SciCombinator

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Concept: Decabromodiphenyl ether

210

California’s furniture flammability standard Technical Bulletin 117 (TB 117) is believed to be a major driver of chemical flame retardant (FR) use in residential furniture in the United States. With the phase-out of the polybrominated diphenyl ether (PBDE) FR mixture PentaBDE in 2005, alternative FRs are increasingly being used to meet TB 117; however, it was unclear which chemicals were being used and how frequently. To address this data gap, we collected and analyzed 102 samples of polyurethane foam from residential couches purchased in the United States from 1985 to 2010. Overall, we detected chemical flame retardants in 85% of the couches. In samples purchased prior to 2005 (n = 41) PBDEs associated with the PentaBDE mixture including BDEs 47, 99, and 100 (PentaBDE) were the most common FR detected (39%), followed by tris(1,3-dichloroisopropyl) phosphate (TDCPP; 24%), which is a suspected human carcinogen. In samples purchased in 2005 or later (n = 61) the most common FRs detected were TDCPP (52%) and components associated with the Firemaster550 (FM 550) mixture (18%). Since the 2005 phase-out of PentaBDE, the use of TDCPP increased significantly. In addition, a mixture of nonhalogenated organophosphate FRs that included triphenyl phosphate (TPP), tris(4-butylphenyl) phosphate (TBPP), and a mix of butylphenyl phosphate isomers were observed in 13% of the couch samples purchased in 2005 or later. Overall the prevalence of flame retardants (and PentaBDE) was higher in couches bought in California compared to elsewhere, although the difference was not quite significant (p = 0.054 for PentaBDE). The difference was greater before 2005 than after, suggesting that TB 117 is becoming a de facto standard across the U.S. We determined that the presence of a TB 117 label did predict the presence of a FR; however, lack of a label did not predict the absence of a flame retardant. Following the PentaBDE phase out, we also found an increased number of flame retardants on the market. Given these results, and the potential for human exposure to FRs, health studies should be conducted on the types of FRs identified here.

Concepts: United States, Mixture, Fire retardant, Flame retardant, Decabromodiphenyl ether, Polychlorinated biphenyl, Flame retardants, De facto

181

BACKGROUND: Flame retardant chemicals are used in materials on airplanes to slow the propagation of fire. These chemicals migrate from their source products and can be found in the dust of airplanes, creating the potential for exposure. METHODS: To characterize exposure to flame retardant chemicals in airplane dust, we collected dust samples from locations inside 19 commercial airplanes parked overnight at airport gates. In addition, hand-wipe samples were also collected from 9 flight attendants and 1 passenger who had just taken a cross-country (USA) flight. The samples were analyzed for a suite of flame retardant chemicals. To identify the possible sources for the brominated flame retardants, we used a portable XRF analyzer to quantify bromine concentrations in materials inside the airplanes. RESULTS: A wide range of flame retardant compounds were detected in 100% of the dust samples collected from airplanes, including BDEs 47, 99, 153, 183 and 209, tris(1,3-dichloro-isopropyl)phosphate (TDCPP), hexabromocyclododecane (HBCD) and bis-(2-ethylhexyl)-tetrabromo-phthalate (TBPH). Airplane dust contained elevated concentrations of BDE 209 (GM: 500 ug/g; range: 2,600 ug/g) relative to other indoor environments, such as residential and commercial buildings, and the hands of participants after a cross-country flight contained elevated BDE 209 concentrations relative to the general population. TDCPP, a known carcinogen that was removed from use in children’s pajamas in the 1970’s although still used today in other consumer products, was detected on 100% of airplanes in concentrations similar to those found in residential and commercial locations. CONCLUSION: This study adds to the limited body of knowledge regarding exposure to flame retardants on commercial aircraft, an environment long hypothesized to be at risk for maximum exposures due to strict flame retardant standards for aircraft materials. Our findings indicate that flame retardants are widely used in many airplane components and all airplane types, as expected. Most flame retardants, including TDCPP, were detected in 100% of dust samples collected from the airplanes. The concentrations of BDE 209 were elevated by orders of magnitude relative to residential and office environments.

Concepts: Fire retardant, Flame retardant, Decabromodiphenyl ether, Bromine, Brominated flame retardant, Flame retardants, Hexabromocyclododecane, Aircraft

57

Children are exposed to flame retardants from the built environment. Brominated diphenyl ethers (BDE) and organophosphate-based flame retardants (OPFRs) are associated with poorer neurocognitive functioning in children. Less is known, however, about the association between these classes of compounds and children’s emotional and social behaviors. The objective of this study was to determine if flame retardant exposure was associated with measurable differences in social behaviors among children ages 3-5 years.

