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     

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.     

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.     

Field testing a flow-through sampler for semivolatile organic compounds in air

Even without access to the electrical grid, a flow-through sampler (FTS) can collect gaseous and particle-bound semivolatile organic compounds (SOCs) from large volumes of air by turning into the wind and having the wind blow through a porous sampling medium. To test its performance under field conditions, a FTS and a traditional pumped high volume air sampler, both using polyurethane foam (PUF) as sampling medium, were codeployed at the campus of the University of Toronto Scarborough from August 2006 to June 2007. Quantitative relationships between the wind speed outside the sampler and after passage through the PUF were established and allow the accurate estimation of sampling volumes under conditions of low and high wind speed. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were quantified in the samples taken by both air samplers. Separate analysis of seven PUF disks arranged sequentially within the FTS, confirm that even relatively volatile SOCs do not experience serious break-through. Theoretical plate number analysis of the break-through curves yields an understanding of the effect of temperature and wind speed on FTS sampling efficiency, and reveals different behavior of gaseous and particle-bound-compounds on the PUF. Air concentrations of PCBs and PAHs obtained with the FTS compare favorably with those obtained by averaging the concentrations of several 24 h active high volume samples taken during the same time period.     

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.     

Bromobenzene flame retardants in the great lakes atmosphere

Seven bromobenzene flame retardants were measured in vapor-phase samples collected at five sites, all near the shores of the North American Great Lakes during 2008-2009, inclusive. The target compounds were hexabromobenzene (HBB), pentabromobenzene (PBBz), pentabromotoluene (PBT), pentabromobenzylacrylate (PBBA), pentabromobenzyl bromide (PBBB), tetrabromo-p-xylene (pTBX), and pentabromoethyl benzene (PBEB). Detection frequencies were, on average, higher than 50% for all of the compounds, with the exception of PBBA, which was detected only in 22% of all the samples. Considering all the sampling sites together, HBB showed the highest average concentration (4.6 ± 1.0 pg/m(3)), followed by PBBB (3.3 ± 0.5 pg/m(3)) and PBEB (1.0 ± 0.1 pg/m(3)). The concentrations of these compounds were generally significantly correlated with one another, with the exception of PBBA, which was correlated only to PBBB. The atmospheric concentrations of PBT, pTBX, PBBB, and PBBA tracked local human population density, suggesting that these compounds are or were used in a variety of commercial products. Unexpectedly, the concentration of PBEB was highest at the remote site of Eagle Harbor in northern Michigan, whereas that of HBB was highest at Sturgeon Point, ～25 km southwest of Buffalo, New York. The lack of dependence of these two compounds' concentrations on human population suggests local point sources.     

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.     

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.     

Brominated flame retardants in the atmosphere of the East-Central United States

Air samples were collected at five sites (urban, semiurban, agricultural, and remote) from Lake Michigan through the U. S. Midwest to the Gulf of Mexico every 12 days during 2002-2003 using high-volume samplers so that we could study the spatial trends of brominated flame retardants (polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), and 1,2-bis(2,4,6-tribromophenoxy)-ethane (TBE)). The mean sigmaPBDE atmospheric concentration was 100 +/- 35 pg/m3 at the Chicago site, which was 3-6 times higher than that at the other sites. The sigmaPBDE atmospheric concentrations at the Chicago site were significantly higher than previous measurements made in 1997-1999. Unlike these former measurements, BDE-209 is now relatively abundant. Lower BDEs (tri- through hex-BDEs) were detected in both the particle and the gas phases, and the partitioning of these compounds between phases was highly dependent on atmospheric temperature. Higher BDEs (hepta- through deca-BDEs) were mostly detected in the particle phase. On the basis of the congener distributions in the samples, the concentrations were divided into three groups: penta-BDEs, octa-BDEs, and deca-BDEs. Penta-BDEs were the most concentrated at the Chicago site and the least concentrated at the Louisiana site; octa-BDE concentrations were low at all of the sites; deca-BDEs were the most concentrated at the Chicago site and notably high atthe Arkansas site. High concentrations of deca-BDEs, HBCDs, and TBE at the Arkansas site suggest that manufacturing areas in southern Arkansas could be the source regions. Backward trajectories for air masses with high concentrations of deca-BDEs coming to the Arkansas site suggestthat deca-BDEs bound to particles can move long distances from source regions to nonsource regions.     

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.     

