brominated organic compounds such as polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans were formed in the cooling flue gases. The incineration of fuels that contain both chlorine and bromine leads to the formation of a complex mixture of polybrominated/chlorinated dibenzo-p-dioxins and dibenzofurans. More bromination than chlorination was observed in these experiments, and the chlorination levels increased when bromine was added to the fuel. The most favored reactions led to the formation of dibromodichlorodibenzo-p-dioxin and dibromodichlorodibenzofuran. Theoretical calculations show that there is more Br2 than Cl2 in the flue gas when the two halogens are present at equimolar levels, because chlorine is mainly found in the form of HCl. This may explain the higher bromination level. BrCl is also present, which drives the chlorination observed when bromine is added.     

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.     

Emerging brominated flame retardants in the sediment of the Great Lakes

The concentrations of 13 currently used brominated flame retardants (BFRs) were analyzed in 16 sediment cores collected from the North American Great Lakes. Among them, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromocyclododecane (HBCD), 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), and hexachlorocyclopentadienyl dibromocyclooctane (HCDBCO) were more frequently detected than others. In general, these emerging BFRs have much lower concentrations than polybromodiphenyl ethers (PBDEs) and dechloranes. Inventories of the five BFRs named above, given on a logarithm basis, were found to decrease linearly with the increasing latitude of the sampling locations, but with weaker statistics than those previously reported for the dechloranes. Logarithm of surface fluxes, on the other hand, was found to be a better parameter in correlating with the longitude. With regard to time trends, the exponential increases in concentrations of these BFRs, particularly DBDPE and BTBPE, in recent years are particularly disturbing. The sediment concentration of DBDPE doubles every 3-5 years in Lake Michigan, and approximately every 7 years in Lake Ontario. The corresponding doubling times for BTBPE are about 5 and 7 years in Lakes Ontario and Michigan, respectively, although declines or leveling off were observed in the top sediment layers in Lake Ontario. In contrast to PCBs, PBDEs, and most dechloranes, the correlations between the surface concentration of emerging BFRs and the latitude or longitude of the sampling sites were not strengthened by normalization of the concentration based on the organic matter content of the sediment.     

Fate of brominated flame retardants and organochlorine pesticides in urban soil: volatility and degradation

As the uses of polybrominated diphenyl ethers (BDEs) are being phased out in many countries, soils could become a secondary emission source to the atmosphere. It is also anticipated that the demand for alternative brominated flame retardants (BFRs) will grow, but little is known about their environmental fate in soils. In this study, the volatility and degradation of BFRs and organochlorine pesticides (OCPs) in soil was investigated. A low organic carbon (5.6%) urban soil was spiked with a suite of BFRs and OCPs, followed by incubation under laboratory condition for 360 days. These included BDE- 17, -28, -47, -99; α- and β-1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), β-1,2,5,6-tetrabromocyclooctane (TBCO), and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), OCPs: α-hexachlorocyclohexane (α-HCH) and (13)C(6)-α-HCH, trans-chlordane (TC), and (13)C(10)-TC. The volatility of spiked chemicals was investigated using a fugacity meter to measure the soil-air partition coefficient (K(SA)). K(SA) of some spiked BFRs and OCPs increased from Day 10 to 60 or 90 and leveled off afterward. This suggests that the volatility of BFRs and OCPs decreases over time as the chemicals become more strongly bound to the soil. Degradation of alternative BFRs (α- and β-TBECH, β-TBCO, DPTE), BDE-17, and α-HCH ((13)C-labeled and nonlabeled) was evident in soils over 360 days, but no degradation was observed for the BDE-28, -47, -99, and TC ((13)C-labeled and nonlabeled). A method to separate the enantiomers of α-TBECH and β-TBCO was developed and their degradation, along with α-HCH ((13)C-labeled and nonlabeled) was enantioselective. This is the first study which reports the enantioselective degradation of chiral BFRs in soils. Discrepancies between the enantiomer fraction (EF) of chemicals extracted from the soil by dichloromethane (DCM) and air were found. It is suggested that DCM removes both the sequestered and loosely bound fractions of chemicals in soil, whereas air accesses only the loosely bound fraction, and these two pools are subject to different degrees of enantioselective degradation. This calls for caution when interpreting EFs obtained from DCM extraction of soil with EFs in ambient air.     

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 assessment of fetus and newborn to brominated flame retardants in France: preliminary data

Brominated flame retardants (BFR) are chemicals extensively used in many manufactured products to reduce the risk of fire, but also environmental pollutants. In order to assess the potential risk linked to these compounds in human, a French monitoring study was initiated to evaluate the exposure of fetus and newborn. A previously described multi-residue analytical method was used, for measuring the main classes of BFR (hexabromocyclododecane, tetrabromobisphenol-A, and tri- to deca-polybromodiphenylethers) in various biological matrices. These analyzed samples (maternal and umbilical serum, adipose tissue and breast milk) were collected on volunteer women during caesarean deliveries. Preliminary results obtained on 26 individuals (mother/newborn pairs) mainly demonstrated the presence of polybromodiphenylethers (PBDE) and tetrabromobisphenol A both in maternal and fetal matrices, and a possible risk of overexposure of newborns through breastfeeding. Contaminations levels were found globally in the ng/g lipid weight range, consistent with other published European data. Exposure results regarding highly brominated PBDE congeners (octa- to deca-BDE) appeared particularly informative and non-commonly reported, these compounds accounting for around 50% of the total PBDE load. Additional data collection and metabolism investigations are now on-going. A more complete statistical analysis related to this BFR exposition study will be provided in a next future.     

