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Sample records for polybrominated flame retardants

  1. In vitro estrogenicity of polybrominated flame retardants.

    PubMed

    Nakari, Tarja; Pessala, Piia

    2005-09-10

    Estrogenicity of five brominated flame retardants (BFRs), namely BDE-47, BDE-99, BDE-205, PBB-153 and technical Firemaster BP-6, were assessed by in vitro assays developed to detect chemicals with estrogenic properties. Recombinant yeast cells containing a human estrogen receptor gene failed to give any response to the chemicals tested. However, the positive control compound, estradiol-17beta, showed that the yeast cell assays had worked properly. The freshly separated fish hepatocyte assay based on the synthesis and secretion of vitellogenin from the isolated liver cells produced a clear dose-response curve in the presence of all tested flame retardants except Firemaster BP-6. The toxicity of the BFRs was detected by determining the cell ethoxyresorufin-O-deethylase activity (EROD). The BFRs tested induced hepatic EROD activity at low test concentrations, but started to inhibit activity at higher concentrations. The decreased detoxification capacity of the hepatocytes resulted in a decrease in the vitellogenin production of the cells. The capability of in vitro assays to detect estrogenic properties of chemicals seems to vary. Thus, further work is needed to understand the mechanisms responsible for these reactions. PMID:16024102

  2. DEVELOPMENTAL NEUROTOXICITY OF POLYBROMINATED DIPHENYL ETHER (PBDE) FLAME RETARDANTS

    PubMed Central

    Costa, Lucio G.; Giordano, Gennaro

    2007-01-01

    Polybrominated diphenyl ethers (PBDEs) are a class of flame retardants used in a variety of consumer products. In the past 25 years, PBDEs have become ubiquitous environmental contaminants. They have been detected in soil, air, sediments, birds, marine species, fish, house dust, and human tissues, blood and breast milk. Diet and house dust appear to be the major sources of PBDE exposure in the general population, though occupational exposure can also occur. Levels of PBDEs in human tissues are particularly high in North America, compared to Asian and European countries, and have been increasing in the past 30 years. Concentrations of PBDEs are particularly high in breast milk, resulting in high exposure of infants. In addition, for toddlers, dust has been estimated to account for a large percentage of exposure. PBDEs can also cross the placenta, as they have been detected in fetal blood and liver. Tetra-, penta- and hexa BDEs are most commonly present in human tissues. The current greatest concern for potential adverse effects of PBDEs relates to their developmental neurotoxicity. Pre- or postnatal exposure of mice or rats to various PBDEs has been shown to cause long-lasting changes in spontaneous motor activity, mostly characterized as hyperactivity or decreased habituation, and to disrupt performance in learning and memory tests. While a reduction in circulating thyroid hormone (T4) may contribute to the developmental neurotoxicity of PBDEs, direct effects on the developing brain have also been reported. Among these, PBDEs have been shown to affect signal transduction pathways and to cause oxidative stress. Levels of PBDEs causing developmental neurotoxicity in animals are not much dissimilar from levels found in highly exposed infants and toddlers. PMID:17904639

  3. Polybrominated diphenyl ethers and new polybrominated flame retardants in tree bark from western areas of China.

    PubMed

    Li, Qiuxu; Jin, Jun; Lu, Yao; Li, Guangyao; He, Chang; Wang, Ying; Li, Peng; Hu, Jicheng

    2016-06-01

    Tree bark samples were collected from 15 sites across western China in 2013, and the polybrominated diphenyl ether (PBDE) and new polybrominated flame retardant (NBFR) concentrations in the samples were determined. The mean total PBDE concentration was 51.8 ng/g lipid weight, which was 85.2% to 99.4% lower than in Chinese eastern coastal areas and the E-waste recycling areas. The dominant PBDE congener was BDE209, and its mean concentration was 49 ng/g lipid weight. The mean 2,3,5,6-tetrabromo-p-xylene, pentabromobenzene, pentabromotoluene, and hexabromobenzene concentrations were 0.61 ng/g, 0.97 ng/g, 0.68 ng/g, and 0.68 ng/g lw, respectively. The PBDE and NBFR concentrations in the air at the sampling sites were estimated from the concentrations in the tree bark samples. The estimated mean total PBDE and total NBFR concentrations in air were 58.5 pg/m(3) and 2.76 pg/m(3) , respectively. The sources of NBFR emissions were found to be different from the sources of PBDE emissions, as no relationship was found between the NBFR and PBDE concentrations, and it appeared that sources of measured hexabromobenzene, pentabromobenzene, and pentabromotoluene in tree bark in western China include industrial activity related to the aluminum industry. Environ Toxicol Chem 2016;35:1364-1370. © 2015 SETAC. PMID:26492098

  4. Brominated flame retardants in Chinese air before and after the phase out of polybrominated diphenyl ethers

    NASA Astrophysics Data System (ADS)

    Li, Wen-Long; Qi, Hong; Ma, Wan-Li; Liu, Li-Yan; Zhang, Zhi; Mohammed, Mohammed O. A.; Song, Wei-Wei; Zhang, Zifeng; Li, Yi-Fan

    2015-09-01

    Brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs) and novel non-BDE flame retardants (NBFRs), were analyzed in Chinese air during China's POPs Soil and Air Monitoring Program Phase I (SAMP-I) and Phase II (SAMP-II). The levels of Σ12PBDEs and Σ6NBFRs in urban sites were significantly higher than those in rural sites and background sites. The higher detection rate and concentrations of high molecular weight PBDEs and NBFRs in Phase II indicated the changing of the commercial pattern of BFRs after the phase out of PBDEs in China. Temperature was the major factor affecting the seasonal variations of molecular weight BFRs in atmosphere. A significant correlation between BFRs concentration and gross domestic product (GDP) was observed, with the GDP parameter explained 59.4% and 72.7% of the total variability for Octa-BDEs and low molecular weight NBFRs, respectively. Our findings indicated an evolving commercial usage of BFRs from SAMP-I to SAMP-II, i.e. shifting from lower molecular weight to higher molecular weight congeners in China.

  5. Emission behavior of hexabromocyclododecanes and polybrominated diphenyl ethers from flame-retardant-treated textiles.

    PubMed

    Kajiwara, Natsuko; Takigami, Hidetaka

    2013-10-01

    To evaluate the emission behavior of hexabromocyclododecanes (HBCDs) and polybrominated diphenyl ethers (PBDEs) added to textile products as flame retardants, we used a small stainless steel container (7 cm i.d. × 5.5 cm height, ca. 210 cm(3)) to conduct emission tests on three upholstery textile samples at temperatures of 20, 40, 60, and 80 °C. The textile samples, which were intended for use in curtain manufacture and had been treated with either technical HBCD or technical DecaBDE, emitted HBCDs and PBDEs, including BDE 209, even at room temperature (20 °C), and the emission rates increased with increasing test temperature. These results indicate that flame-retardant-treated upholstery textiles have the potential to be major sources of brominated flame retardant contamination in indoor air and dust. The HBCD diastereomer emission profiles at the test temperatures of 20 and 40 °C were similar to the profiles of the original textile samples; in contrast, at the higher test temperatures, the proportion of α-HBCD was larger (up to 70% of the total HBCD emission) than in the original samples. At the higher test temperatures, the proportions of di- to hexa-BDEs in the emissions were clearly larger than in the original sample, suggesting that the textile products treated with technical DecaBDE could be a source of environmentally relevant PBDE congeners such as BDE 47, 99, and 100. The emission rates of HBCDs from the textiles were two orders of magnitude higher than those of PBDEs, suggesting that HBCDs volatilize more easily from textile products to the indoor environment than PBDEs. PMID:24056914

  6. Bioaccumulation kinetics of brominated flame retardants (polybrominated diphenyl ethers) in blue mussels (Mytilus edulis)

    SciTech Connect

    Gustafsson, K.; Bjoerk, M.; Burreau, S.; Gilek, M. )

    1999-06-01

    Baltic Sea blue mussels, Mytilus edulis, were exposed to polybrominated diphenyl ethers (PBDEs, IUPAC congeners 47, 99, and 153) and polychlorinated biphenyls (PCBs, congeners 31, 52, 77, 118, and 153) in a flow-through experimental setup for 44 d. After the exposure phase, the mussels were allowed to depurate in natural brackish water for 26 d. After analyses, uptake clearance rate coefficients (k[sub u]), depuration rate coefficients (k[sub d]), and bioaccumulation factors (BAF) were calculated. A rapid uptake of all PBDEs and PCBs was observed, especially for PBDE congeners 47 and 99. The depuration rate decreased with increasing hydrophobicity as expected for the PCBs, but for the PBDEs, depuration rate coefficients appeared to be of the same magnitude for all three congeners independently of log K[sub OW]. The BAFs obtained for PBDE 47 and PBDE 99 were higher than for all other substances in the study, severalfold higher than for PCBs of similar hydrophobicity. The presented data indicate that the bioaccumulation potential of PBDEs, extensively used as flame retardants, is similar or higher than that of PCBs for filter feeding organisms such as blue mussels.

  7. Exposure to organophosphate and polybrominated diphenyl ether flame retardants via indoor dust and childhood asthma.

    PubMed

    Canbaz, D; van Velzen, M J M; Hallner, E; Zwinderman, A H; Wickman, M; Leonards, P E G; van Ree, R; van Rijt, L S

    2016-06-01

    Although the ubiquitous detection of polybrominated diphenyl ether (PBDE) and organophosphate flame retardants (PFRs) in indoor dust has raised health concerns, only very few epidemiological studies have assessed their impact on human health. Inhalation of dust is one of the exposure routes of FRs, especially in children and can be hazardous for the respiratory health. Moreover, PFRs are structurally similar to organophosphate pesticides, which have been associated with allergic asthma. Thus, we investigated whether the concentrations of PFRs and PBDEs in indoor dust are associated with the development of childhood asthma. We selected 110 children who developed asthma at 4 or at 8 years old and 110 matched controls from a large prospective birth cohort (BAMSE - Barn, Allergy, Milieu Stockholm Epidemiology). We analyzed the concentrations of 7 PFRs and 21 PBDEs in dust collected around 2 months after birth from the mother's mattress. The abundance rank in dust was as follows: TBOEP⪢TPHP>mmp-TMPP>EHDPHP~TDCIPP>TCEP~TCIPP~BDE-209⪢BDE-99>BDE-47>BDE-153>BDE-183>BDE-100. There was no positive association between the FRs in mattress dust and the development of childhood asthma. In contrast, dust collected from mattresses of the mothers of children who would develop asthma contained significant lower levels of TPHP and mmp-TMPP. This study provides data on a wide range of PFRs and PBDEs in dust samples and development of asthma in children. PMID:25952720

  8. Effects of selected polybrominated diphenyl ether flame retardants on lake trout (Salvelinus namaycush) thymocyte viability, apoptosis, and necrosis

    USGS Publications Warehouse

    Birchmeier, Kelly L.; Smith, Kimberly A.; Passino-Reader, Dora R.; Sweet, Leonard I.; Chernyak, Sergei M.; Adams, Jean V.; Omann, Geneva M.

    2005-01-01

    Polybrominated diphenyl ether (PBDE) flame-retardants have been identified as an emergent contaminants issue in many parts of the world. In vitro analyses were conducted to test the hypothesis that selected PBDEs congeners affect viability, apoptosis, and necrosis of thymocytes from laboratory-reared lake trout (Salvelinus namaycush). At current environmental levels (<1 mg/L), effects of the tested PBDEs on thymocytes were negligible. However, at 100 mg/L, major effects were seen for congener brominated diphenyl ether 47 (BDE-47) and minor effects were seen for congener BDE-99.

  9. Neurotoxicity of brominated flame retardants

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) have been commonly used as commercial flame retardants in a variety of products including plastics and textiles. Despite their decreasing usage worldwide, congeners continue to accumulate in the environment, including soil, dust, food, anima...

  10. INTRODUCTION TO BROMINATED FLAME RETARDANTS

    EPA Science Inventory

    Brominated flame retardants (BFRs) are a large and diverse class of major industrial products used to provide fire safety. Tetrabromobisphenol A (TBBPA), Hexabromocylocodecane (HBCD), and Polybrominated Diphenyl Ethers (PBDEs) are the major commercial compounds. TBBPA is a react...

  11. Polybrominated diphenyl ether flame retardants in the U.S. marine environment: a review.

    PubMed

    Yogui, G T; Sericano, J L

    2009-04-01

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in polymeric materials such as furnishing foam, rigid plastics and textiles. The U.S. has historically led the world production of these man-made chemicals and was responsible for about 50% of the total global demand in 2001. Paradoxically, scientific studies addressing sources, behavior and fate of PBDEs in the U.S. environment are limited when compared to those in Europe. This paper reviews the distribution of PBDEs in marine and estuarine matrices of the three U.S. coasts (Atlantic, Pacific and Gulf of Mexico) and Alaska. PBDEs are ubiquitous in all compartments including water, sediment and biota. Contamination is higher in urbanized regions such as the coast of California. In numerous cases, concentrations of PBDEs in U.S. marine matrices are among the highest in the world. Higher PBDE levels in the U.S. marine environment reflect that over 90% of the Penta-BDE global production has been utilized in the United States. BDEs 47, 99 and 100 typically dominate the composition of PBDEs in most samples and exhibit high concentrations in several matrices. BDEs 17, 28, 33, 49, 153, 154 and 155 are also of concern since they are known to be present in a minor proportion in the Penta-BDE products. BDEs 206, 207, 208 and 209 which occur in Deca-BDE products do not appear to accumulate in most marine organisms although they may be debrominated into more toxic congeners. There is still no regulation addressing PBDEs contamination in the U.S. aquatic environments. Thus, efforts to understand the cycling of PBDEs in the environment as well as toxic effects in organisms are needed to support the development of quality criteria. Some PBDE congeners fulfill the criteria to be recognized as persistent organic pollutants (POPs). The addition of PBDEs to the list of POPs established by the United Nations Stockholm Convention will be important in elevating environmental concerns regarding these chemicals to an

  12. Determination of emerging halogenated flame retardants and polybrominated diphenyl ethers in serum by gas chromatography mass spectrometry.

    PubMed

    Cequier, Enrique; Marcé, Rosa Maria; Becher, Georg; Thomsen, Cathrine

    2013-10-01

    Emerging flame retardants are used in a great variety of household goods and thus have the potential to pollute our indoor environment. Health concerns regarding exposure to these flame retardants demand new methods to survey their occurrence in humans. This work describes development and optimization of an analytical method comprising solid phase extraction and gas chromatography coupled to mass spectrometry for the determination of besides 15 polybrominated diphenyl ethers, 7 emerging halogenated flame retardants in human serum (1,2-bis[2,4,6-tribromophenoxy] ethane, decabromodiphenyl ethane, hexabromobenzene, Dechlorane Plus(®), hexachlorocyclopentenyl-dibromocyclooctane, dechlorane 602 and 603). The method was thoroughly validated at three spiking levels obtaining averaged recoveries >80% with a RSD of 5% (n=12). Accuracies ranged from 88 to 125% except for DBDPE, which averaged 66% with overall RSD of 11% (n=12). Method limits of detection (MLD) ranged from 0.3 to 5.4 pg/mL serum, except for decabromodiphenyl ether and decabromodiphenyl ethane for which MLDs were 14 and 20 pg/mL serum, respectively. In human serum samples from Norway, we were able to detect and quantify hexabromobenzene, 1,2-bis[2,4,6-tribromophenoxy] ethane, Dechlorane Plus(®), Dechlorane 602 and 603. PMID:23992842

  13. Multi-class, multi-residue analysis of pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers and novel flame retardants....mass spectrometry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A multi-class, multi-residue method for the analysis of 13 novel flame retardants, 18 representative pesticides, 14 polychlorinated biphenyl (PCB) congeners, 16 polycyclic aromatic hydrocarbons (PAHs), and 7 polybrominated diphenyl ether (PBDE) congeners in catfish muscle was developed and evaluated...