Concepts: Fire retardant, Flame retardant, Decabromodiphenyl ether, Polychlorinated biphenyl, Brominated flame retardant, Flame retardants, Antimony trioxide

34

Higher house dust levels of PBDE flame retardants (FRs) have been reported in California than other parts of the world, due to the state’s furniture flammability standard. However, changing levels of these and other FRs have not been evaluated following the 2004 U.S. phase-out of PentaBDE and OctaBDE. We analyzed dust collected in 16 California homes in 2006 and again in 2011 for 62 FRs and organohalogens, which represents the broadest investigation of FRs in homes. Fifty-five compounds were detected in at least one sample; 41 in at least 50% of samples. Concentrations of chlorinated OPFRs, including two (TCEP and TDCIPP) listed as carcinogens under California’s Proposition 65, were found up to 0.01% in dust, higher than previously reported in the U.S. In 75% of the homes, we detected TDBPP, or brominated “Tris,” which was banned in children’s sleepwear because of carcinogenicity. To our knowledge, this is the first report on TDBPP in house dust. Concentrations of Firemaster 550 components (EH-TBB, BEH-TEBP, and TPHP) were higher in 2011 than 2006, consistent with its use as a PentaBDE replacement. Results highlight the evolving nature of FR exposures and suggest that manufacturers continue to use hazardous chemicals and replace chemicals of concern with chemicals with uncharacterized toxicity.

Concepts: DNA, United States, Fire retardant, Plastic, Decabromodiphenyl ether, Brominated flame retardant, Flame retardants, Dust explosion

6

A total of 23 PBDE congeners were measured in soil samples collected in areas with no known point source (urban/rural/background sites, U/R/B sites) and in contaminated areas (brominated flame retardants (BFRs) related industrial and e-waste recycling sites) across five Asian countries. The highest PBDE concentrations were found in BFRs related industrial and e-waste recycling sites. The concentrations of PBDEs in U/R/B sites followed the order of: urban > rural > background sites. Total PBDE concentrations were dominated by BDE-209, while BDE-17, -85, -138, -191, -204 and -205 were the least abundant compounds. In both urban sites and rural sites, the mean concentrations of total PBDEs (∑23BDEs) in soils followed the order of: Japan > China > South Korea > India > Vietnam. The concentrations of PBDEs in soils were comparable with those reported in other studies. Among the three commercial PBDE mixtures, relatively high contribution of commercial penta-BDE were observed in Vietnam, whereas deca-BDE was the dominant mixtures contributing from 55.8 ± 2.5% to 100.0 ± 1.2% of the total PBDEs in soils collected from other four countries. Regression analysis suggested that local population density (PD) is a good indicator of PBDEs in soils of each country. Significant and positive correlation between soil organic content and PBDE level was observed in Chinese soil for most non-deca-BDE homologues with their usage stopped 10 years ago, indicating its important role in controlling the re-volatilization of PBDEs from soil and changing the spatial trend of PBDE in soil from the primary distribution pattern to the secondary distribution pattern, especially when primary emission is ceased.

Concepts: Population, Flame retardant, Decabromodiphenyl ether, Polybrominated diphenyl ethers, Persistent organic pollutants, Brominated flame retardant, Flame retardants, Organobromides

5

Polybrominated diphenyl ethers (PBDEs) were used extensively as flame retardants in furniture containing polyurethane foam until they were phased out of use, beginning in 2004. We examined temporal changes in plasma PBDE concentrations from 1998 to 2013 and characterized patterns of exposure over the early lifecourse among 334 children (903 samples) between birth and 9 years. We examined time trends by regressing PBDE concentration on year of sample collection in age-adjusted models and characterized developmental trajectories using latent class growth analysis (LCGA). Controlling for age, BDE-47 concentrations decreased 5% (95% confidence interval (CI): -9, -2) per year between 1998 and 2013. When considering only postnatal samples, this reduction strengthened to 13% (95% CI: -19, -9). Findings for BDE-99, 100 and 153 were similar, except that BDE-153 decreased to a lesser extent when both prenatal and postnatal samples were considered (-2%, 95% CI: -7, 0). These findings suggest that, on average, pentaBDE body burdens have decreased since the 2004 phase-out of these chemicals. When examining developmental period, PBDE concentrations peaked during toddler years for the majority of children, however, our observation of several unique trajectories suggests that a single measure may not accurately reflect exposure to PBDEs throughout early life.

Concepts: Childbirth, Concentration, Chemistry, Fire retardant, Decabromodiphenyl ether, Polychlorinated biphenyl, Polybrominated diphenyl ethers, Flame retardants

4

Furniture flammability standards are typically met with chemical flame retardants (FRs). FRs can migrate out of products into dust and are linked to cancer, neurological impairment, and endocrine disruption. We collected 95 dust samples from dormitory common areas and student rooms on two U.S. college campuses adhering to two different furniture flammability standards: Technical Bulletin 117 (TB117) and Technical Bulletin 133 (TB133). Because TB133 requires furniture to withstand a much-more-demanding test flame than TB117, we hypothesized that spaces with TB133 furniture would have higher levels of FRs in dust. We found all 47 targeted FRs, including 12 polybrominated diphenyl ether (PBDE) congeners, 19 other brominated FRs, 11 phosphorus FRs (PFRs), 2 Dechlorane-Plus (DP) isomers, and 3 hexabromocyclododecane (HBCDD) isomers in the 95 dust samples. We measured the highest reported U.S. concentrations for a number of FRs, including BDE 209 (up to 990 000 ng/g), which may be used to meet the TB133 standard. We prioritized 16 FRs and analyzed levels in relation to flammability standard as well as presence and age of furniture and electronics. Adherence to TB133 was associated with higher concentrations of BDE 209, decabromodiphenylethane (DBDPE), DPs, and HBCDD compared to adherence to TB117 in univariate models (p < 0.05). Student dormitory rooms tended to have higher levels of some FRs compared to common rooms, likely a result of the density of furniture and electronics. As flammability standards are updated, it is critical to understand their impact on exposure and health risks.

