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.     

Brominated flame retardants in tree bark from North America

Brominated flame retardants were measured in 87 tree bark samples from 29 locations in North America. The concentrations of total polybrominated diphenyl ethers (PBDEs) ranged from 2.3 to 5700 ng/g lipid weight, with the highest concentrations found near or in Arkansas. A simple radial dilution model nicely describes the distribution of total PBDE concentrations in these samples and indicates the likely sources ofthese chemicals are emissions from the two brominated flame retardant manufacturing facilities, operated by Great Lakes Chemicals and Albemarle, located in southern Arkansas. The congener profiles of PBDEs are similar for all the tree bark samples and can be described by a mixture of the congener profiles of the penta- and deca-BDE commercial products combined in a ratio of 1:2. Two unusual BFRs, 1,2-bis(2,4,6-tribromophenoxy)ethane and decabromodiphenyl ethane, were also detected in tree bark samples collected in Arkansas, suggesting the two manufacturing facilities are the sources of these compounds as well. A polybrominated biphenyl congener (BB-153) was present in most tree bark samples at low levels relative to the PBDEs.     

Brominated flame retardants in US food

We and others recently began studying brominated flame retardant levels in various matrices in the US including human milk and other food. This paper reviews the food studies. In our studies, ten to thirteen polybrominated diphenyl ether (PBDE) congeners were measured, usually including BDE 209. All US women's milk samples were contaminated with PBDEs from 6 to 419 ng/g, lipid, orders of magnitude higher than levels reported in European studies, and are the highest reported worldwide. We compared our market basket studies of meat, fish and dairy products with other US food studies of meat and fish. US studies showed somewhat higher levels of PBDEs than reported elsewhere. Fish were most highly contaminated (median 616 pg/g), then meat (median190 pg/g) and dairy products (median 32.2 pg/g). However, unlike some European countries where fish predominates, dietary intake of PBDEs in the US is mostly from meat, then fish and then dairy products. Broiling can decrease the amount of PBDEs per serving. We also measured levels of hexabromocyclododecane (HBCD), another brominated flame retardant, in human milk. The levels are lower than PBDEs, 0.16-1.2 ng/g, similar to European levels, unlike PBDEs where US levels are much higher than European levels.     

纺织品阻燃剂的安全评估和绿色品种最新开发

世界上纺织品引发的火灾数量和死亡率都比其他原因引起的高,造成生命财产的巨大损失,因此,各国纷纷出台纺织品燃烧性技术法规,规定某些纺织品必需进行阳燃整理.现用阻燃剂中有些品种自身有毒或燃烧时产生有毒物质,本文对其安全性进行评估,以利选用符合生态环保的阻燃剂.特别对于世界有关无卤、低毒、抑烟的现代阻燃剂开发作了详细介绍.     

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.     

Brominated flame retardants in sediment cores from Lakes Michigan and Erie

The history of polybrominated diphenyl ethers (PBDEs) and the major polybrominated biphenyl congener (BB-153) was studied in dated sediment cores taken from Lakes Michigan and Erie. The surficial concentration of total PBDE (65 [corrected] ng/g dry weight) in Lake Michigan was about 1.6 [corrected] times higher than that in Lake Erie (40 ng/g) and about 5 times higher than that [corrected] in Lake Superior (approximately 12 ng/g). The concentrations of total PBDEs in these sediments have increased rapidly, with doubling times of 5-10 years, reflecting the increasing market demand for these flame retardants over the last 30 years. BDE-209 was found to be the predominant congener in both sediment cores, making up approximately 95% [corrected] of the total PBDE load. The inventories of total PBDEs in Lakes Michigan and Erie were both [corrected] 40 ng/cm2 [corrected] The total burdens of these compounds in the sediment of Lakes Michigan and Erie were 23 [corrected] and 10 metric tons, respectively. We estimate [corrected] the total burden of these compounds in all of the Great Lakes is on the order of 100 [corrected] tons. In both lakes, BB-153 was found to increase rapidly during the 1970s and to peak around 1980.     

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     

阻燃剂的应用与发展

简要说明了纸张防火性能的获得,造纸用阻燃剂的种类、特性。概括了阻燃剂在造纸中的使用方法及相应的阻燃机理。介绍了阻燃剂的发展方向,对各类阻燃剂的发展趋势和防火纸应用技术的研究热点进行了展望。     

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.     

Brominated flame retardants in Canadian chicken egg yolks

Chicken eggs categorised as conventional, omega-3 enriched, free range and organic were collected at grading stations in three regions of Canada between 2005 and 2006. Free run eggs, which were only available for collection from two regions, were also sampled during this time frame. Egg yolks from each of these egg types (n = 162) were analysed to determine brominated flame retardant levels, specifically polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). PBDEs were detected in 100% of the 162 samples tested, while HBCD was observed in 85% of the egg yolks. Total PBDE concentrations in egg yolks ranged from 0.018 to 20.9 ng g(-1) lipid (median = 3.03 ng g(-1) lipid), with PBDE 209 identified as being the major contributor to ΣPBDE concentrations. In addition to PBDE 209, PBDE 99, 47, 100, 183 and 153 were important contributors to ΣPBDE concentrations. Total HBCD concentrations ranged from below the limit of detection to a maximum concentration of 71.9 ng g(-1) lipid (median = 0.053 ng g(-1) lipid). The α-isomer was the dominant contributor to ΣHBCD levels in Canadian egg yolks and was the most frequently detected HBCD isomer. ΣPBDE levels exhibited large differences in variability between combinations of region and type. ΣHBCD concentrations were not significantly different among regions, although differences were observed between the different types of egg yolks analysed in the present study.     