  14. Contamination and distribution of heavy metals, polybrominated diphenyl ethers and alternative halogenated flame retardants in a pristine mangrove.

    PubMed

    Wu, Qihang; Leung, Jonathan Y S; Tam, Nora F Y; Peng, Yisheng; Guo, Pengran; Zhou, Song; Li, Qing; Geng, Xinhua; Miao, Shenyu

    2016-02-15

    Owing to the expanding metal and electronics industries, pollution in the Pearl River Estuary needs special concern. Given the hydrodynamic effect, the pristine mangrove in Qi'ao Island would be contaminated by tidal flushing. Thus, we examined (1) the contamination of pollutants in this mangrove, including heavy metals, polybrominated diphenyl ethers (PBDEs) and alternative halogenated flame retardants (AHFRs), and (2) how habitat characteristics and sediment properties affect their distribution. Results showed that the sediment in Qi'ao mangrove had higher concentrations of heavy metals, PBDEs and AHFRs than that in other pristine mangroves, and similar concentrations to those mangroves impacted by point sources. Heavy metal concentrations were lower in the vegetated areas than mudflat, while the opposite was found for PBDEs and AHFRs. The findings imply that tidal flushing was an important pollution source, while mangrove plants have the capacity to minimize the impact of heavy metals, but not PBDEs and AHFRs. PMID:26759186

  15. Polybrominated diphenyl ethers and alternative flame retardants in air and precipitation samples from the northern Lake Victoria region, East Africa.

    PubMed

    Arinaitwe, Kenneth; Muir, Derek C G; Kiremire, Bernard T; Fellin, Phil; Li, Henrik; Teixeira, Camilla

    2014-01-01

    High volume air and precipitation samples were collected close to the shore of Lake Victoria at Entebbe, Uganda, between October 2008 and July 2010 inclusive. Polybrominated diphenyl ethers (PBDEs) and alternative flame retardants (AFRs) were analyzed by GC-MS. BDEs 47, 99, and 209 were the predominant PBDEs with mean concentrations (in air) of 9.84, 4.38, 8.27 pg m(-3) and mean fluxes in precipitation of 3.40, 6.23, and 7.82 ng m(-2) sample(-1), respectively. 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and hexabromocyclododecane (HBCDD), anti- and syn-Dechlorane plus were detected at levels comparable with those of PBDEs. Both PBDEs and AFRs in air generally increased from 2008 to 2010. Elevated PBDE concentrations in air were associated with slow moving low altitude air masses from the region immediately adjacent to the lake, while low concentrations were mostly associated with fast moving westerly and southwesterly air masses. Analysis of the octa- and nona-BDE profiles suggested photolysis and pyrolytic debromination of BDE-209 in the air samples. The highly halogenated and most abundant PBDEs and AFRs in air also predominated in precipitation samples. This is the first study to report flame retardants in high volume air samples and precipitation in Equatorial Africa. PMID:24400732

  16. Flame retardants

    NASA Technical Reports Server (NTRS)

    Troitzsch, J.

    1988-01-01

    The use of flame retardants in plastics has grown only slightly in recent years and will probably grow slowly in the future. The reasons for this are slow economic growth and the absence of fundamentally new requirements for future fire prevention. The trends are toward the increasing use of easily handled, dust-free and well-dispersed flame retardant compounds and master batches; there are no spectacular new developments. In the future, questions of smoke evolution, toxicity and corrosiveness of combustion gases will become increasingly important, especially due to new regulations and rising requirements for environmental protection.

  17. Levels of polybrominated diphenyl ethers and novel flame retardants in microenvironment dust from Egypt: an assessment of human exposure.

    PubMed

    Hassan, Yasmeen; Shoeib, Tamer

    2015-02-01

    There are very few studies reporting concentrations of polybrominated diphenyl ethers (PBDEs) and novel flame retardants (FRs) or non-PBDEs in Africa and the Middle East. The present work reported concentrations of fourteen PBDE congeners and eleven non-PBDE flame retardants in dust samples collected from homes (n=17), workplaces (n=9) and cars (n=5) in the greater Cairo region. The median ∑PBDE concentrations were 57, 425 and 1608 ng g(-1) in homes, workplaces and cars respectively. The highest PBDE levels were observed for BDE 209, with a median concentration of 40.2, 366 and 1540 ng g(-1) representing 70% to 95% of the total PBDEs in homes, workplaces and cars respectively. This is about 8 to 46 times greater than the median concentration of the pentaBDE (represented by the most abundant compounds in this formulation, ∑BDE 47, 99 and 100). In the case of non-PBDE flame retardants, a detection frequency between 52% and 100% was observed for several compounds including: hexabromocyclododecane (HBCD), hexabromobenzene (HBB), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), bis (2-ethyl-1-hexyl) tetrabromophthalate (TBPH), 1,2-bis (2,4,6-tribromophenoxy) ethane (TBPE), ally-2,4,6-tribromophenyl ether (ATE) and Dechlorane Plus (DP). The ∑non-PBDE median concentrations were 8.30, 28.9 and 49.9 ng g(-1) in homes, workplaces and cars respectively with the highest level observed for HBCD in the three microenvironments. The detection of novel flame retardants in indoor environments may be due to their wide usage after the ban of the penta and octa BDE formulation. Results show the levels of PBDEs and non-PBDEs in Egyptian dust to be among the lowest levels reported from other countries. Different dust exposure scenarios using 5th percentile, median, 95th percentile and maximum levels were estimated for adult and children. The estimated dust intake results were several orders of magnitude lower than the oral reference dose values. PMID:25306095

  18. Polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and "novel" brominated flame retardants in house dust in Germany.

    PubMed

    Fromme, H; Hilger, B; Kopp, E; Miserok, M; Völkel, W

    2014-03-01

    Brominated flame retardants (BFRs) are used in a wide variety of products such as electronic devices, upholstery and carpets and in insulation boards. The study presented here aimed to quantify the amounts of BFRs in house dust in Germany. For this purpose 20 residences' dust samples were collected from vacuum cleaner bags and analysed with LC-MS/MS and simultaneously with GC/MS. Using GC/MS, the median (95th percentile) concentrations of PBDEs (sum of tetra- to hepta-congeners), BDE 209, Σ-HBCD (sum of three congeners), and decabromodiphenylethane (DBDPE) were 42ng/g (230ng/g), 950ng/g (3426ng/g), 335ng/g (1545ng/g), and 146ng/g (1059ng/g), respectively. Using LC-MS/MS some "novel" flame retardants were found in median concentrations of 343ng/g (bis(2-ethyl-1-hexyl)tetrabromophthalate, TBPH), and 28ng/g (tetrabromobisphenol A, TBBPA). Whilst 1,2-bis-(2,4,6-tribromophenoxy)ethane (BTBPE) and 2-ethyl-1-hexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) could not be detected. Based on these measurements an exposure assessment for the sum of tetra- to heptabrominated congeners, BDE 209, and Σ-HBCD resulted in a "high" daily intake for toddlers (based on 95th percentiles) of 1.2ng/kg b.w., 0.69ng/kg b.w., and 8.9ng/kg b.w., respectively. For TBPH the "high" intake was calculated at 4.1ng/kg b.w. and for DBDPE at 5.3ng/kg b.w. A clear tendency was observed to apply "novel" BFRs in Germany. Moreover, the results suggest that the recent exposure to PBDEs and HBCD via house dust in Germany is well below the levels that are associated with health effects. For the "novel" brominated flame retardants such an assessment is not possible due to limited toxicological information. PMID:24368294

  19. A rapid throughput approach identifies cognitive deficits in adult zebrafish from developmental exposure to polybrominated flame retardants

    PubMed Central

    Truong, Lisa; Mandrell, David; Mandrell, Rick; Simonich, Michael; Tanguay, Robert L.

    2014-01-01

    A substantial body of evidence has correlated the human body burdens of some polybrominated diphenyl ether (PBDE) flame retardants with cognitive and other behavioral deficits. Adult zebrafish exhibit testable learning and memory, making them an increasingly attractive model for neurotoxicology. Our goal was to develop a rapid throughput means of identifying the cognitive impact of developmental exposure to flame retardants in the zebrafish model. We exposed embryos from 6 hours post fertilization to 5 days post fertilization to either PBDE 47 (0.1 uM), PBDE 99 (0.1 uM) or PBDE 153 (0.1 uM), vehicle (0.1% DMSO), or embryo medium (EM). The larvae were grown to adulthood and evaluated for the rate at which they learned an active-avoidance response in an automated shuttle box array. Zebrafish developmentally exposed to PBDE 47 learned the active avoidance paradigm significantly faster than the 0.1% DMSO control fish (P < 0.0001), but exhibited significantly poorer performance when retested suggestive of impaired memory retention or altered neuromotor activity. Learning in the PBDE 153 group was not significantly different from the DMSO group. Developmental exposure to 0.1% DMSO impaired adult active avoidance learning relative to the sham group (n = 39; P < 0.0001). PBDE 99 prevented the DMSO effect, yielding a learning rate not significantly different from the sham group (n = 36; P > 0.9). Our results underscore the importance of vehicle choice in accurately assessing chemical effects on behavior. Active avoidance response in zebrafish is an effective model of learning that, combined with automated shuttle box testing, will provide a highly efficient platform for evaluating persistent neurotoxic hazard from many chemicals. PMID:24674958

  20. Analysis of polybrominated diphenyl ethers and emerging halogenated and organophosphate flame retardants in human hair and nails.

    PubMed

    Liu, Liang-Ying; Salamova, Amina; He, Ka; Hites, Ronald A

    2015-08-01

    A method for the digestion, extraction, fractionation, and analysis of three classes of flame retardants, including 36 polybrominated diphenyl ethers (PBDEs), 9 halogenated alternative flame retardants (AFRs), and 12 organophosphate esters (OPEs) in human hair and nail samples was developed. The method employed HNO3/H2O2 digestion, liquid-liquid extraction with (4:1 vol) hexane:dichloromethane, fractionation on a 6g column of 2.5% water deactivated Florisil, and analysis by gas chromatographic mass spectrometry. The accuracy and precision of the method was validated using spiked samples of 6 replicates for both hair and nail samples. The method validation results showed good accuracy and precision for all PBDEs except BDE-209, all AFRs except hexabromobenzene (HBB), and all of the 12 OPEs, with average recovery efficiencies>90% and relative standard deviations (RSDs)<10%. The average recovery efficiencies for HBB were between 60% and 86%, with RSDs<10%. BDE-209 had recovery efficiencies of 64% (RSD, 13%) for hair and 71% (RSD, 10%) for nail. This method was applied to analyze 5 human hair and 5 fingernail samples from the general student population at Indiana University Bloomington campus. BDE-47 and BDE-99 were the predominant PBDEs detected in both hair and nail samples, with a concentration range of 11-620 and 4.6-780ng/g (dry weight) in hair and 7.3-43 and 2.1-11ng/g in nails, respectively. Di-(2-ethylhexyl)-tetrabromophthalate (TBPH) and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) were detected in all the samples, with concentrations of 20-240 and 11-350ng/g in hair and <17-80 and <9.2-71ng/g in nails, respectively. Among the 12 OPEs analyzed, tris(2-chloroethyl)phosphate (TCEP), tris(1-chloro-2-propyl)phosphate (TCIPP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), and triphenyl phosphate (TPHP) were most often detected. The concentrations of these OPEs (summed together) were 1100-3900 and 380-18,000ng/g in hair and nails, respectively. These levels

  1. Behavioral Changes in Aging but Not Young Mice after Neonatal Exposure to the Polybrominated Flame Retardant DecaBDE

    PubMed Central

    Rice, Deborah C.; Thompson, W. Douglas; Reeve, Elizabeth A.; Onos, Kristen D.; Assadollahzadeh, Mina; Markowski, Vincent P.

    2009-01-01

    Background After several decades of commercial use, the flame-retardant chemicals polybrominated diphenyl ethers (PBDEs) and their metabolites are pervasive environmental contaminants and are detected in the human body. Decabrominated diphenyl ether (decaBDE) is currently the only PBDE in production in the United States. Objectives Little is known about the health effects of decaBDE. In the present study we examined the effects of neonatal decaBDE exposure on behavior in mice at two ages. Methods Neonatal male and female C57BL6/J mice were exposed to a daily oral dose of 0, 6, or 20 mg/kg decaBDE from postnatal days 2 through 15. Two age groups were examined: a cohort that began training during young adulthood and an aging cohort of littermates that began training at 16 months of age. Both cohorts were tested on a series of operant procedures that included a fixed-ratio 1 schedule of reinforcement, a fixed-interval (FI) 2-min schedule, and a light–dark visual discrimination. Results We observed minimal effects on the light–dark discrimination in the young cohort, with no effects on the other tasks. The performance of the aging cohort was significantly affected by decaBDE. On the FI schedule, decaBDE exposure increased the overall response rate. On the light–dark discrimination, older treated mice learned the task more slowly, made fewer errors on the first-response choice of a trial but more perseverative errors after an initial error, and had lower latencies to respond compared with controls. Effects were observed in both dose groups and sexes on various measures. Conclusions These findings suggest that neonatal decaBDE exposure produces effects on behavioral tasks in older but not younger animals. The behavioral mechanisms responsible for the pattern of observed effects may include increased impulsivity, although further research is required. PMID:20049210

  2. Brominated flame retardants in Korean river sediments, including changes in polybrominated diphenyl ether concentrations between 2006 and 2009.

    PubMed

    Lee, In-Seok; Kang, Hee-Hyung; Kim, Un-Jung; Oh, Jeong-Eun

    2015-05-01

    Brominated flame retardants were analyzed in sediment samples from the Nakdong River basin, Korea. The total concentrations of the 27 polybrominated diphenyl ethers (PBDEs), including decabrominated diphenyl ether (BDE 209), analyzed were 0.55-300 ng g(-1) dry weight (dw), the BDE 209 concentrations were 0.39-190 ng g(-1) dw, the tetrabromobisphenol A (TBBPA) concentrations were 0.05-150 ng g(-1) dw, and the total hexabromocyclododecane (sum of α-, β-, γ-HBCDs) concentrations were 0.11-19 ng g(-1) dw. The PBDE and HBCD concentrations were comparable to or lower than the concentrations found in sediments from other countries, whereas the TBBPA concentrations were comparable to or higher than the concentrations found in other countries. The TBBPA concentrations were similar to or lower than the PBDE concentrations, even though more than twice as much TBBPA as total PBDEs is consumed in Korea, and this phenomenon was probably caused by TBBPA and PBDEs being used differently during the manufacture of products, and their different half-lives in sediment and affinities for the particle phase in aquatic environments. Sediment samples from several sampling sites close to facilities where expandable polystyrene, epoxy, and polycarbonate resins are manufactured and handled had relatively high TBBPA and HBCD concentrations. Temporal changes in the PBDE concentration strongly correlated with temporal variations in the geochemical compositions such as total organic carbon content and grain size value of the sediment. The PBDE and HBCD distribution profiles in the sediment samples indicated that commercial PBDE and HBCD products were released locally. PMID:25655576

  3. Determination of Polychlorinated Biphenyls, Selected Persistent Organochlorine Pesticides, and Polybrominated Flame Retardants in Fillets of Fishes from the 2007 Missouri Department of Conservation Monitoring Program

    USGS Publications Warehouse

    Gale, Robert W.; Orazio, Carl E.; McKee, Michael J.