Alternate and new brominated flame retardants detected in U.S. house dust

Due to the voluntary withdrawals and/or bans on the use of two polybrominated diphenyl ether (PBDE) commercial mixtures, an increasing number of alternate flame retardant chemicals are being introduced in commercial applications. To determine if these alternate BFRs are present in indoor environments, we analyzed dust samples collected from 19 homes in the greater Boston, MA area during 2006. Using pure and commercial standards we quantified the following brominated flame retardant chemicals using GC/ECNI-MS methods: hexabromocyclododecane (sigma HBCD), bis(2,4,6,-tribromphenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), and the brominated components found in Firemaster 550 (FM 550): 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB) and (2-ethylhexyl)tetrabromophthalate (TBPH), the latter compound being a brominated analogue of di(2-ethylhexyl)phthalate (DEHP). The concentrations of all compounds were log-normally distributed and the largest range in concentrations was observed for HBCD (sum of all isomers), with concentrations ranging from <4.5 ng/g to a maximum of 130,200 ng/g with a median value of 230 ng/g. BTBPE ranged from 1.6 to 789 ng/g with a median value of 30 ng/g and DBDPE ranged from <10.0 to 11,070 ng/g with a median value of 201 ng/g. Of the FM 550 components, TBB ranged from <6.6 to 15,030 ng/g with a median value of 133 ng/g; whereas TBPH ranged from 1.5 to 10,630 ng/g with a median value of 142 ng/g. Furthermore, the ratio of TBB/TBPH present in the dust samples ranged from 0.05 to 50 (average 4.4), varying considerably from the ratio observed in the FM 550 commercial mixture (4:1 by mass), suggesting different sources with different chemical compositions, and/or differential fate and transport within the home. Analysis of paired dust samples collected from different rooms in the same home suggests HBCD, TBB, and TBPH are higher in dust from the main living area compared to dust collected in bedrooms; however, BTBPE and DBDPE levels were comparable between rooms. This study highlights the fact that numerous types of brominated flame retardants are present in indoor environments, raising questions about exposure to mixtures of these contaminants.     

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.     

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.     

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.     

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.     

Accumulation of organochlorines and brominated flame retardants in the eggs and nestlings of great tits, Parus major

Insectivorous birds may be very useful sentinels for local point-source contamination with persistent pollutants, such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and organochlorine pesticides (OCPs). Eggs have been used extensively to monitor lipophilic contaminants, as females can pass contaminants stored in their body tissues into their eggs. Concentrations and profiles in eggs therefore relate to contamination in the female. Because nestlings are raised on food items collected locally, it is expected that the body burden in nestlings would reflect their diet and local pollution levels better than eggs. In this study we compared the accumulation and the profile of PCBs, PBDEs, and OCPs in great tit (Parus major) eggs, nestlings (5-, 10-, and 15-days old), and their food in two study sites. Our results showed that concentrations in great tit eggs were 4 to 6 times higher than those in nestlings. Concentrations in nestling great tits corresponded with concentrations predicted by a bioenergetics-based model. Most of the persistent organic pollutants in 15-day old nestlings were still from maternal origin. The profile of these persistent pollutants in eggs and nestlings also gradually changed during development. With increasing age, the proportion of the most persistent compounds decreased. This study shows that most of the persistent pollutants in fully grown nestlings may still be from maternal origin. For nestlings to be suitable as indicators of local contamination, most of the POPs they accumulate should originate from dietary sources rather than from maternal transfer via the egg. Nestling birds may therefore not be good sentinels for local contamination with persistent pollutants.     

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.     

Occurrence of brominated flame retardants in black thermo cups and selected kitchen utensils purchased on the European market

In order to screen for the presence of a recycled polymer waste stream from waste electric and electronic equipment (WEEE), a market survey was conducted on black plastic food-contact articles (FCA). An analytical method was applied combining X-ray fluorescence spectrometry (XRF) with thermal desorption gas chromatography coupled with mass spectrometry (thermal desorption GC-MS). Firstly, XRF spectrometry was applied to distinguish bromine-positive samples. Secondly, bromine-positive samples were submitted for identification by thermal desorption GC-MS. Generally, the bromine-positive samples contained mainly technical decabromodiphenyl ether (decaBDE). Newer types of BFRs such as tetrabromobisphenol A (TBBPA), tetrabromobisphenol A bis(2,3-dibromopropyl), ether (TBBPA-BDBPE) and decabromodiphenylethane (DBDPE), replacing the polybrominated diphenyleters (PBDEs) and polybrominated diphenyls (PBBs), were also identified. In none of the tested samples were PBBs or hexabromocyclododecane (HBCD) found. Polymer identification was carried out using Fourier-transformed infrared spectroscopy measurement (FTIR) on all samples. The results indicate that polypropylene–polyethylene copolymers (PP-PE) and mainly styrene-based food-contact materials, such as acrylonitrile-butadiene-styrene (ABS) have the highest risk of containing BFRs.