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 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.     

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.     

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.     

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.     

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.     

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.     

Dechlorane plus and other flame retardants in tree bark from the northeastern United States

Previous work has shown that certain parts of the Great Lakes region are polluted with Dechlorane Plus (DP), a highly chlorinated flame retardant that was used as a replacement for Dechlorane/Mirex. It was suspected that a source of DP to the environment might be its manufacturing facility located in the city of Niagara Falls, New York. To confirm this source location and to determine DP's spatial distribution, 26 tree bark samples were collected in triplicate from the northeastern United States, and the concentrations of DP and several brominated flame retardants (BFRs) were measured. Most concentrations of DP in tree bark were found to be much higher than those of the BFRs. The highest DP concentrations were >100 ng g(-1) bark in the city of Niagara Falls, dropping rapidly with distance from the potential source. A simple one-dimensional, Gaussian diffusion model was used to explain the spatial distribution of DP and to locate the source. The calculated source location was <7 km away from the DP manufacturing plant in Niagara Falls, New York.     

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 the atmosphere of E-waste and rural sites in southern China: seasonal variation, temperature dependence, and gas-particle partitioning

The recycling of electrical and electronic waste(e-waste) in developing countries has attracted much attention as a significant source of brominated flame retardants (BFRs).Gaseous and particle-bound BFRs were measured in the atmosphere at e-waste and rural sites in southern China during 2007-2008. The annual average concentrations in the air were 3260 ± 3370 and 219 ± 192 pg/m3 for polybrominated diphenyl ethers (PBDEs) and were 546 ± 547 and 165 ± 144 pg/m3 for non-PBDE BFRs at the e-waste and rural sites,respectively. PBDEs had unusually high relative concentrations of di- and tribrominated congeners at the e-waste site. The Clausius-Clapeyron (CC) plots showed that the gaseous concentrations of less brominated BFRs (di- through hexa-BFRs) were strongly controlled by temperature-driven evaporation from contaminated surfaces (e.g., e-waste, soils, and recycled e-waste remains) except for winter. However, weak temperature dependence at the rural site suggests that regional or long-range atmospheric transport was largely responsible for the air concentrations. Gas-particle partitioning (KP) of PBDEs correlated well with the subcooled liquid vapor pressure (PL(o)) for most sampling events. The varied slopes of log KP versus log PL(o) plots for the e-waste site (-0.59 to -1.29) indicated an influence of ambient temperature and atmospheric particle properties on the partitioning behavior of BFRs. The flat slopes (-0.23 to -0.80) for the rural site implied an absorption-dominant partitioning. This paper suggests that e-waste recycling in Asian low-latitude regions is a significant source of less brominated BFRs and has important implications for their global transport from warm to colder climate     

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.     

Brominated flame retardants in glaucous gulls from the Norwegian Arctic: more than just an issue of polybrominated diphenyl ethers

Several, unregulated, current-use brominated flame retardants (BFRs), including hexabromobenzene (HBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), and hexabromocyclododecane (as total-(alpha)-HBCD), were examined in egg yolk and plasma of male and female glaucous gulls (Larus hyperboreus) from the Norwegian Arctic. Also examined were BDE209 and 38 tri- to nona-BDE congeners and brominated biphenyl (BB) 101. The HBB, BTBPE, PBEB, and PBT had high detection frequencies and variability in male and female plasma and egg yolk samples, and their concentrations ranged from nondetectable (< 0.02-0.27 ng/g wet wt) to 2.64 ng/g wet wt. The detection frequencies and range of concentrations of non-BDE BFRs were generally highest in plasma of males relative to females. Total-(alpha)-HBCD concentrations were highest among the non-PBDE BFRs (up to 6.12 and 63.9 ng/g wet wt in plasma and egg yolk, respectively). Next highest was HBB with concentrations within a range comparable to the minor PBDEs monitored (e.g., BDE28, 116 and 155). Sum (sigma)38PBDE concentrations ranged from 2.49 to 54.5 ng/g wet wt in plasma and 81.2 to 321 ng/g wet wt in egg yolk. The BDE209 was virtually nondetectable, whereas six octa-BDEs (i.e., BDE196, 197, 201, 202, 203, and 205), as well as three nona-BDEs (i.e., BDE206, 207, and 208, and potential BDE209 debromination products) were found sporadically in plasma and egg yolk. The results from this study suggestthat in addition to PBDEs, several current-use, non-BDE BFRs undergo long-range atmospheric transport and bioaccumulate at low levels in and are maternally transferred (to eggs) in glaucous gulls from the Norwegian Arctic.     

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.     