    2009-01-01

    This report presents the results of a study to determine polychlorinated biphenyl, organochlorine pesticide, and polybrominated diphenylether flame retardant concentrations in selected fishes from lakes and streams across Missouri. Fillets were collected from each fish sample and after homogenization, compositing, and preparation, analyte concentrations were determined with dual column capillary gas chromatography-electron-capture detection. Total concentrations of polychlorinated biphenyls in samples ranged from background levels of about 50 to 300 nanograms per gram. In samples with elevated contaminant concentrations, chlordanes, DDT-related chemicals, and dieldrin constituted the primary classes of pesticides present, and ranged from 5 to 75 nanograms per gram. Total concentrations of polybrominated diphenyl ethers in samples ranged from background levels of 5 to 86 nanograms per gram. Channel catfish from the upper and lower Blue River and lake sturgeon from the Mississippi River at Saverton exhibited different polybrominated diphenyl ethers ratios. Concentrations of polychlorinated biphenyls, chlordanes, DDT-related compounds, and polybrominated diphenyl ethers all were greatest in samples of channel catfish from the upper and lower Blue River, and in samples of lake sturgeon from the Mississippi River at Saverton.

  4. Sublethal responses of avian embryos exposed to polybrominated diphenyl ether flame retardants

    USGS Publications Warehouse

    Rattner, B.A.; McKernan, M.A.; Ottinger, M.

    2007-01-01

    Polybrominated diphenyl ethers PBDEs) have been detected in bird eggs worldwide, and despite increasing concentrations over the past 25 years, toxicological thresholds have yet to be established. We previously reported embryonic survival, and pipping and hatching success in chicken (Gallus gallus), mallard (Anas platyrhynchos) and American kestrel (Falco sparverius) embryos receiving 0.01-20 :g PBDE/g egg. Survival, pipping and hatching success were decreased in kestrels, suggesting that they are more sensitive to PBDEs than chickens and mallards. Adverse effects were detected in kestrels at levels (> 1 :g/g egg) believed to approach environmentally relevant PBDE concentrations. Polychlorinated biphenyl congener 126 (PCB 126) was used as a positive control (1000 pg/g egg) in this study, and survival endpoints in chicken and kestrel were decreased at this dose. Some PBDE and PCB congeners are structurally similar to thyroid hormones and have been demonstrated to affect thyroid homeostasis in laboratory rodents. In the present study, thyroid glands collected from day old hatchling chickens, mallards, and kestrels and were analyzed for thryoxine (T4) using a solid phase radioimmunoassay (DPC, Inc.) specifically validated for each of these species. Results indicated that thyroid gland T4 stores (total gland content and T4 /mg thyroid) in these species were relatively consistent and not significantly affected by PBDE exposure. In contrast, glandular T4 stores were significantly lower (P < 0.01) in PCB 126 treated kestrels. Decreases in circulating T4 levels in response to contaminants (e.g., PCBs, ammonium perchlorate) may lead to greater release of glandular T4 to maintain a euthyroid state, which could decrease thyroidal T4 stores. While PBDEs have been suggested to influence circulating T4 in kestrel fledglings (Fernie et al., 2005), it appears that glandular T4 was not affected in chicken, mallard or kestrel hatchlings exposed in ovo. Histopathological changes in

  5. Flame retardant exposure: polybrominated diphenyl ethers in blood from Swedish workers.

    PubMed Central

    Sjödin, A; Hagmar, L; Klasson-Wehler, E; Kronholm-Diab, K; Jakobsson, E; Bergman, A

    1999-01-01

    Polybrominated diphenyl ethers (PBDEs) are used as additives in polymers and textiles to prohibit the development of fires. Because of the production and use of PBDEs, their lipophilic characteristics, and persistence, these compounds have become ubiquitous environmental contaminants. The aim of the present study was to determine potential exposures of PBDEs to clerks working full-time at computer screens and personnel at an electronics-dismantling plant, with hospital cleaners as a control group. Five PBDE congeners--2,2',4,4'-tetraBDE; 2,2',4,4',5,5'-hexaBDE; 2,2',4,4',5, 6'-hexaBDE; 2,2',3,4,4',5',6-heptaBDE; and decaBDE--were quantified in blood serum from all three categories of workers. Subjects working at the dismantling plant showed significantly higher levels of all PBDE congeners in their serum as compared to the control group. Decabromodiphenyl ether is present in concentrations of 5 pmol/g lipid weight (lw) in the personnel dismantling electronics; these concentrations are comparable to the concentrations of 2,2',4, 4'-tetraBDE. The latter compound was the dominating PBDE congener in the clerks and cleaners. The major compound in personnel at the dismantling plant was 2,2',3,4,4',5',6-heptaBDE. Concentrations of this PBDE congener are almost twice as high as for 2,2',4, 4'-tetraBDE in these workers and seventy times the level of this heptaBDE in cleaners. The total median PBDE concentrations in the serum from workers at the electronics-dismantling plant, clerks, and cleaners were 37, 7.3, and 5.4 pmol/g lw, respectively. The results show that decabromodiphenyl ether is bioavailable and that occupational exposure to PBDEs occurs at the electronics-dismantling plant. Images Figure 1 Figure 2 PMID:10417362

  6. Brominated flame retardants as food contaminants

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This book chapter reviews analytical methods for the three major brominated flame retardant (BFR) classes in use today, tetrabromobisphenol-A (TBBP-A), hexabromocyclododecanes (HBCDs), and polybrominated diphenyl ethers (PBDEs), a "legacy" BFR no longer in use, polybrominated biphenyls (PBBs), and a...

  7. Polybrominated diphenyl ether flame retardants in eggs may reduce reproductive success of ospreys in Oregon and Washington, USA.

    PubMed

    Henny, Charles J; Kaiser, James L; Grove, Robert A; Johnson, Branden L; Letcher, Robert J

    2009-10-01

    Spatial and temporal assessments and reports of polybrominated diphenyl ether (PBDE) flame retardants in birds remain sparse. In the present study, PBDEs were detected in all 120 osprey (Pandion haliaetus) eggs collected. The eggs were collected from nests along the Columbia, Willamette and Yakima rivers of Oregon (OR) and Washington (WA) and in Puget Sound (WA) between 2002 and 2007. PBDE congeners: 17, 28, 47, 49, 66, 85, 99, 100, 138, 153, 154 (possible coelution with brominated biphenyl 153 [BB153]), 183, 190 (detected in one egg), 209 (not detected), and BB101 (only detected in 2006 and 2007) and total-alpha-hexabromocyclododecane (only detected in five eggs) were analyzed for in the egg samples. Eggs from reservoirs in the forested headwaters of the Willamette River (2002) contained the lowest concentrations of SigmaPBDEs (geometric mean [range], 98 [55.2-275] ng/g wet weight [ww]), while those from the middle Willamette River (2006) contained the highest (897 [507-1,880] ng/g ww). Concentrations in eggs from the Columbia River progressively increased downstream from Umatilla, OR (River Mile [RM] 286) to Skamokoa, WA (RM 29), which indicated additive PBDE sources along the river. In general, regardless of the year of egg collection, differences in PBDE concentrations reported in osprey eggs along the three major rivers studied (Columbia, Willamette and Yakima) seem to reflect differences in river flow (dilution effect) and the extent of human population and industry (source inputs) along the rivers. PBDE concentrations increased over time at two locations (Seattle, WA; Columbia River, RM 29-84) where temporal patterns could be evaluated. Only during 2006 (on the middle Willamette River, RM 61-157) and 2007 (on the lower Columbia River, RM 29-84) did SigmaPBDE concentrations in osprey eggs exceed 1,000 ng/g ww with negative relationships indicated at both locations between productivity and SigmaPBDE concentrations in eggs (P = 0.008, P = 0.057). Osprey eggs

  8. Optimization and development of analytical methods for the determination of new brominated flame retardants and polybrominated diphenyl ethers in sediments and suspended particulate matter.

    PubMed

    López, P; Brandsma, S A; Leonards, P E G; de Boer, J

    2011-05-01

    With more stringent legislation on brominated flame retardants, it is expected that increasing amounts of substitutes would replace polybrominated diphenylethers (PBDEs). Therefore, the development and optimization of analytical methodologies that allow their identification and quantification are of paramount relevance. This work describes the optimization of an analytical procedure to determine pentabromochlorocyclohexane, tetrabromo-o-chlorotoluene, 2,3,5,6-tetrabromo-p-xylene, tetrabromophthalic anhydride, 2,3,4,5,6-pentabromotoluene, tris(2,3-dibromopropyl)phosphate, decabromodiphenylethane and 1,2-bis(2,4,6-tribromophenoxy)ethane together with PBDEs in sediments and in suspended particulate matter. This method comprises a pressurized liquid extraction followed by three cleanup steps (gel permeation chromatography and solid phase extraction on Oasis™ HLB and on silica cartridges). Gas chromatography-mass spectrometry, using electron capture negative chemical ionization, is used for the final analysis. The proposed method provides recoveries >85%. The method was applied to sediment and suspended particulate matter samples from different locations in the Western Scheldt estuary (the Netherlands). To the best of our knowledge, this is the first time that the occurrence of the additive flame retardants 2,3,5,6-tetrabromo-p-xylene, 3,4,5,6-tetrabromo-o-chlorotoluene and 2,3,4,5,6-pentabromochlorocyclohexane is reported in the literature. The concentrations of these new flame retardants ranged from 0.05 to 0.30 μg/kg dry weight. PMID:21369755

  9. Determination of Polychlorinated Biphenyls, Selected Persistent Organochlorine Pesticides, and Polybrominated Flame Retardants in Fillets of Fishes from the 2006 Missouri Department of Conservation Monitoring Programs

    USGS Publications Warehouse

    Gale, Robert W.; May, Thomas W.; Orazio, Carl E.; McKee, Michael J.

    2008-01-01

    This report presents the results of a study to determine polychlorinated biphenyl, organochlorine pesticide, and polybrominated diphenyl ether flame retardant concentrations in selected fishes from lakes and streams across Missouri. Fillets were collected from each fish sample, and after homogenization, compositing, and preparation, analyte concentrations were determined with dual column capillary gas chromatography-electron-capture detection. Total concentrations of polychlorinated biphenyls in samples ranged from background levels of about 20 to 1,200 nanograms per gram. Chlordanes and DDT-related chemicals constituted the primary classes of pesticides present at elevated concentrations in most samples, and ranged from 5 to 340 nanograms per gram. Total concentrations of polybrominated diphenyl ethers in samples ranged from background levels of about 5 to about 410 nanograms per gram. Concentrations of total technical chlordane ranged from less than 5 to 260 nanograms per gram. Concentrations of polychlorinated biphenyls, chlordanes, DDT-related compounds, and polybrominated diphenyl ethers were all greatest in samples of blue catfish from Cape Girardeau and Weldon Spring.

  10. Brominated Flame Retardants

    EPA Science Inventory

    Brominated flame retardants (BFRs) belong to a large class of compounds known as organohalogens. BFRs are currently the largest marketed flame retardant group due to their high performance efficiency and low cost. In the commercial market, more than 75 different BFRs are recogniz...

  11. Polybrominated diphenyl ethers listed as Stockholm Convention POPs, other brominated flame retardants and heavy metals in e-waste polymers in Nigeria.

    PubMed

    Sindiku, Omotayo; Babayemi, Joshua; Osibanjo, Oladele; Schlummer, Martin; Schluep, Mathias; Watson, Alan; Weber, Roland

    2015-10-01

    Polybrominated diphenyl ethers (PBDEs) were the first brominated persistent organic pollutants (POPs) listed in the Stockholm Convention. Parties to the convention are currently establishing inventories for developing action plans for the environmentally sound management of PBDE-containing materials. The major use of commercial octabromodiphenyl ether (c-OctaBDE) has been in casings from cathode ray tube (CRT) TVs and computer monitors. Large quantities of used e-waste and electronic equipment have been exported to developing countries with Nigeria being a major importer in Africa. The casings from 382 TVs and computers imported from major world regions to Nigeria were sampled in backyards and waste dumps. The samples were screened with X-ray flourescence (XRF) for bromine and analysed by gas chromatography/ electron capture detection (GC/ECD) for brominated flame retardants (BFRs). A high proportion of the CRT casings (61 %) contained more than 10,000 ppm bromine from BFRs. Decabromodiphenyl ether (DecaBDE) was the major flame retardant used in TV sets and tetrabromobisphenol A (TBBPA) for computer CRTs.The screening suggests that average PBDE levels (of c-OctaBDE + DecaBDE) in Nigerian-stockpiled CRT casings were 1.1 % for TV and 0.13 % for PC CRTs. These are above the Restriction of Hazardous Substances (RoHS) limit and should be separated for RoHS compliant recycling. The Nigerian e-waste inventory of 237,000 t of CRT plastic would therefore contain approx. 594 t c-OctaBDE and 1,880 t of DecaBDE. In Nigeria, as for most developing countries, there is currently no adequate e-waste management, plastic separation or destruction capacity. The data highlight the urgent need to develop environmentally sound management for this large material flow. PMID:25062546

  12. Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants (aBFRs) in sediments from four bays of the Yellow Sea, North China.

    PubMed

    Zhen, Xiaomei; Tang, Jianhui; Xie, Zhiyong; Wang, Runmei; Huang, Guopei; Zheng, Qian; Zhang, Kai; Sun, Yongge; Tian, Chongguo; Pan, Xiaohui; Li, Jun; Zhang, Gan

    2016-06-01

    The distribution characteristics and potential sources of polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants (aBFRs) were investigated in 54 surface sediment samples from four bays (Taozi Bay, Sishili Bay, Dalian Bay, and Jiaozhou Bay) of North China's Yellow Sea. Of the 54 samples studied, 51 were collected from within the four bays and 3 were from rivers emptying into Jiaozhou Bay. Decabromodiphenylethane (DBDPE) was the predominant flame retardant found, and concentration ranged from 0.16 to 39.7 ng g(-1) dw and 1.13-49.9 ng g(-1) dw in coastal and riverine sediments, respectively; these levels were followed by those of BDE 209, and its concentrations ranged from n.d. to 10.2 ng g(-1) dw and 0.05-7.82 ng g(-1) dw in coastal and riverine sediments, respectively. The levels of DBDPE exceeded those of decabromodiphenyl ether (BDE 209) in most of the samples in the study region, whereas the ratio of DBDPE/BDE 209 varied among the four bays. This is indicative of different usage patterns of brominated flame retardants (BFRs) and also different hydrodynamic conditions among these bay areas. The spatial distribution and composition profile analysis indicated that BFRs in Jiaozhou Bay and Dalian Bay were mainly from local sources, whereas transport from Laizhou Bay by coastal currents was the major source of BFRs in Taozi Bay and Sishili Bay. Both the ∑PBDEs and ∑aBFRs (sum of pentabromotoluene (PBT), 2,3-diphenylpropyl-2,4,6-tribromophenyl ether (DPTE), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB)) were at low concentrations in all the sediments. This is probably attributable to a combination of factors such as low regional usage of these products, atmospheric deposition patterns, coastal currents transportation patterns, and degradation processes for higher BDE congeners. This paper is the first study that has investigated the levels of DBDPE in the coastal sediments of China's Yellow Sea. PMID:26942686

  13. Concentrations and distributions of polybrominated diphenyl ethers and novel brominated flame retardants in tree bark and human hair from Yunnan Province, China.