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.     

Levels of polybrominated diphenyl ether flame retardants in sediment cores from Western Europe

The levels of 14 brominated diphenyl ether (BDE)-congeners in sediment cores from three locations in Western Europe have been determined by GC/MS (negative chemical ionization mode). Sediments from the Drammenfjord (Norway), the western Wadden Sea (The Netherlands), and the freshwater Lake Woserin (Mecklenburg-Vorpommern, Germany) showed a time-dependent pattern in the distribution of BDEs since the beginning of the industrial production of polybrominated diphenyl ether (PBDE) formulations. Two out of three commercially available PBDE formulations could be distinguished. Starting from the beginning of the 1970s, the penta-mix formulation is clearly present, but the deca-mix formulation is only present since the late 1970s. The octa-mix formulation appeared to be still absent in these sediments, as its marker-congener, BDE183, was never detected. In the cores from the western Wadden Sea and Lake Woserin, all TOC-normalized concentrations of the penta-BDE-derived congeners were leveling off in the most recent sediment layers representing 1995 and 1997, whereas those in the Drammenfjord were still increasing in 1999. The levels of BDE209, however, decreased in the most recent layer of all three cores. In Lake Woserin, the concentrations of BDE209 were much less elevated above those of the tri- to hexa-BDEs than in the other the two areas. This might be due to the absence of a significant PBDE input from sources other than the atmosphere to this rural lake. The absence of all PBDE congeners in the older layers of the three sediment cores, as well as in several 100-150-My-old layers from an extremely organic-rich marine sediment from the Kimmeridge clay formation in Dorset (UK), indicated the absence of natural production of the BDE congeners analyzed.     

Release of CFC-11 from disposal of polyurethane foam waste

The halocarbon CFC-11 has extensively been used as a blowing agent for polyurethane (PUR) insulation foams in home appliances and for residential and industrial construction. Release of CFCs is an important factor in the depletion of the ozone layer. For CFC-11 the future atmospheric concentrations will mainly depend on the continued release from PUR foams. Little is known about rates and time frames of the CFC release from foams especially after treatment and disposal of foam containing waste products. The CFC release is mainly controlled by slow diffusion out through the PUR. From the literature and by reevaluation of an old reported experiment, diffusion coefficients in the range of 0.05-1.7 x 10(-14) m2 s-1 were found reflecting differences in foam properties and experimental designs. Laboratory experiments studying the distribution of CFC in the foam and the short-term releases after shredding showed that about 40% of the CFC is solubilized in the PUR phase, and that up to 10% of the total content will be released within a few weeks if the foam is shredded down to 2-cm sized pieces. For smaller pieces the quick release will be larger. Fifty percent of residual CFC content will be released within 9-300 years from 2-cm pieces based on the range in diffusion coefficients reported. For larger pieces the initial release is insignificant, and the release time frames are much longer than for the shredded foam.     

Characterisation of silver release from nanoparticle-treated baby products

ABSTRACT

We tested six kinds of commercially available baby products containing nano-silver and divided them into two categories: baby food containers and baby oral care products, according to usage. We measured the total mass of silver, particle size, particle number concentration and the mobility under different simulated conditions. The total mass of silver in baby products and migration solutions was quantified by ICP-MS analysis, and the size of the migrated particles was investigated by single particle ICP-MS and transmission electron microscopy-energy dispersive spectrometer. Nano-silver has different migration behaviour in different materials, and the total mass of silver released in 3% acetic acid was generally highest for plastic material, while highest in 10% ethanol for silicone material. For baby food containers and baby oral care products, the total amount of silver in the migration solutions varied from 2.98 to 126.46 ng/dm² and from 2.01 to 2.83 ng/g, respectively. The research shows that the use of baby products containing silver may expose babies to silver nanoparticles.     

Dechlorane plus and other flame retardants in a sediment core from Lake Ontario

Our previous research on atmospheric samples suggested that Lake Ontario might receive significant amounts of Dechlorane Plus (DP), a highly chlorinated flame retardant, from the atmosphere and from inputs from DP's manufacturing facility in Niagara Falls, New York. To confirm this suspicion, a sediment core from the central basin of Lake Ontario was analyzed for the two isomers of DP, for polybrominated diphenyl ethers (PBDEs), and for 1,2-bis-(2,4,6-tribromophenoxy)ethane (TBE). The results showed that the concentration of DP in sediment increased rapidly starting in the mid-1970s and reached its peak concentration (310 ng g(-1) dry weight) in the mid-1990s. The peak flux and total inventory of DP were estimated to be 9.3 ng cm(-2) yr(-1) and 120 ng cm(-2), respectively. These values suggest that the total burden of DP in Lake Ontario is approximately 20 tons and that the maximum load rate was approximately 2 tons per year. The highest concentrations of PBDEs and TBE were found in the surficial sediment, with average concentrations of 2.8, 14, and 6.7 ng g(-1) d.w. for PBDE(3-7) (tri-through hepta-BDEs), BDE-209, and TBE, respectively. The surface fluxes were 0.08, 0.43, and 0.20 ng cm(-2) yr(-1), and the inventories were 0.87, 3.9, and 1.8 ng cm(-2) for PBDE3-7, BDE-209, and TBE, respectively. The concentration of DP in Lake Ontario sediment exceeds that of the brominated flame retardants combined.