Brominated flame retardants in archived serum samples from Norway: a study on temporal trends and the role of age

The temporal trends and influence of age and gender on levels of selected brominated flame retardants (BFRs) in human serum have been assessed by analyzing archived samples from Norway. Serum from 40 to 50 year old men collected at six time periods during 1977 to 1999 and from eight groups of differing age and gender sampled in 1998 were pooled into six and eight samples, respectively. The BFRs were isolated using solid-phase extraction (SPE) and the serum lipids decomposed bytreatmentwith concentrated sulfuric acid directly on the polystyrene-divinylbenzene SPE column, prior to elution of the BFRs. Following diazomethane derivatization, the samples were analyzed by gas chromatography-electron capture mass spectrometry. Eight BFRs were quantified in the serum samples: 2,4,4'-tribromodiphenyl ether (BDE-28), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), 2,2',4,4',6-pentabromodiphenyl ether (BDE-100), 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE-154), 2,4,6-tribromophenol (TriBP), and tetrabromobisphenol A (TBBP-A). The serum concentrations of all the BFRs, increased during the entire period with the exception of TriBP, and the sum of the six polybrominated diphenyl ethers increased from 0.44 ng/g lipids in 1977 to 3.3 ng/g lipids in 1999. The BFR concentrations in the serum from the different age groups were relatively similar, except for the age group 0-4 years, which had 1.6-3.5 times higher serum concentrations. Women older than 25 years had lower serum concentrations of BFRs compared to the corresponding group of men. No trend related to age or gender, nor time during the period 1977 to 1999 was observed for TriBP. The present study indicates an ongoing increase in human exposure to BFRs, and the current body burden appears to be independent of age, except for infants (0-4 years old), who seem to experience elevated exposure.     

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.     

Brominated flame retardants and halogenated phenolic compounds in North American west coast bald eaglet (Haliaeetus leucocephalus) plasma

We report on the identity, characterization, and spatial trends of several brominated flame retardants and hydroxylated (OH-) and methoxylated (MeO-) organohalogen contaminants in bald eagle (Haliaeetus leucocephalus) nestling plasma collected from sites along the west coast of North America. Samples were from four southwestern British Columbia (BC) locations, a reference site in northern BC (Fort St. James; FSJ), and from Santa Catalina Island, CA (SCI), an area of high DDT and PCB contamination. Mean concentrations of sigma polybrominated diphenyl ether (sigma PBDE (8 congeners monitored); 1.78-8.49 ng/g), sigma OH-polychlorinated biphenyl (sigma OH-PCB (30 congeners monitored); 0.44-0.87 ng/g), and sigma OH-PBDE (14 congeners monitored; 0.31-0.92 ng/g) were similar in eaglets from southwestern BC yet lower than for SCl and significantly higher than for FSJ. Dominant PBDE congeners were BDE47, BDE99, and BDE100, but SCl eaglets also contained low levels of higher brominated congeners. 4-OH-CB187 and 4'-OH-CB202 accounted for 65-100% of sigma OH-PCB in all BC eaglets, with 4'-OH-CB202 as well as 3'-OH-CB138 and 4-OH-CB146 dominating in SCl eaglets. Ostensibly of biogenic origin, 6'-OH-BDE49 and 6-OH-BDE47 were found in BC nestlings. Only 4'-OH-BDE49 (2.10 ng/g) was found in SCl eaglets. MeO-PBDEs and total hexabromocyclododecane (HBCD) were not found in any birds, but the polybrominated biphenyl BB101 was detected in southwestern BC samples. This study demonstrates that west coast North American bald eagles contain previously unreported organohalogens, which have the potential to impact the health and survival of these raptors.     

2-Ethylhexyl tetrabromobenzoate and bis(2-ethylhexyl) tetrabromophthalate flame retardants in the Great Lakes atmosphere

Two relatively new flame retardants, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) and bis(2-ethylhexyl)-tetrabromophthalate (TBPH), were identified and quantitated in gas and particle-phase air samples collected from six sites near the shores of the Great Lakes. TBB and TBPH were detected in more than half of the samples collected from 2008 to 2010. Urban areas, such as Chicago and Cleveland, showed the highest concentrations (0.36-290 pg/m(3)), while remote areas, such as Eagle Harbor and Sleeping Bear Dunes, exhibited the lowest levels (0.050-32 pg/m(3)). The atmospheric concentrations of TBB and TBPH increased rapidly and significantly over this time period, perhaps indicating that these compounds are replacing the polybrominated diphenyl ethers (PBDEs), which have been removed or soon will be removed from the marketplace.     

Brominated flame retardants in polar bears (Ursus maritimus) from Alaska, the Canadian Arctic, East Greenland, and Svalbard

Polybrominated diphenyl ethers (PBDEs) were determined in adipose tissue of adult and subadult female polar bears sampled between 1999 and 2002 from sub-populations in Arctic Canada, eastern Greenland, and Svalbard, and in males and females collected from 1994 to 2002 in northwestern Alaska. Only 4 congeners (BDE47, 99, 100, and 153) were consistently identified in all samples. BDE47 was the major PBDE congener representing from 65% to 82% of the sum (sigma) PBDEs. Age was not a significant covariate for individual PBDEs or sigmaPBDE. Higher proportions of BDE 99, 100, and 153 were generally found in samples from the Canadian Arctic than from Svalbard or the Bering-Chukchi Sea area of Alaska. Geometric mean sigmaPBDE concentrations were highest for female polar bear fat samples collected from Svalbard (50 ng/g lipid weight (lw)) and East Greenland (70 ng/g lw). Significantly lower sigmaPBDE concentrations were found in fat of bears from Canada and Alaska (means ranging from 7.6 to 22 ng/g lw).     