    PubMed

    Yuan, Haodong; Jin, Jun; Bai, Yao; Li, Qiuxu; Wang, Ying; Hu, Jicheng

    2016-07-01

    The concentrations and distributions of polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) in tree bark and hair samples from the same area in Yunnan Province, China, were determined. The total PBDE and NBFR concentrations in the tree bark samples were 3.8 ng/g lipid weight to 91 ng/g lipid weight and 0.23 ng/g lipid weight to 5.0 ng/g lipid weight, respectively. The total PBDE and NBFR concentrations in the hair samples were 2.1 ng/g dry weight to 14 ng/g dry weight and 0.083 ng/g dry weight to 0.29 ng/g dry weight, respectively. Decabromodiphenyl ether had similar distributions in the tree bark and hair samples, but other PBDE congeners and NBFRs had different distributions in the tree bark and hair samples. External exposure was found to be mainly responsible for the total PBDE and pentabromotoluene concentrations in hair, but both external and internal exposure were responsible for the pentabromophenyl and hexabromobenzene concentrations in hair. PMID:27060640

  14. Predictors of serum concentrations of polybrominated flame retardants among healthy pregnant women in an urban environment: a cross-sectional study

    PubMed Central

    2013-01-01

    Background Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants commonly used in a wide range of products. Prenatal exposure to PBDEs has been associated with adverse neurodevelopment. Our objective was to characterize predictors of exposure to PBDEs among a multi-ethnic, low-income cohort of pregnant women enrolled from highly urban communities in New York City between years 2009–2010. Methods During the first half of pregnancy we collected 316 maternal serum samples and administered an extensive questionnaire including items on demographics, diet and lifestyle. We measured 12 PBDE congeners in blood samples. Using bivariate and multivariate approaches, we regressed the most commonly detected PBDE congeners (PBDE-47, -99, -100 and -153) against potential demographic, dietary and lifestyle predictor variables. Results At least one PBDE congener was detected in each serum sample. Our analyses demonstrate unique predictor patterns for PBDE-47, -99, -100 and -153 based on demographic, lifestyle and dietary characteristics of women. Higher education and increased use of household electronics were associated with higher levels of all 4 congeners. Six characteristics were associated with PBDE-153 serum concentrations, more than for any other congener. These include maternal education, household income, body mass index, solid dairy consumption, processed meat consumption and frequent use of household electronics. Conclusions PBDE exposure in this widespread in this cohort, though levels are lower than previous assessments of US pregnant women. Lower levels may be in response to legislation restricting the production, sale and use of these compounds. In our cohort, we did not observe any individual predictor or a consistent pattern of several predictors representing a significant source of PBDE exposure. These data suggest that legislation and policy may be more effective at reducing exposure than personal lifestyle modifications. PMID

  15. Species-specific accumulation of polybrominated diphenyl ether flame retardants in birds of prey from the Chesapeake Bay region, USA.

    PubMed

    Chen, Da; Hale, Robert C; Watts, Bryan D; La Guardia, Mark J; Harvey, Ellen; Mojica, Elizabeth K

    2010-05-01

    Compared to organochlorines, little is known about polybrominated diphenyl ether (PBDE) contamination of birds of prey breeding in the Chesapeake Bay, the largest estuary in the U.S. This study examined and compared PBDE contamination in eggs of osprey, double-crested cormorant, brown pelican and peregrine falcon from this area. Several legacy persistent organic pollutants such as PCBs and DDE were also investigated. The level of urbanization of the landscape appeared to influence the level of PBDE exposure. PBDE congener distribution patterns varied between piscivorous and terrestrial-feeding birds. This suggests individual congeners may be subject to differences in bioaccumulation, biomagnification or metabolism in the aquatic and terrestrial food webs. Biomagnification of PBDEs was studied in the Bay aquatic food chains for the first time. A biomagnification factor of 25.1 was estimated for SigmaPBDEs for the fish - osprey egg food chain. Hazard quotients, applied as a preliminary evaluation, indicated that PBDEs may pose a moderate hazard to ospreys and peregrine falcons through impairment of reproductive performance. PMID:19948372

  16. Flame retardant spandex type polyurethanes

    NASA Technical Reports Server (NTRS)

    Howarth, J. T.; Sheth, S.; Sidman, K. R.; Massucco, A. A. (Inventor)

    1978-01-01

    Flame retardant elastomeric compositions were developed, comprised of: (1) spandex type polyurethane having incorporated into the polymer chain, halogen containing polyols; (2) conventional spandex type polyurethanes in physical admixture flame retardant additives; and (3) fluoroelastomeric resins in physical admixture with flame retardant additives. Methods of preparing fibers of the flame retardant elastomeric materials are presented and articles of manufacture comprised of the elastomeric materials are mentioned.

  17. Flame Retardant Epoxy Resins

    NASA Technical Reports Server (NTRS)

    Thompson, C. M.; Smith, J. G., Jr.; Connell, J. W.; Hergenrother, P. M.; Lyon, R. E.

    2004-01-01

    As part of a program to develop fire resistant exterior composite structures for future subsonic commercial aircraft, flame retardant epoxy resins are under investigation. Epoxies and their curing agents (aromatic diamines) containing phosphorus were synthesized and used to prepare epoxy formulations. Phosphorus was incorporated within the backbone of the epoxy resin and not used as an additive. The resulting cured epoxies were characterized by thermogravimetric analysis, propane torch test, elemental analysis and microscale combustion calorimetry. Several formulations showed excellent flame retardation with phosphorous contents as low as 1.5% by weight. The fracture toughness of plaques of several cured formulations was determined on single-edge notched bend specimens. The chemistry and properties of these new epoxy formulations are discussed.

  18. Brominated flame retardants: cause for concern?

    PubMed Central

    Birnbaum, Linda S; Staskal, Daniele F

    2004-01-01

    Brominated flame retardants (BFRs) have routinely been added to consumer products for several decades in a successful effort to reduce fire-related injury and property damage. Recently, concern for this emerging class of chemicals has risen because of the occurrence of several classes of BFRs in the environment and in human biota. The widespread production and use of BFRs; strong evidence of increasing contamination of the environment, wildlife, and people; and limited knowledge of potential effects heighten the importance of identifying emerging issues associated with the use of BFRs. In this article, we briefly review scientific issues associated with the use of tetrabromobisphenol A, hexabromocyclododecane, and three commercial mixtures of polybrominated diphenyl ethers and discuss data gaps. Overall, the toxicology database is very limited; the current literature is incomplete and often conflicting. Available data, however, raise concern over the use of certain classes of brominated flame retardants. PMID:14698924

  19. Pilot study on the dietary habits and lifestyles of girls with idiopathic precocious puberty from the city of Rome: potential impact of exposure to flame retardant polybrominated diphenyl ethers.

    PubMed

    Tassinari, Roberta; Mancini, Francesca R; Mantovani, Alberto; Busani, Luca; Maranghi, Francesca

    2015-11-01

    Puberty is regulated by the endocrine system, which when disrupted can affect reproductive health. Endocrine disrupters (ED) are involved in the pathogenesis of idiopathic central precocious puberty (ICPP). Polybrominated diphenyl ethers (PBDE) are lipophilic, persistent ED used as flame retardants in several products; thus, human population is exposed through food and domestic dust. PBDE exposure during the peripubertal period is suspected to interfere with reproductive development. The study aimed to investigate PBDE serum concentration in 31 girls with ICPP as well as describe their dietary habits and lifestyles. The PBDE median level was 59 ng/g of lipids, higher than in healthy girls in comparable studies. Interestingly, elder girls and girls with higher body mass index (BMI) showed higher PBDE serum levels. Considering the relevance of altered puberty onset as a risk factor for reproductive health, studies on food contribution to PBDE exposure in Italian children, and efforts to ameliorate risk assessment for emerging chemicals are suggested. PMID:26226124

  20. Flame retarded asphalt blend composition

    SciTech Connect

    Walters, R.B.

    1987-04-21

    This patent describes a flame retarded asphalt composition consisting essentially of a blend of: (a) thermoplastic elastomer modified bitumen; (b) 20-30 wt % inert filler; (c) 1-20 wt % of at least one halogenated flame retardant; and (d) 1-5 wt % of at least one inorganic phosphorus containing compound selected from the group consisting of ammonium phosphate compounds and red phosphorus.

  1. Acute Neurobehavorial Toxicity of Flame Retardant Replacement Compounds in Zebrafish Larvae

    EPA Science Inventory

    As polybrominated diphenyl ethers (PBDEs) are phased out, numerous compounds areemerging as potential replacement flame retardants for use in consumer and electronicproducts. Little is known, however, about the neurobehavioral toxicity of thesereplacements. This study evaluated t...

  2. OVERVIEW AND EVALUATION OF NEUROBEHAVIORAL EFFECTS OF FLAME RETARDANTS IN LABORATORY ANIMALS.

    EPA Science Inventory

    Polybrominated diphenyl ether (PBDE) flame retardants are used worldwide and have been detected in numerous environmental, including human, samples. Concern has been raised regarding their potential developmental neurotoxic effects. There is an emerging literature on behavioral...

  3. Acute and Developmental Behavioral Effects of Flame Retardants and Related Chemicals in Zebrafish

    EPA Science Inventory

    As polybrominated diphenyl ethers are phased out, numerous compounds are emerging as potential replacement flame retardants for use in consumer and electronic products. Little is known, however, about the neurobehavioral toxicity of these replacements. This study evaluated the ne...

  4. BROMINATED FLAME RETARDANTS: WHAT WE KNOW, AND WHAT WE DON’T

    EPA Science Inventory

    Brominated flame retardants (BFRs) represent a large and diverse class of high volume industrial chemicals which have been developed to provide fire safety. There are many other BFRs which have been used and are under development. Historically, polybrominated biphenyls (PBBs) ...

  5. Flame Retardant Applications in Camping Tents and Potential Exposure.

    PubMed

    Keller, Alexander S; Raju, Nikhilesh P; Webster, Thomas F; Stapleton, Heather M

    2014-02-11

    Concern has mounted over health effects caused by exposure to flame retardant additives used in consumer products. Significant research efforts have focused particularly on exposure to polybrominated diphenyl ethers (PBDEs) used in furniture and electronic applications. However, little attention has focused on applications in textiles, particularly textiles meeting a flammability standard known as CPAI-84. In this study, we investigated flame retardant applications in camping tents that met CPAI-84 standards by analyzing 11 samples of tent fabrics for chemical flame retardant additives. Furthermore, we investigated potential exposure by collecting paired samples of tent wipes and hand wipes from 27 individuals after tent setup. Of the 11 fabric samples analyzed, 10 contained flame retardant additives, which included tris(1,3-dichloroisopropyl) phosphate (TDCPP), decabromodiphenyl ether (BDE-209), triphenyl phosphate, and tetrabromobisphenol-A. Flame retardant concentrations were discovered to be as high as 37.5 mg/g (3.8% by weight) in the tent fabric samples, and TDCPP and BDE-209 were the most frequently detected in these samples. We also observed a significant association between TDCPP levels in tent wipes and those in paired hand wipes, suggesting that human contact with the tent fabric material leads to the transfer of the flame retardant to the skin surface and human exposure. These results suggest that direct contact with flame retardant-treated textiles may be a source of exposure. Future studies will be needed to better characterize exposure, including via inhalation and dermal sorption from air. PMID:24804279

  6. Flame Retardant Applications in Camping Tents and Potential Exposure

    PubMed Central

    2015-01-01

    Concern has mounted over health effects caused by exposure to flame retardant additives used in consumer products. Significant research efforts have focused particularly on exposure to polybrominated diphenyl ethers (PBDEs) used in furniture and electronic applications. However, little attention has focused on applications in textiles, particularly textiles meeting a flammability standard known as CPAI-84. In this study, we investigated flame retardant applications in camping tents that met CPAI-84 standards by analyzing 11 samples of tent fabrics for chemical flame retardant additives. Furthermore, we investigated potential exposure by collecting paired samples of tent wipes and hand wipes from 27 individuals after tent setup. Of the 11 fabric samples analyzed, 10 contained flame retardant additives, which included tris(1,3-dichloroisopropyl) phosphate (TDCPP), decabromodiphenyl ether (BDE-209), triphenyl phosphate, and tetrabromobisphenol-A. Flame retardant concentrations were discovered to be as high as 37.5 mg/g (3.8% by weight) in the tent fabric samples, and TDCPP and BDE-209 were the most frequently detected in these samples. We also observed a significant association between TDCPP levels in tent wipes and those in paired hand wipes, suggesting that human contact with the tent fabric material leads to the transfer of the flame retardant to the skin surface and human exposure. These results suggest that direct contact with flame retardant-treated textiles may be a source of exposure. Future studies will be needed to better characterize exposure, including via inhalation and dermal sorption from air. PMID:24804279

  7. Halogenated flame retardants in the Great Lakes environment.

    PubMed

    Venier, Marta; Salamova, Amina; Hites, Ronald A

    2015-07-21

    Flame retardants are widely used industrial chemicals that are added to polymers, such as polyurethane foam, to prevent them from rapidly burning if exposed to a small flame or a smoldering cigarette. Flame retardants, especially brominated flame retardants, are added to many polymeric products at percent levels and are present in most upholstered furniture and mattresses. Most of these chemicals are so-called "additive" flame retardants and are not chemically bound to the polymer; thus, they migrate from the polymeric materials into the environment and into people. As a result, some of these chemicals have become widespread pollutants, which is a concern given their possible adverse health effects. Perhaps because of their environmental ubiquity, the most heavily used group of brominated flame retardants, the polybrominated diphenyl ethers (PBDEs), was withdrawn from production and use during the 2004-2013 period. This led to an increasing demand for other flame retardants, including other brominated aromatics and organophosphate esters. Although little is known about the use or production volumes of these newer flame retardants, it is evident that some of these chemicals are also becoming pervasive in the environment and in humans. In this Account, we describe our research on the occurrence of halogenated and organophosphate flame retardants in the environment, with a specific focus on the Great Lakes region. This Account starts with a short introduction to the first generation of brominated flame retardants, the polybrominated biphenyls, and then presents our measurements of their replacement, the PBDEs. We summarize our data on PBDE levels in babies, bald eagles, and in air. Once these compounds came off the market, we began to measure several of the newer flame retardants in air collected on the shores of the Great Lakes once every 12 days. These new measurements focus on a tetrabrominated benzoate, a tetrabrominated phthalate, a hexabrominated diphenoxyethane

  8. Characterization of Liver Toxicity in F344/N Rats and B6C3F1 mice after Exposure to a Flame Retardant containing lower molecular weight Polybrominated Diphenyl Ethers

    PubMed Central

    Dunnick, June K.; Nyska, Abraham

    2009-01-01

    Lower molecular weight polybrominated diphenylethers (PBDEs), components of flame retardants, are found in the environment and in human and animal tissues. Toxicity studies were conducted in F344/N rats and B6C3F1 mice by administering a flame retardant containing these lower molecular weight PBDEs (BDE-47, BDE-99, BDE-100, and BDE153) by oral gavage 5 days/week for 13 weeks at doses of 0.01, 5, 50, 100 or 500 mg/kg/day. Liver was the primary target organ in rats and mice. Treatment-related increases in liver weights, liver cytochrome P450 (1A1, 1A2, 2B) and UDPGT (rats only) levels, and liver lesions were seen in both rats and mice. Hepatocyte hypertrophy and vacuolization increased in incidence and severity with treatment, and occurred at levels of 50 mg/kg and above in rats, and at 100 mg/kg and above in mice. Liver Cyp 1A1, 1A2, and 2B levels were increased at exposure levels of 50 mg/kg and above in rats and mice. In addition, treatment-related thyroid lesions occurred particularly in rats. The most sensitive parameter for PBDE toxicity was the increase in liver weights which occurred at 5 mg/kg above in rats and 50 mg/kg and above in mice. These results suggest that liver may be a target organ for carcinogenesis processes after long-term administration of PBDEs. A chronic PBDE study is currently being conducted by the National Toxicology Program. PMID:18774282

  9. Multi-class, multi-residue analysis of pesticides, polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenyl ethers and novel flame retardants in fish using fast, low-pressure gas chromatography-tandem mass spectrometry.