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.     

Discontinued and alternative brominated flame retardants in the atmosphere and precipitation from the great lakes basin

Air (vapor and particle) and precipitation samples were collected at five sites (two urban, one rural, and two remote) around the Great Lakes during 2005-2009 as a part of the Integrated Atmospheric Deposition Network (IADN). The concentrations of polybrominated diphenyl ethers (PBDEs), decabromodiphenylethane (DBDPE), hexabromobenzene (HBB), pentabromoethylbenzene (PBEB), and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were measured in these samples. The highest concentrations of these compounds were generally observed at the two urban sites-Chicago and Cleveland-with a few exceptions: The remote site at Eagle Harbor had particularly high levels of PBEB in all three phases, and the rural Sturgeon Point site had the highest HBB concentrations in the vapor phase. The sources of HBB and PBEB to these sites are unknown. A multiple linear regression model was applied to the concentrations of these compounds in the vapor phase, particle phase, precipitation, and the three phases combined. This regression resulted in overall (three phases combined) halving times for total PBDE concentrations of 6.3 ± 1.1 years. The overall halving times for HBB and BTBPE were 9.5 ± 4.6 years and 9.8 ± 2.8 years, respectively. For PBEB and DBDPE, the regression was not statistically significant for the combined phases, indicating that the atmospheric concentrations of these compounds have not changed between 2005 and 2009.     

Temporal trends and spatial distributions of brominated flame retardants in archived fishes from the Great Lakes

To explore the geographical distribution and temporal trends of polybrominated diphenyl ethers (PBDEs) in the Great Lakes, lake trout from Lakes Superior, Michigan, Huron, and Ontario and walleye from Lake Erie, collected during the period of 1980-2000, were analyzed. The concentrations of fifteen PBDE congeners and one polybrominated biphenyl (PBB-153) were determined in each fish sample. Lake trout from Lakes Michigan and Ontario had the highest sigmaPBDE concentrations during the years investigated. The sigmaPBDE concentrations in fishes from the five lakes increased exponentially with time, doubling every 3-4 years. The relative proportion of BDEs-47, -99, and -100 compared to BDEs-153 and -154 increased significantly as a function of time. Over the period 1980-2000, the concentrations of PBB-153, which was a component of a flame retardant banned in the 1970s, generally remained the same in these Great Lakes fishes, except for lake trout from Lake Huron, where the PBB-153 concentrations decreased significantly, but slowly.     

Development of U.S. EPA method 527 for the analysis of selected pesticides and flame retardants in the UCMR survey

Method 527 was developed to address the occurrence monitoring needs of the U.S. Environmental Protection Agency (EPA) under its second unregulated contaminant monitoring rule (UCMR 2). This method includes a wide range of semivolatile organic contaminants, including pesticides that were deferred during the first UCMR, flame retardants, and pyrethroid pesticides. This paper discusses the rationale for selection and inclusion of the various contaminants included in Method 527 and describes the challenges associated with developing analytical methods that will be used for the occurrence monitoring of such a diverse group of organic molecules. Method 527 employs solid-phase extraction with analysis by gas chromatography/ mass spectrometry (GC/MS). The final method preservation scheme requires the storage of samples in amber bottles buffered at pH 3.8 using citric acid to prevent degradation from acid-catalyzed hydrolysis and from UV light. Citric acid is also an effective antimicrobial reagent, preventing this mode of loss during storage. Ethylenediaminetetraacetic acid (EDTA) is added to remove transition metals such as copper, which was determined to degrade target analytes upon storage. Finally, free available chlorine (FAC), which is present in many finished waters and found to degrade a number of the targets, is removed using ascorbic acid. The final method meets all of the EPA UCMR survey requirements for sample storage, precision, accuracy, and sensitivity and will be proposed for use under the UCMR 2.     