Concepts: Fire retardant, Flame retardant, Decabromodiphenyl ether, Polychlorinated biphenyl, Brominated flame retardant, Flame retardants, Hexabromocyclododecane, Dormitory

4

Gymnastics training facilities contain large volumes of polyurethane foam, a material that often contains additive flame retardants such as PentaBDE. While investigations of human exposure to flame retardants have focused on the general population, potentially higher than background exposures may occur in gymnasts and certain occupational groups. Our objectives were to compare PentaBDE body burden among gymnasts to the general U.S. population and characterize flame retardants levels in gym equipment, air and dust. We recruited 11 collegiate female gymnasts (ages 18-22) from one gym in the Eastern U.S. The geometric mean (GM) concentration of BDE-153 in gymnast sera (32.5 ng/g lipid) was 4-6.5 times higher than general U.S. population groups. Median concentrations of PentaBDE, TBB and TBPH in paired handwipe samples were 2-3 times higher after practice compared to before, indicating the gymnasts contacted these flame retardants during practice. GM concentrations of PentaBDE, TBB and TBPH were 1-3 orders of magnitude higher in gym air and dust than in residences. Our findings suggest that these collegiate gymnasts experienced higher exposures to PentaBDE flame retardants compared to the general U.S. population and that gymnasts may also have increased exposure to other additive flame retardants used in polyurethane foam such as TBB and TBPH.

Concepts: Arithmetic mean, Fire retardant, Flame retardant, Mean, Decabromodiphenyl ether, Flame retardants, Gymnastics, Gymnastics at the 2008 Summer Olympics

3

A high molecular weight compound, 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ), was detected during the analysis of brominated flame retardants in dust samples collected from an electrical and electronic waste (e-waste) recycling facility in Ontario, Canada. Gas chromatography coupled with both high-resolution and low-resolution mass spectrometry (MS) was used to determine TTBP-TAZ’s chemical structure and concentrations. To date, TTBP-TAZ has only been detected in plastic casings of electrical and electronic equipment and house dust from The Netherlands. Here we report on the concentrations of TTBP-TAZ in selected samples from North America: e-waste dust ( n = 7) and air ( n = 4), residential dust ( n = 30), and selected outdoor air ( n = 146), precipitation ( n = 19), sediment ( n = 11) and water ( n = 2) samples from the Great Lakes environment. TTBP-TAZ was detected in all the e-waste dust and air samples, and in 70% of residential dust samples. The median concentrations of TTBP-TAZ in these three types of samples were 5540 ng/g, 5.75 ng/m3and 6.76 ng/g, respectively. The flame retardants 2,4,6-tribromophenol, tris(2,3-dibromopropyl) isocyanurate, and 3,3',5,5'-tetrabromobisphenol A bis(2,3-dibromopropyl) ether, BDE-47 and BDE-209 were also measured for comparison. None of these other flame retardants concentrations was significantly correlated with those of TTBP-TAZ in any of the sample types suggesting different sources. TTBP-TAZ was not detected in any of the outdoor environmental samples, which may relate to its application history and physicochemical properties. This is the first report of TTBP-TAZ in North America.

Concepts: United States, Fire retardant, Flame retardant, Decabromodiphenyl ether, North America, Brominated flame retardant, Flame retardants, Hexabromocyclododecane

3

Flame retardants are widely used in polyurethane foam materials including gymnastics safety equipment such as pit cubes and landing mats. We previously reported elevated concentrations of flame retardants in the air and dust of a U.S. gymnastics training facility and elevated PentaBDE in the serum of collegiate gymnasts. Our objective in this pilot study was to compare urinary biomarkers of exposure to other flame retardants and additives of polyurethane foam including tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), triphenyl phosphate (TPHP) and 2-ethylhexyl- 2,3,4,5-tetrabromobenzoate (EH-TBB) in samples collected from 11 collegiate gymnasts before and after a gymnastics practice (n=53 urine samples total). We identified a 50% increase in the TPHP biomarker (p=0.03) from before to after practice, a non-significant 22% increase in the TDCIPP biomarker (p=0.14) and no change for the EH-TBB biomarker. These preliminary results indicate that the gymnastics training environment can be a source of recreational exposure to flame retardants. Such exposures are likely widespread, as we identified flame retardants in 89% of foam samples collected from gyms across the U.S.

Concepts: Fire retardant, Flame retardant, Decabromodiphenyl ether, Flame retardants