    PubMed

    Sapozhnikova, Yelena; Lehotay, Steven J

    2013-01-01

    A multi-class, multi-residue method for the analysis of 13 novel flame retardants, 18 representative pesticides, 14 polychlorinated biphenyl (PCB) congeners, 16 polycyclic aromatic hydrocarbons (PAHs), and 7 polybrominated diphenyl ether (PBDE) congeners in catfish muscle was developed and evaluated using fast low pressure gas chromatography triple quadrupole tandem mass spectrometry (LP-GC/MS-MS). The method was based on a QuEChERS (quick, easy, cheap, effective, rugged, safe) extraction with acetonitrile and dispersive solid-phase extraction (d-SPE) clean-up with zirconium-based sorbent prior to LP-GC/MS-MS analysis. The developed method was evaluated at 4 spiking levels and further validated by analysis of NIST Standard Reference Materials (SRMs) 1974B and 1947. Sample preparation for a batch of 10 homogenized samples took about 1h/analyst, and LP-GC/MS-MS analysis provided fast separation of multiple analytes within 9min achieving high throughput. With the use of isotopically labeled internal standards, recoveries of all but one analyte were between 70 and 120% with relative standard deviations less than 20% (n=5). The measured values for both SRMs agreed with certified/reference values (72-119% accuracy) for the majority of analytes. The detection limits were 0.1-0.5ng g(-1) for PCBs, 0.5-10ng g(-1) for PBDEs, 0.5-5ng g(-1) for select pesticides and PAHs and 1-10ng g(-1) for flame retardants. The developed method was successfully applied for analysis of catfish samples from the market. PMID:23245899

  10. Novel flame retardants (N-FRs), polybrominated diphenyl ethers (PBDEs) and dioxin-like polychlorinated biphenyls (DL-PCBs) in fish, penguin, and skua from King George Island, Antarctica.

    PubMed

    Wolschke, Hendrik; Meng, Xiang-Zhou; Xie, Zhiyong; Ebinghaus, Ralf; Cai, Minghong

    2015-07-15

    Persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs), are frequently detected in biota from Antarctica, whereas no data are available for their replacements, such as novel flame retardants (N-FRs). This study presented the occurrence of several N-FRs, PBDEs, and PCBs in tissue samples of an Antarctic rock cod (Trematomus bernacchii), a young gentoo penguin (Pygoscelis papua), and a brown skua (Stercorarius antarcticus) collected from King George Island. The total concentrations of N-FRs (ΣN-FRs; mean: 931 pg/g dry weight (dw)) were comparable to PBDEs (Σ8PBDEs; 681 pg/gdw), which were much lower than PCBs (ΣDL-PCBs; 12,800 pg/gdw). Overall, skua contained two to three orders of magnitude higher contamination than penguin and fish. In the future, more attention should be focused on the fate of N-FRs in Antarctica, where usages have increased since PBDEs were banned. To our knowledge, this is the first report of N-FRs in biota from Antarctica. PMID:25912262

  11. Levels of Non-Polybrominated Diphenyl Ether Brominated Flame Retardants in Residential House Dust Samples and Fire Station Dust Samples in California

    PubMed Central

    Brown, F Reber; Whitehead, Todd P; Park, June-Soo; Metayer, Catherine; Petreas, Myrto X

    2014-01-01

    Eleven novel brominated flame retardants (NBFRs) were analyzed in dust samples from California homes as a part of the Northern California Childhood Leukemia Study (NCCLS) and from the living quarters of California fire stations as a part of the Firefighter Occupational Exposure (FOX) study using high resolution gas chromatography/mass spectrometry. The eleven NBFRs, were: α- and β-1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (α- and β-DBE-DBCH), 2-bromoallyl 2,3,6-tribromophenylether (BATE), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), 2,3-dibromopropyl 2,4,6-tribromophenyl ether (TBP-DBPE), hexabromobenzene (HBB), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP), and decabromodiphenylethane (DBDPE). Six of the seven NBFRs that are produced in relatively small quantities (i.e., α−, β−DBE-DBCH, BATE, PBEB, PBT, TBP-DBPE) were measured close to or below the limit of quantitation (0.64 ng/g) in both the NCCLS and FOX samples, and the seventh, HBB, was measured at median concentrations of 1.85 ng/g and 9.40 ng/g in the NCCLS and FOX samples, respectively. The remaining four NBFRs, EH-TBB, BEH-TEBP, BTBPE, and DBDPE, are produced in higher quantities, and were detected at median concentrations of 337 ng/g, 186 ng/g, 22.3, ng/g, and 82.8 ng/g, respectively in the NCCLS samples, and at median concentrations of 2687 ng/g, 2076 ng/g, 28.4 ng/g, and 161 ng/g, respectively, in the FOX samples. Concentrations of NBFRs in the NCCLS and FOX dust samples were several times lower than concentrations of PBDEs previously measured in the same samples. Concentrations of NBFRs in the NCCLS and FOX dust samples were generally comparable to concentrations of NBFRs in other studies of house dust from the US and Canada. PMID:25261858

  12. Levels of non-polybrominated diphenyl ether brominated flame retardants in residential house dust samples and fire station dust samples in California.

    PubMed

    Brown, F Reber; Whitehead, Todd P; Park, June-Soo; Metayer, Catherine; Petreas, Myrto X

    2014-11-01

    Eleven novel brominated flame retardants (NBFRs) were analyzed in dust samples from California homes as a part of the Northern California Childhood Leukemia Study (NCCLS) and from the living quarters of California fire stations as a part of the Firefighter Occupational Exposure (FOX) study using high resolution gas chromatography/mass spectrometry. The eleven NBFRs were α- and β-1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (α- and β-DBE-DBCH), 2-bromoallyl 2,3,6-tribromophenylether (BATE), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), 2,3-dibromopropyl 2,4,6-tribromophenyl ether (TBP-DBPE), hexabromobenzene (HBB), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP), and decabromodiphenylethane (DBDPE). Six of the seven NBFRs that are produced in relatively small quantities (i.e., α-, β-DBE-DBCH, BATE, PBEB, PBT, TBP-DBPE) were measured close to or below the limit of quantitation (0.64 ng/g) in both the NCCLS and FOX samples, and the seventh, HBB, was measured at median concentrations of 1.85 ng/g and 9.40 ng/g in the NCCLS and FOX samples, respectively. The remaining four NBFRs, EH-TBB, BEH-TEBP, BTBPE, and DBDPE, are produced in higher quantities, and were detected at median concentrations of 337 ng/g, 186 ng/g, 22.3 ng/g, and 82.8 ng/g, respectively in the NCCLS samples, and at median concentrations of 2687 ng/g, 2076 ng/g, 28.4 ng/g, and 161 ng/g, respectively, in the FOX samples. Concentrations of NBFRs in the NCCLS and FOX dust samples were several times lower than concentrations of PBDEs previously measured in the same samples. Concentrations of NBFRs in the NCCLS and FOX dust samples were generally comparable to concentrations of NBFRs in other studies of house dust from the US and Canada. PMID:25261858

  13. Flame retardant polyphosphazenes

    NASA Technical Reports Server (NTRS)

    Paciorek, K. L.; Karle, D. W.; Kratzer, R. H.

    1973-01-01

    Six polyphosphazene compositions were prepared by reaction of three bis-tertiary phosphines with two phenyl-s-triazine derived diazides. All six polyphosphazenes produced were completely characterized, four of them were furthermore subjected to isothermal gravimetric analysis, smoke density measurements, flammability and oxidative thermal degradation testing. The results of the characterization studies indicate that only low molecular weight oligomers, possibly of a cyclic structure, were obtained in the polymerization reactions. Despite this, however, two of the materials showed no weight loss after 96 hr at 200 C, one did not autoignite at 500 C in air, and all four self extinguished when exposed to a flame as soon as contact between flame and resin was lost. The only toxic decomposition products to be concerned about were found to be hydrogen cyanide and benzene. Under the conditions employed it was proven, however, that the quantities of toxic products are greatly reduced if no ignition takes place, e.g., if thermal decomposition proceeds at a sufficiently low rate.

  14. Effects of the bioaccumulative polybrominated diphenyl ether flame retardant congener BDE-47 on growth, development, and reproductive success in zebra finches.

    PubMed

    Currier, Heidi A; Letcher, Robert J; Williams, Tony D; Elliott, John E

    2015-02-01

    This study investigated the effects of the polybrominated diphenyl ether congener, 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) on the growth and development, and subsequent breeding success of exposed zebra finches (Taeniopygia guttata). Using oral dosing procedures and treatments adjusted by weight, we treated newly hatched chicks daily for the first 20-days-post-hatch (dph) with varying treatments of BDE-47 (0, 5, 50, and 500 ng/g bw/day). Weight and tarsal measurements were monitored from hatch to 90 dph, but no differences were observed between treatment groups at any age. Treated females that reached sexual maturity were mated with untreated males; however, again no treatment effects were observed on breeding success. Analysis of tissue samples at 21 dph did indicate that debromination of BDE-47 had occurred resulting in BDE-28 and BDE-17 metabolites. PMID:25283367

  15. Polybrominated diphenyl ether flame retardants in Chesapeake Bay region, U.S.A., peregrine falcon (Falco peregrinus) eggs: urban/rural trends.

    PubMed

    Potter, Katherine E; Watts, Bryan D; La Guardia, Mark J; Harvey, Ellen P; Hale, Robert C

    2009-05-01

    A total of 23 peregrine falcon (Falco peregrinus) eggs were obtained between 1993 and 2002 from 13 nests, encompassing 11 locations in the Chesapeake Bay region, U.S.A. When multiple eggs were available from the same clutch, average clutch contaminant concentrations were calculated. An overall median total polybrominated diphenyl ether (PBDE) level of 201 ng/g wet weight was determined for the eggs/clutches examined. The maximum in an individual egg, from an urban highway bridge site, was 354 ng/g. This egg also exhibited the highest BDE 209 burden (48.2 ng/g). Compared to distributions reported in fish and piscivorous birds, falcon eggs were enriched in the more brominated congeners. The BDE congeners 153, 99, and 100 constituted 26.0, 24.8, and 13.1%, respectively, of total PBDEs. In most aquatic species, BDE 47 is the most abundant congener reported; however, it constituted only 4.4% of total PBDEs in the eggs of the present study. The median BDE 209 concentration was 6.3 ng/g. The sum of the octa- to nonabrominated congeners (BDEs 196, 197, 206, 207, and 208) contributed, on average, 14.0% of total PBDEs, exceeding the contribution of BDE 209 (5.9%). Concentrations of polychlorinated biphenyls (PCBs) and 1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene (4,4'-DDE) also were determined in a subset of 16 eggs (collected in 2001-2002 from six nests) and were an order of magnitude greater than the corresponding PBDEs. Median BDE 209 concentrations were significantly correlated (p < 0.01, Spearman R = 0.690) with the human population density of the area surrounding the nest. Total PBDEs, total PCBs, and 4,4'-DDE levels were not correlated to human population density. PMID:19102579

  16. Relationships between polybrominated diphenyl ethers and transcription and activity of type 1 deiodinase in a gull highly exposed to flame retardants.

    PubMed

    François, Anthony; Técher, Romy; Houde, Magali; Spear, Philip; Verreault, Jonathan

    2016-09-01

    Deca-brominated diphenyl ether (deca-BDE), composed mainly of BDE-209, is subject to usage restrictions in North America and Europe, although global action on its continued use has yet to be undertaken. Relatively large concentrations of polybrominated diphenyl ethers (PBDEs), especially BDE-209 and its higher brominated degradation products, have been reported in tissues of ring-billed gulls (Larus delawarensis) breeding near the densely populated city of Montreal (QC, Canada). There is limited knowledge of BDE-209 biotransformation and toxicokinetics in birds. Deiodinases, a class of enzymes catalyzing thyroid hormone conversion, have been suggested to be involved in BDE-209 debromination in birds. The objective of the present study was to investigate the relationships between PBDE concentrations and type 1 deiodinase (D1) transcription and in vitro activity (microsomes) in livers of Montreal-breeding ring-billed gulls. The ring-billed gulls exhibiting the highest D1 activity in liver microsomes accumulated the greatest liver concentrations of hepta-BDEs and octa-BDEs. Activity of D1 was inversely related to concentration ratios of BDE-209 to octa-BDEs and ∑hepta-BDE. An even stronger inverse relation was found between D1 activity and BDE-209 to ∑nona + octa + hepta-BDE concentration ratios. The messenger ribonucleic acid (mRNA) levels of D1 in gull livers were inversely associated with liver concentrations of ∑octa-BDE. The present study's findings suggest that D1 is potentially involved in BDE-209 biotransformation and accumulation of higher brominated PBDEs in livers of ring-billed gulls. Environ Toxicol Chem 2016;35:2215-2222. © 2016 SETAC. PMID:27336952

  17. Associations between human exposure to polybrominated diphenyl ether flame retardants via diet and indoor dust, and internal dose: A systematic review.

    PubMed

    Bramwell, Lindsay; Glinianaia, Svetlana V; Rankin, Judith; Rose, Martin; Fernandes, Alwyn; Harrad, Stuart; Pless-Mulolli, Tanja

    2016-01-01

    The aim of this review was to identify and appraise the current international evidence of associations between concentrations of polybrominated diphenyl ethers (PBDEs) in humans and their indoor dusts and food. We systematically searched Medline, Embase, Web of Science and Scopus (up to Jan 2015), using a comprehensive list of keywords, for English-language studies published in peer-reviewed journals. We extracted information on study design, quality, participants, sample collection methods, adjustments for potential confounders and correlations between PBDE concentrations in internal and external matrices. Of 131 potential articles, 17 studies met the inclusion criteria and were included in the narrative synthesis. We concluded that three key factors influenced correlations between external and internal PBDE exposure; half-life of individual congeners in the human body; proximity and interaction between PBDE source and study subject; and time of study relative to phase out of PBDE technical products. Internal dose of Penta-BDE technical mix congeners generally correlated strongly with dust. The exception was BDE-153 which is known to have higher persistence in human tissues. Despite the low bioaccessibility and short half-life of BDE-209, its high loading in dusts gave strong correlations with body burden where measured. Correlations between PBDE concentrations in duplicate diet and body burden were not apparent from the included studies. Whether dust or diet is the primary exposure source for an individual is tied to the loading of PBDE in dust or food items and the amounts ingested. Simple recommendations such as more frequent hand washing may reduce PBDE body burden. PMID:27066981

  18. Neurotoxicity of Brominated Flame Retardants: (In)direct Effects of Parent and Hydroxylated Polybrominated Diphenyl Ethers on the (Developing) Nervous System

    PubMed Central

    van den Berg, Martin; Westerink, Remco H.S.

