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Concept: Flame retardant

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

200

Women have elevated rates of thyroid disease compared to men. Environmental toxicants have been implicated as contributors to this dimorphism, including polybrominated diphenyl ethers (PBDEs), flame retardant chemicals that disrupt thyroid hormone action. PBDEs have also been implicated in the disruption of estrogenic activity, and estrogen levels regulate thyroid hormones. Post-menopausal women may therefore be particularly vulnerable to PBDE induced thyroid effects, given low estrogen reserves. The objective of this study was to test for an association between serum PBDE concentrations and thyroid disease in women from the United States (U.S.), stratified by menopause status.

Concepts: Hormone replacement therapy, Hormone, Menopause, Estrogen, Luteinizing hormone, Thyroid hormone, Flame retardant, Flame retardants

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

130

Lifetime contaminant and hormonal profiles have been reconstructed for an individual male blue whale (Balaenoptera musculus, Linnaeus 1758) using the earplug as a natural aging matrix that is also capable of archiving and preserving lipophilic compounds. These unprecedented lifetime profiles (i.e., birth to death) were reconstructed with a 6-mo resolution for a wide range of analytes including cortisol (stress hormone), testosterone (developmental hormone), organic contaminants (e.g., pesticides and flame retardants), and mercury. Cortisol lifetime profiles revealed a doubling of cortisol levels over baseline. Testosterone profiles suggest this male blue whale reached sexual maturity at approximately 10 y of age, which corresponds well with and improves on previous estimates. Early periods of the reconstructed contaminant profiles for pesticides (such as dichlorodiphenyltrichloroethanes and chlordanes), polychlorinated biphenyls, and polybrominated diphenyl ethers demonstrate significant maternal transfer occurred at 0-12 mo. The total lifetime organic contaminant burden measured between the earplug (sum of contaminants in laminae layers) and blubber samples from the same organism were similar. Total mercury profiles revealed reduced maternal transfer and two distinct pulse events compared with organic contaminants. The use of a whale earplug to reconstruct lifetime chemical profiles will allow for a more comprehensive examination of stress, development, and contaminant exposure, as well as improve the assessment of contaminant use/emission, environmental noise, ship traffic, and climate change on these important marine sentinels.

Concepts: Hormone, Cortisol, Flame retardant, Puberty, Polychlorinated biphenyl, Biphenyl, Humpback whale, Whale song

95

Evidence from animal studies suggests that exposure to organophosphate flame retardants (PFRs) can disrupt endocrine function and impair embryo development. However, no epidemiologic studies have been conducted to evaluate effects on fertility and pregnancy outcomes.

Concepts: Pregnancy, Embryo, Fetus, Fertility, In vitro fertilisation, Fire retardant, Flame retardant, Flame retardants

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

46

About 200 second-hand plastic toys sourced in the UK have been analysed by x-ray fluorescence spectrometry for hazardous elements (As, Ba, Cd, Cr, Hg, Pb, Sb, Se) and Br as a proxy for brominated flame retardants. Each element was detected in > 20 toys or components thereof with the exception of As, Hg and Se, with the frequent occurrence of Br, Cd and Pb and at maximum concentrations of about 16,000, 20,000 and 5000 μg g-1, respectively, of greatest concern from a potential exposure perspective. Migration was evaluated on components of 26 toys under simulated stomach conditions (0.07 M HCl) with subsequent analysis by inductively coupled plasma spectrometry. In eight cases, Cd or Pb exceeded their migration limits as stipulated by the current EU Toy Safety Directive (17 and 23 μμ g-1, respectively), with Cd released from yellow and red Lego bricks exceeding its limit by an order of magnitude. Two further cases were potentially non-compliant based on migratable Cr, with one item also containing > 250 μg g-1 migratable Br. While there is no retroactive regulation on second-hand toys, consumers should be aware that old, mouthable, plastic items may present a source of hazardous element exposure to infants.

Concepts: Spectroscopy, X-ray fluorescence, Chemistry, Flame retardant, Plasma, Brominated flame retardant, Toy, Lego

35

Wristbands are increasingly used for assessing personal chemical exposures. Unlike some exposure assessment tools, guidelines for wristbands, such as preparation, applicable chemicals, and transport and storage logistics, are lacking. We tested the wristband’s capacity to capture and retain 148 chemicals including polychlorinated biphenyls (PCBs), pesticides, flame retardants, polycyclic aromatic hydrocarbons (PAHs), and volatile organic chemicals (VOCs). The chemicals span a wide range of physical-chemical properties, with log octanol-air partitioning coefficients from 2.1 to 13.7. All chemicals were quantitatively and precisely recovered from initial exposures, averaging 102% recovery with relative SD ≤21%. In simulated transport conditions at +30 °C, SVOCs were stable up to 1 month (average: 104%) and VOC levels were unchanged (average: 99%) for 7 days. During long-term storage at -20 °C up to 3 (VOCs) or 6 months (SVOCs), all chemical levels were stable from chemical degradation or diffusional losses, averaging 110%. Applying a paired wristband/active sampler study with human participants, the first estimates of wristband-air partitioning coefficients for PAHs are presented to aid in environmental air concentration estimates. Extrapolation of these stability results to other chemicals within the same physical-chemical parameters is expected to yield similar results. As we better define wristband characteristics, wristbands can be better integrated in exposure science and epidemiological studies.Journal of Exposure Science and Environmental Epidemiology advance online publication, 26 July 2017; doi:10.1038/jes.2017.9.

Concepts: Epidemiology, Polycyclic aromatic hydrocarbon, Flame retardant, Organic chemistry, Volatile organic compound, Organic compounds, Polychlorinated biphenyl, Biphenyl

28

In order to confirm the possibility that recycled fractions from the Waste Electrical and Electronic Equipment (WEEE) stream were illegally entering the European market in black polymeric food-contact articles (FCAs), bromine quantification, brominated flame retardant (BFR) identification combined with WEEE relevant elemental analysis and polymer impurity analysis were performed. From the 10 selected FCAs, seven samples contained a bromine level ranging from 57 till 5975 mg kg(-1) which is lower than expected to achieve flame retardancy. The BFRs which were present were tetrabromobisphenol A (TBBPA), decabromodiphenylether (decaBDE), decabromodiphenylethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE). Typical elements used in electronic equipment and present in WEEE were detected either at trace level or at elevated concentrations. In all cases when bromine was detected at higher concentrations, concurrently antimony was also detected which confirms the synergetic use of antimony in combination with BFRs. This study describes also the measurement of rare earth elements (REEs) where combinations of cerium, dysprosium, lanthanum, neodymium, praseodymium and yttrium which were detected in four of the seven BFR positive samples. Additionally, the polymer purity was investigated where in all cases foreign polymer fractions were detected. Despite the fact that this study was carried-out on a very small amount of samples there is a significant likelihood that WEEE has been used for the production of FCAs.

Concepts: Flame retardant, Rare earth element, Chemical elements, Yttrium, Brominated flame retardant, Cerium, Lanthanide, Monazite

28

Brominated flame retardants (BFRs), are chemicals widely used in consumer products including electronics, vehicles, plastics and textiles to reduce flammability. Experimental animal studies have confirmed that these compounds may interfere with thyroid hormone homeostasis and neurodevelopment but to date health effects in humans have not been systematically examined.

Concepts: Organism, Thyroid hormone, Fire retardant, Flame retardant, Decabromodiphenyl ether, Brominated flame retardant, Flame retardants, Hexabromocyclododecane