Deposition of brominated flame retardants to the Devon Ice Cap, Nunavut, Canada

Brominated flame retardants (BFRs) can be transported to Arctic regions via atmospheric long-range transport, however, relatively little is known about their deposition to terrestrial environments. Snow cores from the Devon Ice Cap in Nunavut, Canada served to determine the recent depositional trends of BFRs. Snow pits were dug in 2005, 2006, and 2008. Dating using annual snow accumulation data, ion chemistry, and density measurements established that the pits covered the period from approximately 1993 to spring 2008. Samples were extracted under clean room conditions, and analyzed using GC-negative ion MS for 26 tri- to decabromodiphenyl ethers (BDEs), as well as other BFRs, nonbrominated flame retardants, and industrial chemicals. Decabromodiphenyl ether (BDE-209) was the major congener present in all samples followed by nona-BDEs (BDE-207, BDE-206, and BDE-208), both accounting for 89% and 7% of total BDE, respectively. BDE-209 concentrations were in most cases significantly correlated (P < 0.05) to tri- to nona-BDE homologues, and the strength of the correlations increased with increasing degree of bromination. Prior to or after deposition BDE-209 may be subject to debromination to lighter congeners. Deposition fluxes of BDE-209 show no clear temporal trend and range between 90 and 2000 pg·cm(-2)·year(-1). Back trajectory origin in densely populated areas of northeastern North America is significantly correlated (P < 0.005) with the BDE-209 deposition flux. Several other high production volume and/or alternative BFRs such as hexabromocyclododecane (HBCD), 1,2-bis(2,4,6-dibromophenoxy)ethane (BTBPE), pentabromo ethyl benzene (PBEBz), and pentabromobenzene (PBBz), as well as the industrial chemical 1,3,5-tribromobenzene (135-TBBz) were found consistently in the snow pits.     

Field evaluation of a flow-through sampler for measuring pesticides and brominated flame retardants in the arctic atmosphere

A flow-through sampler (FTS) was codeployed with a super high volume active sampler (SHV) between October 2007 and November 2008 to evaluate its ability to determine the ambient concentrations of pesticides and brominated flame retardants in the Canadian High Arctic atmosphere. Nine pesticides and eight flame retardants, including three polybrominated diphenyl ether (PBDE) replacement chemicals, were frequently detected. Atmospheric concentrations determined by the two systems showed good agreement when compared on monthly and annually integrated time scales. Pesticide concentrations were normally within a factor of 3 of each other. The FTS tended to generate higher PBDE concentrations than the SHV presumably because of the entrainment of blowing snow/ice crystals or large particles. Taking into account uncertainties in analytical bias, sample volume, and breakthrough estimations, the FTS is shown to be a reliable and cost-effective method, which derives seasonally variable concentrations of semivolatile organic trace compounds at extremely remote locations that are comparable to those obtained by conventional high volume air sampling. Moreover, the large sampling volumes captured by the FTS make it suitable for the screening of new and emerging chemicals in the remote atmosphere where concentrations are usually low.     

Development and validation of a quantitative UHPLC-MS/MS method for selected brominated flame retardants in food

An ultra-high performance liquid chromatography – tandem mass spectrometry (UHPLC-MS/MS) method was developed and validated (in-house) for the quantification of selected brominated flame retardants (BFRs), including tetrabromobisphenol A (TBBPA), hexabromocyclododecanes (HBCDs), tetrabromobisphenol S (TBBPS) and bromophenols (BPs), in various food matrices. The sample preparation consisted of extraction of TBBPS with acidified acetonitrile followed by a fast dispersive solid-phase extraction (dSPE) clean-up and extraction of the other BFRs with a mixture of hexane and dichloromethane (1:1, v/v) with subsequent clean-up using acidified silica (44%, w/w). The limits of quantification of the method varied widely for the types of food matrices and the different classes of BFRs from 4 pg g^?1 wet weight (ww) to 8 ng g^?1 ww. For most of the analytes the apparent recovery was in the range 70–120%, and the method precision (under repeatability conditions) was below 20%. The method was successfully applied in proficiency testing exercises as well as for analysis of various food items. Only 25% of the collected food samples contained BFRs, with 4-bromophenol and α-HBCD as the only detected compounds. The contaminated foodstuffs were fish and eggs with concentrations in the range from 48 to 305 pg g^?1 ww.     

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.     

Distribution and fate of HBCD and TBBPA brominated flame retardants in North Sea estuaries and aquatic food webs

Tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereoisomers (alpha-, beta/-, and gamma-HBCD) were investigated in effluents from sewage treatment works, landfill leachates, sediments, and food web organisms of the North Sea basin. Residues were quantified by liquid chromatography-mass spectrometry. Both flame retardants were enriched in sewage sludges, where a maximum total (sigma) HBCD concentration of 9.1 mg/kg (dry weight; d.w.) was found; TBBPA was at levels of 102 microg/kg. Landfill leachates from The Netherlands showed up to 36 mg (sigmaHBCD)/ kg (d.w.). gamma-HBCD dominated isomeric profiles in sediments, and concentrations were elevated near to a site of HBCD manufacture. alpha-HBCD was the primary congener detected in marine mammals; however, very few samples exhibited TBBPA. sigmaHBCD ranged from 2.1 to 6.8 mg/kg (lipid weight; l.w.) in liver and blubber of harbor porpoises (Phocoena phocoena) and seals (Phoca vitulina). TBBPA levels in cormorant (Phalacrocorax carbo) livers were up to 1 order of magnitude lower compared to sigmaHBCD. HBCD in eels (Anguilla anguilla) from the Scheldt basin (Belgium) reflected the spatial distribution of concentrations in local sediments. This study shows evidence of HBCD bioaccumulation at the trophic level and biomagnification in the ascending aquatic food chain, and these findings justify risk assessment studies at the ecosystem level.