    2011-01-01

    Background/objective: Polybrominated diphenyl ethers (PBDEs) and their hydroxylated (OH-) or methoxylated forms have been detected in humans. Because this raises concern about adverse effects on the developing brain, we reviewed the scientific literature on these mechanisms. Data synthesis: Many rodent studies reported behavioral changes after developmental, neonatal, or adult exposure to PBDEs, and other studies documented subtle structural and functional alterations in brains of PBDE-exposed animals. Functional effects have been observed on synaptic plasticity and the glutamate–nitric oxide–cyclic guanosine monophosphate pathway. In the brain, changes have been observed in the expression of genes and proteins involved in synapse and axon formation, neuronal morphology, cell migration, synaptic plasticity, ion channels, and vesicular neurotransmitter release. Cellular and molecular mechanisms include effects on neuronal viability 
(via apoptosis and oxidative stress), neuronal differentiation and migration, neurotransmitter release/uptake, neurotransmitter receptors and ion channels, calcium (Ca2+) homeostasis, and intracellular signaling pathways. Discussion: Bioactivation of PBDEs by hydroxylation has been observed for several endocrine end points. This has also been observed for mechanisms related to neurodevelopment, including binding to thyroid hormone receptors and transport proteins, disruption of Ca2+ homeostasis, and modulation of GABA and nicotinic acetylcholine receptor function. Conclusions: The increased hazard for developmental neurotoxicity by hydroxylated (OH-)PBDEs compared with their parent congeners via direct neurotoxicity and thyroid disruption clearly warrants further investigation into a) the role of oxidative metabolism in producing active metabolites of PBDEs and their impact on brain development; b) concentrations of parent and OH-PBDEs in the brain; and c) interactions between different environmental contaminants during exposure to

  19. Brominated flame retardant exposure of aircraft personnel.

    PubMed

    Strid, Anna; Smedje, Greta; Athanassiadis, Ioannis; Lindgren, Torsten; Lundgren, Håkan; Jakobsson, Kristina; Bergman, Åke

    2014-12-01

    The use of brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) in aircraft is the result of high fire safety demands. Personnel working in or with aircraft might therefore be exposed to several BFRs. Previous studies have reported PBDE exposure in flight attendants and in passengers. One other group that may be subjected to significant BFR exposure via inhalation, are the aircraft maintenance workers. Personnel exposure both during flights and maintenance of aircraft, are investigated in the present study. Several BFRs were present in air and dust sampled during both the exposure scenarios; PBDEs, hexabromocyclododecane (HBCDD), decabromodiphenyl ethane (DBDPE) and 1,2-bis (2,4,6-tribromophenoxy) ethane. PBDEs were also analyzed in serum from pilots/cabin crew, maintenance workers and from a control group of individuals without any occupational aircraft exposure. Significantly higher concentrations of PBDEs were found in maintenance workers compared to pilots/cabin crew and control subjects with median total PBDE concentrations of 19, 6.8 and 6.6 pmol g(-1) lipids, respectively. Pilots and cabin crew had similar concentrations of most PBDEs as the control group, except for BDE-153 and BDE-154 which were significantly higher. Results indicate higher concentrations among some of the pilots compared to the cabin crew. It is however, evident that the cabin personnel have lower BFR exposures compared to maintenance workers that are exposed to such a degree that their blood levels are significantly different from the control group. PMID:24745557

  20. Flame retardant cotton based highloft nonwovens

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flame retardancy has been a serious bottleneck to develop cotton blended very high specific volume bulky High loft fabrics. Alternately, newer approach to produce flame retardant cotton blended High loft fabrics must be employed that retain soft feel characteristics desirable of furnishings. Hence, ...

  1. Brominated flame retardants in fish of Lake Geneva (Switzerland).

    PubMed

    Cheaib, Zeinab; Grandjean, Dominique; Kupper, Thomas; de Alencastro, Luiz F

    2009-04-01

    Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) were determined in fish (Salmo trutta forma lacustris) from Lake Geneva. Brominated flame retardants were detected in all nine samples with an average concentration for the sum of BDE-28, BDE-47, BDE-49, BDE-66, BDE-99, BDE-100, BDE-119, BDE-153, BDE-154 and BDE-209 of 207 ng per g lipid weight (ng g lw(-1)). The congener patterns were dominated by BDE-47. The average concentration of HBCD was 168 ng g lw(-1). PMID:19142559

  2. Effects of brominated flame retardants on calcium buffering mechanisms in rat brain in vitro.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs; used as additive flame-retardants) have been detected in human blood, adipose tissue, and breast milk. Developmental and long-term exposures to these chemicals may pose a human health risk, especially to children. It has been demonstrated th...

  3. BROMINATED FLAME RETARDANTS: WHAT WE KNOW, AND WHAT WE DON�T

    EPA Science Inventory

    Brominated flame retardants (BFRs) represent a large and diverse class of high volume industrial chemicals which have been developed to provide fire safety. There are many other BFRs which have been used and are under development. Historically, polybrominated biphenyls (PBBs) w...

  4. Public health implications of components of plastics manufacture. Flame retardants.

    PubMed Central

    Pearce, E M; Liepins, R

    1975-01-01

    The four processes involved in the flammability of materials are described and related to the various flame retardance mechanisms that may operate. Following this the four practical approaches used in improving flame retardance of materials are described. Each approach is illustrated with a number of typical examples of flame retardants or synthetic procedures used. This overview of flammability, flame retardance, and flame retardants used is followed by a more detailed examination of most of the plastics manufactured in the United States during 1973, their consumption patterns, and the primary types of flame retardants used in the flame retardance of the most used plastics. The main types of flame retardants are illustrated with a number of typical commercial examples. Statistical data on flame retardant market size, flame retardant growth in plastics, and price ranges of common flame retardants are presented. Images FIGURE 1. FIGURE 2. FIGURE 3. FIGURE 4. PMID:1175568

  5. Biodegradation of brominated and organophosphorus flame retardants.

    PubMed

    Waaijers, Susanne L; Parsons, John R

    2016-04-01

    Brominated flame retardants account for about 21% of the total production of flame retardants and many of these have been identified as persistent, bioaccumulative and toxic. Nevertheless, debromination of these chemicals under anaerobic conditions is well established, although this can increase their toxicity. Consequently, the production and use of these chemicals has been restricted and alternative products have been developed. Many of these are brominated compounds and share some of the disadvantages of the chemicals they are meant to replace. Therefore, other, nonbrominated, flame retardants such as organophosphorus compounds are also being used in increasing quantities, despite the fact that knowledge of their biodegradation and environmental fate is often lacking. PMID:26748263

  6. Brominated Flame Retardants and Perfluorinated Chemicals

    EPA Science Inventory

    Brominated flame retardants (BFRs) and perfluorinated chemicals (PFCs) belong to a large class of chemicals known as organohalogens. It is believed that both BFRs and PFCs saved lives by reducing flammability of materials commonly used and bactericidal (biocidal) properties. Thes...

  7. PCBs, PBBs and Brominated Flame Retardants

    EPA Science Inventory

    This chapter introduces selected organohalogen chemicals such as polychlorinated biphenyls (PCB5), polychiorinated biphenyls (PBBs), and brominated flame retardants (BFRs) with emphasis on the background, physicochemical properties, environmental levels, health effects and possib...

  8. Flame retardants: Dust - And not food - Might be the risk.

    PubMed

    de Boer, J; Ballesteros-Gómez, A; Leslie, H A; Brandsma, S H; Leonards, P E G

    2016-05-01

    Flame retardants (FRs) are used to delay ignition of materials such as furniture and electric and electronic instruments. Many FRs are persistent and end up in the environment. Environmental studies on flame retardants (FRs) took off in the late 1990s. Polybrominated diphenylethers (PBDEs) appeared to be bioaccumulative and were found in many organisms all over the world. When PBDEs were banned or their production voluntarily terminated, alternatives appeared on the market that often had similar properties or were of more concern due to their toxicity such as halogenated phosphorus-based FRs. Here we show that in spite of the ban on PBDEs more brominated FRs are being produced, an increasing number of other FRs is being applied and FR levels in our homes are much higher than in the outdoor environment. While nowadays we live in better isolated houses and sit in front of the computer or television, on flame retarded upholstery, we are at risk due to the toxic effects of a suite of FRs. The high exposure to these substances indoors calls for better risk assessments that include mixture effects. PMID:26765313

  9. Engineering Flame Retardant Biodegradable Nanocomposites

    NASA Astrophysics Data System (ADS)

    He, Shan; Yang, Kai; Guo, Yichen; Zhang, Linxi; Pack, Seongchan; Davis, Rachel; Lewin, Menahem; Ade, Harald; Korach, Chad; Kashiwagi, Takashi; Rafailovich, Miriam

    2013-03-01

    Cellulose-based PLA/PBAT polymer blends can potentially be a promising class of biodegradable nanocomposites. Adding cellulose fiber reinforcement can improve mechanical properties of biodegradable plastics, but homogeneously dispersing hydrophilic cellulose in the hydrophobic polymer matrix poses a significant challenge. We here show that resorcinol diphenyl phosphates (RDP) can be used to modify the surface energy, not only reducing phase separation between two polymer kinds but also allowing the cellulose particles and the Halloysite clay to be easily dispersed within polymer matrices to achieve synergy effect using melt blending. Here in this study we describe the use of cellulose fiber and Halloysite clay, coated with RDP surfactant, in producing the flame retardant polymer blends of PBAT(Ecoflex) and PLA which can pass the stringent UL-94 V0 test. We also utilized FTIR, SEM and AFM nanoindentation to elucidate the role RDP plays in improving the compatibility of biodegradable polymers, and to determine structure property of chars that resulted in composites that could have optimized mechanical and thermal properties. Supported by Garcia Polymer Center and NSF Foundation.

  10. Comparison of the recyclability of flame-retarded plastics.

    PubMed

    Imai, Takaretu; Hamm, Stephan; Rothenbacher, Klaus P

    2003-02-01

    Mechanical recycling of plastics from waste from electrical and electronical equipment (WEEE) is increasingly expected by regulators and demanded by original equipment manufacturers (CEMs); however, mechanical recycling is generally recognized to be the most economically costly and technically challenging method of recovering WEEE plastics. With 12% of WEEE plastics requiring the use of flame-retardants in order to ensure appropriate levels of consumer fire safety, there is a distinct need for data from comparative tests on recyclability of various flame-retarded plastics. Ten commercially available flame-retarded plastic grades commonly used in electronic equipment (eight "halogen-free" grades and two grades containing brominated flame-retardants (BFRs)) were subjected to two different recycling scenarios. A standard recycling scenario was carried out by repeatedly extruding the materials and an accelerated hydrolysis scenario was carried out to study the influence of humidity from air during use on the process. Both, virgin and recycled materials were tested for a potential formation of polybrominated dibenzodioxins/furans (PBDD/Fs), their mechanical properties were assessed and the fire safety rating was determined. Results indicate that none of the tested materials showed a potential to form the PBDD/Fs regulated by the German Chemicals Banning Ordinance. The halogen-free plastic grades showed a significant deterioration of mechanical properties after recycling, whereas those plastics containing BFRs were able to pass all test criteria, thus maintaining their original properties. With respect to the fire safety rating, none of the eight tested halogen-free plastic grades could maintain their fire safety rating after five recycling loops, whereas both BFR plastics continued to achieve their fire safety ratings. Therefore the tested BFR containing plastic materials showed superior recycling properties compared to the tested halogen-free plastic grades with

  11. [Concentration and emission fluxes of halogenated flame retardants in sewage from sewage outlet in Dongjiang River].

    PubMed

    Zeng, Yan-Hong; Luo, Xiao-Jun; Sun, Yu-Xin; Yu, Le-Huan; Chen, She-Jun; Mai, Bi-Xian

    2011-10-01

    Fourteen sewage samples from sewage outlets in Dongjiang River were collected. Halogented flame retardants were extracted and purified using dichloromethane and alumina/silica-gel column, respectively. The concentrations of halogenated flame retardants were measured utilizing GC/MS, and the emission fluxes were estimated. Decabromodiphenyl ethane (DBDPE) was the predominant halogenated pollutant (accounting for 64%) in sewage with the concentration ranging from 9.1 ng/L to 990 ng/L. The concentrations of polybrominated biphenyl ether (PBDEs), dominated by BDE209, in the sewage ranged from 6.9 ng/L to 470 ng/L, accounting for 30% of total halogenated flame retardants. The concentrations of other flame retardants, such as dechlorane plus (DP), 1, 2-bis(2, 4, 6-tribromophenoxy) ethane (BTBPE), hexabromobenzene (HBB), and pentabromotoluene (PBT), were ranged within 0.17-23.6, nd-26.3, nd-1.45 and nd-0.45 ng/L, respectively. The concentrations of PBDEs in sewage of Dongjiang River were comparable to those in influent wastewater of sewage treatment plants of Guangzhou, suggesting that the wastewater was discharged directly into Dongjiang River without any treatment. The emission flux of halogenated flame retardants from sewage was 191 kg. Emission from industrial wastewater, contributed to 48%-91% of total emission, was the main source of halogenated flame retardants. PMID:22279897

  12. Exposures, Mechanisms, and Impacts of Endocrine-Active Flame Retardants

    PubMed Central

    Dishaw, Laura; Macaulay, Laura; Roberts, Simon C.; Stapleton, Heather M.

    2014-01-01

    This review summarizes the endocrine and neurodevelopmental effects of two current-use additive flame retardants (FRs), tris (1,3-dichloro-isopropyl) phosphate (TDCPP) and Firemaster® 550 (FM 550), and the recently phased-out polybrominated diphenyl ethers (PBDEs), all of which were historically or are currently used in polyurethane foam applications. Use of these chemicals in consumer products has led to widespread exposure in indoor environments. PBDEs and their hydroxylated metabolites appear to primarily target the thyroid system, likely due to their structural similarity to endogenous thyroid hormones. In contrast, much less is known about the toxicity of TDCPP and FM550. However, recent in vitro and in vivo studies suggest that both should be considered endocrine disruptors as studies have linked TDCPP exposure with changes in circulating hormone levels, and FM 550 exposure with changes in adipogenic and osteogenic pathways. PMID:25306433

  13. Guide to PBDE: Toxic Flame Retardant--What Women, Children and School Personnel Need to Know. Revised

    ERIC Educational Resources Information Center

    Healthy Schools Network, Inc., 2012

    2012-01-01

    Chemical flame-retardants are used in a variety of products to prevent the spread and occurrence of fire. While fire safety is critical, this family of chemicals, known as Polybrominated diphenyl ethers (PBDEs) are highly toxic. They are found in carpeting, foam cushions, polyester clothing and bedding, wallpaper, toys, household dust, a variety…

  14. A polymeric flame retardant additive for rubbers

    SciTech Connect

    Ghosh, S.N.; Maiti, S.

    1993-12-31

    Synthesis of a polyphosphonate by the interfacial polymerization of bisphenol-A (BPA) and dichloro-phenyl phosphine oxide (DCPO) using cetyltrimethyl ammonium chloride (TMAC) as phase transfer catalyst (PTC) was reported. The polyphosphonate was characterized by elemental analysis, IR, TGA, DSC and 1H-NMR spectroscopy. The flame retardancy of the polymer was done by OI study. The polymer was used as a fire retardant additive to rubbers such as natural rubber (NR), styrene-butadiene rubber(SBR), nitrile rubber (NBR) and chloroprene rubber (CR). The efficiency of the fire retardant property of this additive was determined by LOI measurements of the various rubber samples.

  15. [Flame retardants--use and hazards for human].