Brominated flame retardants in fish and shellfish - levels and contribution of fish consumption to dietary exposure of Dutch citizens to HBCD

In order to determine the contamination with brominated flame retardants (BFR) in fish regularly consumed by Dutch citizens, 44 samples of freshwater fish, marine fish, and shellfish were analyzed for polybrominated diphenyl ethers (PBDE), tetrabromobisphenol-A (TBBP-A) and its methylated derivative (me-TBBP-A), and hexabromocyclododecane (HBCD), including its alpha-, beta- and gamma-diastereomers. The highest BFR concentrations were found in pike-perch and eel from the highly industrialized and urbanized rivers Rhine and Meuse. The sum concentrations of BDE 28, 47, 99, 100, 153, 154, 183, 209, and brominated biphenyl (BB) 153 and HBCD (selection based on The European Food Safety Authority monitoring recommendation) ranged from below quantification limits to 17 ng/g wet weight (ww) in marine fish and in freshwater fish from 0.6 ng/g ww in pike-perch to 380 ng/g ww in eel. The BDE congener profile in all fish and shellfish samples is dominated by BDE 47, followed by BDE 99, except for eel in which BDE 100 is higher than BDE 99. BDE 209 was detected in two mussel samples, most likely due to BDE 209 contaminated particulate matter in their intestines. Total-HBCD (as determined by GC/electron capture negative ion (ECNI)-MS) was detected in 22 out of the 44 samples in concentrations between 0.20 ng/g in marine fish and 230 ng/g ww in eel. Three HBCD diastereomers were determined by HPLC/ESI-MS/MS. alpha-HBCD was the prevalent congener in most fish samples, followed by gamma-HBCD. beta-HBCD, TBBP-A and me-TBBP-A were only detected in a few samples and at low concentrations. A considerable difference was found between HBCD results obtained from GC/ECNI-MS and HPLC/ESI-MS/MS: the GC/ECNI-MS results were 4.4 times higher, according to regression analysis. There is hardly any data on human dietary exposure to HBCD available. We have estimated the fish-related dietary exposure of HBCD for the average Dutch population. The medium bound intake was estimated at 8.3 ng/day for a 70-kg person (0.12 ng/kg bodyweight/day). For this estimation, we relied mostly on HPLC/ESI-MS/MS data as we argue that these results are more accurate than those obtained by GC/ECNI-MS.     

Brominated and chlorinated dioxins, PCBs and brominated flame retardants in Scottish shellfish: methodology, occurrence and human dietary exposure

The most commonly consumed shellfish species produced in Scotland - mussels, oysters and scallops - were investigated for the occurrence of a range of brominated and chlorinated contaminants in order to establish current levels and estimate human dietary exposure. Flesh from individual sub-samples was representatively pooled and 35 composites were analysed for brominated and chlorinated dioxins (PBDD/Fs, PCDD/Fs), brominated and chlorinated biphenyls (PBBs, PCBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA). The analytical methodology used (13)C(12) labelled surrogates of the target compounds, with GC coupled to (usually) high resolution MS, and LC-MS/MS for HBCD and TBBPA analysis. Positive identifications were made in the majority of samples for most analytes with the exception of TBBPA and most PBDD congeners measured. None of the levels detected for PCDD/F and PCB were above the maximum permitted levels specified in European Union regulations. The levels of brominated furans predominated over brominated dioxins, reflecting the environmental distribution and source emission profiles of these contaminants, and relatively high levels of the tri-brominated congeners were observed. Levels of the flame retardant chemicals reflected current and legacy use, with appreciable concentrations of PBDEs and HBCDs (predominantly alpha-HBCD) but far lower levels of PBBs. TBBPA was not detected in any of the species. In general, mussels and oysters displayed relatively higher levels of contamination than scallops, although the gonad tissue of the latter showed significant levels of brominated dioxins. The estimated adult dietary intakes of PCDD/Fs and PCBs arising from the consumption of a typical portion of these foods in combination with an otherwise average UK diet were in the range 0.5-0.6 pg World Health Organisation (WHO)-toxic equivalent (TEQ)(2005)/kg bodyweight per day. These estimated dietary intakes are well within the Tolerable Daily Intake for dioxins and dioxin-like PCBs of 2 pg WHO-TEQ(2005)/kg bodyweight/day endorsed by the independent expert Committee on Toxicology of Chemicals in Food, Consumer Products and the Environment. The corresponding intakes for sumPBDEs and sumHBCDs were 5.6-6.1 and 5.9-7.9 ng/kg bodyweight/day respectively.