    PubMed

    Góralczyk, Katarzyna; Struciński, Paweł; Czaja, Katarzyna; Hernik, Agnieszka; Ludwicki, Jan K

    2002-01-01

    Flame retardants (FRs) are chemicals which added to materials during or after manufacture, inhibit or even suppress the combustion process due to their thermal stability. Large quantities of FRs are added to the plastic material (resins) in variety of electrical and electronic appliances including television and computer casing. The other uses of these compounds include production of building materials, upholstered furniture, textiles, wall covering, carpets, hydraulic fluids as well as vehicles and aircraft. Taking into account the chemical structure, there are five main groups of FRs: brominated, chlorinated, phosphorous-containing, nitrogen-containing (i.e. melamines) and inorganic compounds. Halogenated compounds, especially polybrominated diphenyl ethers (PBDEs), a class of brominated flame retardants, due to their lipophilic characteristics and persistence have become ubiquitous environmental contaminants. There are indications that PBDEs may affect hormone function acting as endocrine disruption and may be toxic for developing brain. These compounds have been associated with non-Hodgkin's lymphoma in humans, a variety of cancers in rodents and disruption of thyroid hormones balance. Similarly to other persistent halogenated compounds they are also able to affect the xenobiotic metabolizing enzymes activity. PBDEs are now found as residues in sediments, wildlife and human (milk, serum adipose tissue) samples. The predominant congeners in environmental samples, including human specimens are two congeners: 47 and 99. Currently, the estimated daily intake of PBDEs by adult humans is equal 51 ng x day-1 while by breast-fed infants equals 110 ng x day-1. PMID:12621885

  16. Potential estrogenic effects of phosphorus-containing flame retardants.

    PubMed

    Zhang, Quan; Lu, Meiya; Dong, Xiaowu; Wang, Cui; Zhang, Chunlong; Liu, Weiping; Zhao, Meirong

    2014-06-17

    As the substitute of polybrominated diphenyl ethers (PBDEs), further assessments about the potential ecological safety and health risks of phosphorus-containing flame retardants (PFRs) are required because the worldwide demand for PFRs has been increasing every year. In this study, we examined the agonistic/antagonistic activity of a group of PFRs by three in vitro models (luciferase reporter gene assay, yeast two-hybrid assay, and E-screen assay). Molecule docking was used to further explain the interactions between ERα and PFRs. Data from luciferase reporter gene analysis showed three members of the nine tested PFRs significantly induced estrogenic effects, with the order of TPP > TCP > TDCPP, while TCEP and TEHP have remarkable antiestrogenic properties with calculated REC20 and RIC20 values of 10(-6) M or lower. Results from the luciferase reporter gene method are generally consistent with results obtained from the yeast two-hybrid assay and E-screen, except for the positive estrogenic activity of TBP in E-screen testing. Docking results showed that binding between ligands and ERα was stabilized by hydrophobic interactions. As a proposed alternative for brominated flame retardant, PFRs may have anti/estrogenic activity via ERα at the low dose typical of residue in environmental matrix or animals. PFRs with a short chain, halogen, and benzene ring in the substituent group tend to be estrogenic. Our research suggests that comprehensive evaluations, including health and ecological assessments, are required in determining whether PFRs are preferable as an emerging industrial substitute. PMID:24844797

  17. BROMINATED FLAME RETARDANTS: CAUSE FOR CONCERN?

    EPA Science Inventory

    Brominated flame retardants (BFRs) have routinely been added to consumer products for several decades in a successful effort to reduce fire-related injury and property damage. Recently, concern for this emerging class of chemicals has risen due to the occurrence of several class...

  18. BROMINATED FLAME RETARDANTS: WHY DO WE CARE?

    EPA Science Inventory

    Brominated flame retardants (BFRs) save lives and property by preventing the spread of fires or delaying the time of flashover, enhancing the time people have to escape. The worldwide production of BFRs exceeded 200,000 metric tons in 2003 placing them in the high production vol...

  19. HEALTH ASPECTS OF BROMINATED FLAME RETARDANTS (BFRS)

    EPA Science Inventory

    In order to reduce the societal costs of fires, flammability standards have been set for consumer products and equipment. Flame retardants containing bromine have constituted the largest share of this market due both to their efficiency and cost. While there are at least 75 dif...

  20. HEALTH EFFECTS OF BROMINATED FLAME RETARDANTS (BFRS)

    EPA Science Inventory

    Abstract Brominated flame retardant use has increased dramatically in order to provide fire safety to consumers. However, there is growing concern about widespread environmental contamination and potential health risks from some of these products. The most used products...

  1. Chemistry and toxicity of flame retardants for plastics.

    PubMed Central

    Liepins, R; Pearce, E M

    1976-01-01

    An overview of commercially used flame retardants is give. The most used flame retardants are illustrated and the seven major markets, which use 96% of all flame-retarded polymers, are described. Annual flame retardant growth rate for each major market is also projected. Toxicity data are reviewed on only those compositions that are considered commercially significant today. This includes 18 compounds or families of compounds and four inherently flame-retarded polymers. Toxicological studies of flame retardants for most synthetic materials are of recent origin and only a few of the compounds have been evaluated in any great detail. Considerable toxicological problems may exist in the manufacturing of some flame retardants, their by-products, and possible decomposition products. PMID:1026419

  2. Shuttle Environmental Assurance: Brominated Flame Retardants - Concerns, Drivers, Potential Impacts and Mitigation Strategies

    NASA Technical Reports Server (NTRS)

    Clark-Ingram, Marceia

    2010-01-01

    Brominated Flame Retardants (BFRs) are widely used in the manufacture of electrical and electronic components and as additives in formulations for foams, plastics and rubbers. The United States (US) and the European Union (EU)have increased regulation and monitoring of of targeted BFRs, such as Polybrominated Diphenyl Ethers (PBDEs) due to the bioaccumulative effects in humans and animals. In response, manufacturers and vendors of BFR-containing materials are changing flame-retardant additives, sometimes without notifying BFR users. In some instances, Deca-bromodiphenylether (Deca-BDE) and other families of flame retardants are being used as replacement flame retardants for penta-BDE and octa-BDE. The reformulation of the BFR-containing material typically results in the removal of the targeted PBDE and replacement with a non-PBDE chemical or non-targeted PBDE. Many users of PBDE -based materials are concerned that vendors will perform reformulation and not inform the end user. Materials performance such as flammability, adhesion , and tensile strength may be altered due to reformulation. The requalification of newly formulated materials may be required, or replacement materials may have to be identified and qualified. The Shuttle Enviornmental Assurance (SEA) team indentified a risk to the Space Shuttle Program associated with the possibility that targeted PBDEs may be replaced without notification. Resultant decreases in flame retardancy, Liquid Oxygen (LOX) compatibility, or material performance could have serious consequences.

  3. Flame retardant transfers from U.S. households (dust and laundry wastewater) to the aquatic environment.

    PubMed

    Schreder, Erika D; La Guardia, Mark J

    2014-10-01

    Levels of flame retardants in house dust and a transport pathway from homes to the outdoor environment were investigated in communities near the Columbia River in Washington state (WA). Residential house dust and laundry wastewater were collected from 20 homes in Vancouver and Longview, WA and analyzed for a suite of flame retardants to test the hypothesis that dust collecting on clothing and transferring to laundry water is a source of flame retardants to wastewater treatment plants (WWTPs) and subsequently to waterways. Influent and effluent from two WWTPs servicing these communities were also analyzed for flame retardants. A total of 21 compounds were detected in house dust, including polybrominated diphenyl ethers (PBDEs), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB or EH-TBB), bis(2-ethylhexyl) 3,4,5,6-tetrabromophthalate (TBPH), 1,2-bis(2,4,6,-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), hexabromocyclododecane (HBCD or HBCDD), tetrabromobisphenol A (TBBPA), and three chlorinated organophosphate flame retardants (ClOPFRs), tris(1,3-dichloro-2-propyl)phosphate (TDCPP or TDCIPP), tris(1-chloro-2-propyl)phosphate (TCPP or TCIPP), and tris(2-chloroethyl)phosphate (TCEP). Levels ranged from 3.6 to 82,700 ng g(-1) (dry weight). Of the 21 compounds detected in dust, 18 were also detected in laundry wastewater. Levels ranged from 47.1 to 561,000 ng L(-1). ClOPFRs were present at the highest concentrations in both dust and laundry wastewater, making up 72% of total flame retardant mass in dust and 92% in laundry wastewater. Comparison of flame retardant levels in WWTP influents to estimates based on laundry wastewater levels indicated that laundry wastewater may be the primary source to these WWTPs. Mass loadings to the Columbia River from each treatment plant were by far the highest for the ClOPFRs and ranged up to 114 kg/yr for TCPP. PMID:25288150

  4. Using silicone wristbands to evaluate preschool children's exposure to flame retardants.

    PubMed

    Kile, Molly L; Scott, Richard P; O'Connell, Steven G; Lipscomb, Shannon; MacDonald, Megan; McClelland, Megan; Anderson, Kim A

    2016-05-01

    Silicone wristbands can be used as passive sampling tools for measuring personal environmental exposure to organic compounds. Due to the lightweight and simple design, the wristband may be a useful technique for measuring children's exposure. In this study, we tested the stability of flame retardant compounds in silicone wristbands and developed an analytical approach for measuring 41 flame retardants in the silicone wristband in order to evaluate exposure to these compounds in preschool-aged children. To evaluate the robustness of using wristbands to measure flame retardants, we evaluated the stability of 3 polybrominated diphenyl ethers (BDEs), and 2 organophosphate flame retardants (OPFRs) in wristbands over 84 days and did not find any evidence of significant loss over time at either 4 or -20°C (p>0.16). We recruited a cohort of 92 preschool aged children in Oregon to wear the wristband for 7 days in order to characterize children's acceptance of the technology, and to characterize their exposure to flame retardants. Seventy-seven parents returned the wristbands for analysis of 35 BDEs, 4 OPFRs, and 2 other brominated flame retardants although 5 were excluded from the exposure assessment due to protocol deviations (n=72). A total of 20 compounds were detected above the limit of quantitation, and 11 compounds including 4 OPFRs and 7 BDEs were detected in over 60% of the samples. Children's gender, age, race, recruitment site, and family context were not significantly associated with returning wristbands or compliance with protocols. Comparisons between flame retardant data and socio-demographic information revealed significant differences in total exposures to both ΣBDEs and ΣOPFRs based on age of house, vacuuming frequency, and family context. These results demonstrate that preschool children in Oregon are exposed to BDEs that are no longer being produced in the United States and to OPFRs that have been used as an alternative to polybrominated compounds

  5. Brominated and chlorinated flame retardants in San Francisco Bay sediments and wildlife.

    PubMed

    Klosterhaus, Susan L; Stapleton, Heather M; La Guardia, Mark J; Greig, Denise J

    2012-10-15

    Restrictions on the use of polybrominated diphenyl ethers (PBDEs) have resulted in the use of alternative flame retardants in consumer products to comply with flammability standards. In contrast to PBDEs, information on the occurrence and fate of these alternative compounds in the environment is limited, particularly in the United States. In this study, a survey of flame retardants in San Francisco Bay was conducted to evaluate whether PBDE replacement chemicals and other current use flame retardants were accumulating in the Bay food web. In addition to PBDEs, brominated and chlorinated flame retardants (hexabromocyclododecane (HBCD) and Dechlorane Plus (DP)) were detected in Bay sediments and wildlife. Median concentrations of PBDEs, HBCD, and DP, respectively, were 4.3, 0.3, and 0.2 ng g⁻¹ dry weight (dw) in sediments; 1670, <6.0, and 0.5 ng g⁻¹ lipid weight (lw) in white croaker (Genyonemus lineatus); 1860, 6.5, and 1.3 ng g⁻¹ lw in shiner surfperch (Cymatogaster aggregata); 5500, 37.4, and 0.9 ng g⁻¹ lw in eggs of double-crested cormorant (Phalacrocorax auritus); 770, 7.1, and 0.9 ng g⁻¹ lw in harbor seal (Phoca vitulina) adults; and 330, 3.5, and <0.1 ng g⁻¹ lw in harbor seal (P. vitulina) pups. Two additional flame retardants, pentabromoethylbenzene (PBEB) and 1,2-bis(2,4,6 tribromophenoxy)ethane (BTBPE) were detected in sediments but with less frequency and at lower concentrations (median concentrations of 0.01 and 0.02 ng g⁻¹ dw, respectively) compared to the other flame retardants. PBEB was also detected in each of the adult harbor seals and in 83% of the pups (median concentrations 0.2 and 0.07 ng g⁻¹ lw, respectively). The flame retardants hexabromobenzene (HBB), decabromodiphenyl ethane (DBDPE), bis(2-ethylhexyl) tetrabromophthalate (TBPH), and 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), were not detected in sediments and BTBPE, HBB and TBB were not detected in wildlife samples. Elevated concentrations of some flame retardants

  6. EFFECT OF ORGANOPHOSPHORUS FLAME RETARDANTS ON NEURONAL DEVELOPMENT IN VITRO

    EPA Science Inventory

    The increased use of organophosphorus compounds as alternatives to brominated flame retardants (BFRs) has led to widespread human exposure, There is, however, limited information on their potential health effects. This study compared the effects of nii ne organophosphorus flame...

  7. [ORGANOPHOSPHORUS FLAME RETARDANTS - TOXICITY AND INFLUENCE ON HUMAN HEALTH].

    PubMed

    Bruchajzer, Elżbieta; Frydrych, Barbara; Szymańska, Jadwiga Anna

    2015-01-01

    Organophosphorus flame retardants (flame retardants, FRs) have been used for several decades in many industries, including the production of dyes, varnishes, adhesives, synthetic resins, polyvinyl chloride, hydraulic fluids, plastics and textiles. Their importance in recent times has increased due to i.a., significantly reduced use of polybrominated diphenyl ethers (PBDEs) - persistent organic pollutants, dangerous for the environment. The aim of this study was to review the available literature data concerning phosphorous FRs primarily for neurotoxic, fertility, reproductive and carcinogenic effects. The analysis concerned the following most commonly used substances: tris(2-ethylhexyl)phosphate (TEHP), tris(2-butoxyethyl)phosphate (TBEP), triphenyl phosphate (TPP), tris(2-chloroethyl)phosphate (TCEP), tetrakis(hydroxymethyl)-phosphonium chloride (THPC), tributyl phosphate (TBP), tricresyl phosphate (TCP), tris(2-chloroisopropyl)phosphate (TCPP), tris(1,3-dichloroisopropyl)phosphate (TDCP) and tetrakis(hydroxymethyl)phosphonium sulphate (THPS). In animal studies neurotoxic effects were found after exposure to TBEP, THPC, TBP and TCP, while in humans they were observed only after exposure to TCP. TCEP, THPS, TBP, TCP and TDCP caused disorders in fertility and/or fetal development of animals. Adverse effects on reproduction in humans may be caused by TPP, TCP, and TDCP. In laboratory animals the development of tumors was observed after high doses of TEHP, TCEP, TBP and TDCP. None of these compounds is classified as a human carcinogen. The environmental toxicity of phosphate FRs is low (except for TPP, TCEP and TBEP). They are not stable compounds, in living organisms they are metabolised and quickly excreted. Therefore, they can be used as an alternative to PBDEs. PMID:26294315

  8. Polybrominated diphenyl ether (PBDE) concentrations and resulting exposure in homes in California: relationships among passive air, surface wipe and dust concentrations, and temporal variability

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in furniture foam, electronics, and other home furnishings. A field study was conducted that enrolled 139 households from California, which has had more stringent flame retardant requirements than other countries...

  9. TG-FTIR characterization of flame retardant polyurethane foams materials

    NASA Astrophysics Data System (ADS)

    Liu, W.; Tang, Y.; Li, F.; Ge, X. G.; Zhang, Z. J.

    2016-07-01

    Dimethyl methylphosphonate (DMMP) and trichloroethyl phosphtate (TCEP) have been used to enhance the flame retardancy of polyurethane foams materials (PUF). Flame retardancy and thermal degradation of PUF samples have been investigated by the LOI tests and thermal analysis. The results indicate that the excellent flame retardancy can be achieved due to the presence of the flame retardant system containing DMMP and TCEP. TG-FTIR reveals that the addition of DMMP/TCEP can not only improve the thermal stability of PUF samples but can also affect the gaseous phase at high temperature.

  10. Teaching about Flame Retardants. A Joint Israeli-Dutch Project

    NASA Astrophysics Data System (ADS)

    Kesner, Miri; de Vos, Wobbe

    2001-01-01

    Flame retardants make interesting chemistry and moreover, the chemistry is highly relevant from an everyday life point of view. This article reports on a joint Israeli-Dutch project aimed at teaching the production, properties, and applications of some bromine-containing flame retardants, including their environmental aspects, in secondary education. We provide information on the nature of flame retardants in general and the mechanisms of flame retardation. In addition, we offer a complete pedagogical presentation of the topic, including the use of video and some simple laboratory experiments, that was developed and successfully implemented in both countries.

    Featured on the Cover

  11. Exposure to flame retardants in electronics recycling sites.

    PubMed

    Rosenberg, Christina; Hämeilä, Mervi; Tornaeus, Jarkko; Säkkinen, Kirsi; Puttonen, Katriina; Korpi, Anne; Kiilunen, Mirja; Linnainmaa, Markku; Hesso, Antti

    2011-07-01

    Waste electrical and electronic equipment (WEEE) contains various hazardous substances such as flame retardants (FRs). Inhalation exposures to many FRs simultaneously among WEEE recycling site workers have been little studied previously. The breathing zone airborne concentrations of five brominated FR compounds tetrabromobisphenol-A (TBBP-A), decabromodiphenylethane (DBDPE), hexabromocyclododecane, 1,2-bis(2,4,6-tribromophenoxy)ethane, hexabromobenzene, and one chlorinated FR (Dechlorane Plus®) were measured at four electronics recycling sites in two consecutive years. In addition, concentrations of polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyls were measured. The three most abundant FRs in personal air samples were PBDEs (comprising mostly of deca-BDE), TBBP-A, and DBDPE, with mean concentrations ranging from 21 to 2320 ng m(-)(3), from 8.7 to 430 ng m(-3), and from 3.5 to 360 ng m(-3), respectively. At two of the sites, the emission control actions (such as improvements in ventilation and its maintenance and changes in cleaning habits) proved successful, the mean levels of FRs in personal samples being 10-68 and 14-79% of those from the previous year or alternatively below the limit of quantification. At the two remaining sites, the reductions in FR exposures were less consistent. The concentrations reported may pose a health hazard to the workers, although evaluation of the association between FR exposure and adverse health effects is hampered by lacking occupational exposure limits. Therefore, the exposures should be minimized by adequate control measures and maintaining good occupational hygiene practice. PMID:21742626

  12. Nanotechnology finding its way into flame retardancy

    NASA Astrophysics Data System (ADS)

    Schartel, Bernhard

    2014-05-01

    Nanotechnology is one of the key technologies of the 21st century. The exploitation of "new" effects that arise from materials structured on the nano-scale has also been proposed successfully for flame retardancy of polymers since the end of the 90s. Of all of the approaches these include, at this time the use of nanocomposites offers the best potential for industrial application, also some other ideas are sketched, such as using electrospun nanofibers mats or layer-by-layer deposits as protection coatings, as well as sub-micrometer multilayer coatings as effective IR-mirrors. The general phenomena, inducing a flow limit in the pyrolysing melt and changing the fire residue, are identified in nanocomposites. Key experiments are performed such as quasi online investigation of the protection layer formation to understand what is going on in detail. The flame retardancy mechanisms are discussed and their impact on fire behaviour quantified. With the latter, the presentation pushes forward the state of the art. For instance, the heat shielding is experimentally quantified for a layered silicate epoxy resin nanocomposite proving that it is the only import mechanism controlling the reduction in peak heat release rate in the investigated system for different irradiations. The flame retardancy performance is assessed comprehensively illuminating not only the strengths but also the weak points of the concepts. Guidelines for materials development are deduced and discussed. Apart from inorganic fillers (layered silicate, boehmite, etc.) not only carbon nanoobjects such as multiwall carbon nanotubes, multilayer graphene and graphene are investigated, but also nanoparticles that are more reactive and harbor the potential for more beneficial interactions with the polymer matrix.

  13. Nanotechnology finding its way into flame retardancy

    SciTech Connect

    Schartel, Bernhard

    2014-05-15

    Nanotechnology is one of the key technologies of the 21{sup st} century. The exploitation of 'new' effects that arise from materials structured on the nano-scale has also been proposed successfully for flame retardancy of polymers since the end of the 90s. Of all of the approaches these include, at this time the use of nanocomposites offers the best potential for industrial application, also some other ideas are sketched, such as using electrospun nanofibers mats or layer-by-layer deposits as protection coatings, as well as sub-micrometer multilayer coatings as effective IR-mirrors. The general phenomena, inducing a flow limit in the pyrolysing melt and changing the fire residue, are identified in nanocomposites. Key experiments are performed such as quasi online investigation of the protection layer formation to understand what is going on in detail. The flame retardancy mechanisms are discussed and their impact on fire behaviour quantified. With the latter, the presentation pushes forward the state of the art. For instance, the heat shielding is experimentally quantified for a layered silicate epoxy resin nanocomposite proving that it is the only import mechanism controlling the reduction in peak heat release rate in the investigated system for different irradiations. The flame retardancy performance is assessed comprehensively illuminating not only the strengths but also the weak points of the concepts. Guidelines for materials development are deduced and discussed. Apart from inorganic fillers (layered silicate, boehmite, etc.) not only carbon nanoobjects such as multiwall carbon nanotubes, multilayer graphene and graphene are investigated, but also nanoparticles that are more reactive and harbor the potential for more beneficial interactions with the polymer matrix.

  14. New hybrid halogen-free flame retardants

    NASA Astrophysics Data System (ADS)

    Kijowska, Dorota; Jankowski, Piotr

    2014-05-01

    The main objective of this work were researches concerning the methods of the in-situ modification of silicate layer-tubular mineral (SL-TM) halloysite, using the salts of melamine, i.e. melamine cyanurate. The modified mineral was used as flame retardant to thermoplastic polymers. In the case of the application of halloysite modified by melamine cyanurate to polyamide 6 (PA6) the highest parameters of vertical and horizontal flammability were achieved. The mechanical properties of filled polyamide 6 have been improved.

  15. Flame-retardant contamination of firefighter personal protective clothing - A potential health risk for firefighters.

    PubMed

    Alexander, Barbara M; Baxter, C Stuart

    2016-09-01

    There is a high incidence of cardiovascular disease and certain cancers in firefighters that may be related to their occupational exposure to hazardous substances. Exposure may result from contaminated personal protective gear, as well as from direct exposure at fire scenes. This study characterized flame-retardant contamination on firefighter personal protective clothing to assess exposure of firefighters to these chemicals. Samples from used and unused firefighter protective clothing, including gloves, hoods and a coat wristlet, were extracted with methylene chloride and analyzed by EPA method 8270D Specific Ion Method (SIM) for polybrominated diphenyl ethers (PBDEs). Until recently PBDEs were some of the most common flame-retardant chemicals used in the US. Fifteen of the seventeen PBDEs for which analysis was performed were found on at least one clothing swatch. Every clothing sample, including an unused hood and all three layers of an unused glove, held a detectable concentration of at least one PBDE. These findings, along with previous research, suggest that firefighters are exposed to PBDE flame retardants at levels much higher than the general public. PBDEs are found widely dispersed in the environment and still persist in existing domestic materials such as clothing and furnishings. Firefighter exposure to flame retardants therefore merits further study. PMID:27171467

  16. Brominated flame retardants in Canadian chicken egg yolks

    PubMed Central

    Rawn, D.F.K.; Sadler, A.; Quade, S.C.; Sun, W.-F.; Lau, B.P.-Y.; Kosarac, I.; Hayward, S.; Ryan, J.J.

    2011-01-01

    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. PMID:21623506

  17. Flame retardant antibacterial cotton high-loft nonwoven fabrics

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flame retardant treated gray cotton fibers were blended with antibacterial treated gray cotton fibers and polyester/polyester sheath/core bicomponent fibers to form high-loft fabrics. The high flame retardancy (FR) and antibacterial property of these high lofts were evaluated by limiting oxygen inde...

  18. Flame retardant properties of triazine phosphonates derivative with cotton fabric

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The flame retardant behavior of a cotton fabric treated with phosphorus-nitrogen containing triazine compound was evaluated. It was found that cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) is an excellent starting material for the preparation of phosphonates flame retardants that interacts wel...

  19. Novel phosphonates triazine derivative as economic flame retardant for cotton

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Phosphorous-containing flame retardants are widely used in standard and engineering plastics, polyurethane foams, thermosets, coatings, and textiles. Organophosphorous flame retardants have been known to be more effective when used in conjunction with nitrogen-containing systems. Their mixture produ...

  20. IN VITRO DERMAL ABSORPTION OF FLAME RETARDANT CHEMICALS

    EPA Science Inventory

    ABSTRACT
    The use of flame retardant chemicals in furniture fabric could pose a potential health risk to consumers from dermal absorption of these compounds. The objective of this study was to examine the in vitro dermal absorption of two flame retardant chemicals, [14C]-d...

  1. Brominated flame retardant levels in human milk and serum from MAMA study participants: Correlations over time, matrix, and with questionnaire results

    EPA Science Inventory

    Brominated flame retardants (BFRs) are synthetic, lipophilic, and bioaccumulative compounds used to prevent the combustion of a variety of items including electronics and furniture. There are 75 classes of BFRs, two of which are the polybrominated biphenyls (PBB) and the polybrom...

  2. Statewide surveillance of halogenated flame retardants in fish in Illinois, USA.

    PubMed

    Widelka, Margaret; Lydy, Michael J; Wu, Yan; Chen, Da

    2016-07-01

    In order to better understand the exposure of aquatic systems to halogenated flame retardant contaminants, the present study investigated a variety of legacy and emerging flame retardants in common carp and largemouth bass collected from 58 stations across Illinois (United States). The data revealed that polybrominated diphenyl ethers (PBDEs) generally dominated the flame retardant residues in Illinois fish. Concentrations of ΣPBDEs (including all detectable PBDE congeners) ranged from 24.7 to 8270 ng/g lipid weight (median: 135 ng/g lw) in common carp and 15-3870 ng/g lw (median: 360 ng/g lw) in largemouth bass. In addition to PBDEs, Dechlorane analogues (i.e. Dec-603, Dec-604, and Chlordane Plus) were also frequently detected. Median concentrations of ΣDechloranes (including all detected Dechlorane analogues) were 34.4 and 23.3 ng/g lw in common carp and largemouth bass, respectively. Other emerging flame retardants, including tetrabromo-o-chlorotoluene (TBCT), hexabromobenzene (HBBZ), 2-ethylhexyltetrabromobenzoate (EH-TBB), and bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEH-TEBP), were also detected in 40-78% of the fish at the monitored stations. Spatial analysis revealed significantly greater PBDE concentrations in fish living in impaired urban streams and lakes compared to those from the impaired agricultural and unimpaired agricultural/urban waters, demonstrating a significant urban influence on PBDE contamination. Future studies and environmental monitoring are recommended to focus on temporal trends of PBDEs and alternative flame retardants, as well as human exposure risks via edible fishes, in the identified Areas of Concern within Illinois. PMID:27131823

  3. Evaluation of a Fast and Simple Sample Preparation Method for Polybrominated Diphenyl Ether (PBDE) Flame Retardants and Dichlorodiphenyltrichloroethane (DDT) Pesticides in Fish for Analysis by ELISA Compared with GC-MS/MS.

    PubMed

    Sapozhnikova, Yelena; Simons, Tawana; Lehotay, Steven J

    2015-05-13

    A simple, fast, and cost-effective sample preparation method, previously developed and validated for the analysis of organic contaminants in fish using low-pressure gas chromatography-tandem mass spectrometry (LPGC-MS/MS), was evaluated for the analysis of polybrominated diphenyl ethers (PBDEs) and dichlorodiphenyltrichloroethane (DDT) pesticides using enzyme-linked immunosorbent assay (ELISA). The sample preparation technique was based on the quick, easy, cheap, rugged, effective, and safe (QuEChERS) approach with filter-vial dispersive solid phase extraction (d-SPE). Incurred PBDEs and DDTs were analyzed in three types of fish with 3-10% lipid content: Pacific croaker, salmon, and National Institute of Standards and Technology (NIST) Standard Reference Material 1947 (Lake Michigan fish tissue). LPGC-MS/MS and ELISA results were in agreement: 108-111 and 65-82% accuracy ELISA versus LPGC-MS/MS results for PBDEs and DDTs, respectively. Similar detection limits were achieved for ELISA and LPGC-MS/MS. Matrix effects (MEs) were significant (e.g., -60%) for PBDE measurement in ELISA, but not a factor in the case of DDT pesticides. This study demonstrated that the sample preparation method can be adopted for semiquantitative screening analysis of fish samples by commercial kits for PBDEs and DDTs. PMID:25644932

  4. Flame retardant cotton fabrics treated with organophosphorus polymer.

    PubMed

    Abou-Okeil, A; El-Sawy, S M; Abdel-Mohdy, F A

    2013-02-15

    Organo-phosphorus compounds was prepared and applied onto cotton fabrics as flame retarding agent. methacryloloxyethylorthophoshor tetraethyl diamidate (MPD) was prepared and its structure was confirmed by IR, NMR and mass spectroscopy. Pyrovatex as commercial flame retardant was used for comparative study. Impregnation method was used as coating for the application of the organophosphorus compounds to cotton fabrics. The major factors affecting the reaction were studied. The results show that the prepared organophosphorus compound can be successfully used as flame retardant for cotton fabrics. PMID:23399290

  5. Formation of dioxin-like compounds from the pyrolysis of some halogenated flame retardants

    SciTech Connect

    Alsabbagh, A.M.

    1990-01-01

    Polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans as well as polyhalogenated phenazines have been shown to form from the pyrolysis of some flame retardants. In addition, chlorine-bromine exchange was shown to occur in the formation of halogenated dibenzo-p-dioxins and halogenated phenazines when both chlorine and bromine sources are present in the pyrolysis mixture. There was no chlorine-hydrogen exchange observed in the formation of chloro-bromo-dibenzo-dioxins, chloro-bromo-dibenzofurans and chloro-bromophenazines. At high temperatures, the amino-group of the halogenated anilines may be replaced by oxygen and yield halogenated dibenzo-pdioxins and halogenated dibenzofurans, in addition to the halogenated phenazines. The complete substitution of bromine with chlorine was demonstrated to occur, which is probably why chlorinated dibenzo-p-dioxins and chlorinated dibenzofurans are more widely spread than the brominated analogs, since chlorinated compounds are used in much larger quantities than the brominated compounds. The addition of antimony (III) oxide to the flame-retardant formulations showed initial increase in the formation of the halogenated dibenzo-p-dioxins and the halogenated phenazines. The mass spectra of bromo-phenazines, chloro-phenazines and chloro-bromo-phenazines have been presented. The similarity in the structure of the halogenated phenazines and the halogenated dibenzo-p-dioxins may be of interest to be used in the search of compounds with breast cancer therapeutic use, although the toxicity of the halogenated phenazines should be thoroughly investigated.

  6. ANAEROBIC MICROBIAL REDUCTIVE DEBROMINATION OF POLYBROMINATED DIPHENYL ETHERS

    EPA Science Inventory

    Polybrominated diphenyl ether (PBDE) flame retardants have been detected in sediments, sewage sludge, fish, mammals (including humans), and air throughout the northern hemisphere. While concentrations of PCBs, DDT, and PCDDs in biota are generally decreasing, PBDE concentratio...

  7. POLYBROMINATED DIPHENYL ETHERS (PBDES) CONTAMINATION OF UNITED STATES FOOD

    EPA Science Inventory

    Elevated levels of polybrominated diphenyl ethers (PBDEs), a type of brominated flame retardant, were recently detected in United States (U.S.) nursing mothers' milk. These halogenated compounds chemically and toxicologically resemble others such as polychlorinated biphenyls (PC...

  8. POLYBROMINATED DIPHENYL ETHERS IN HOUSE DUST AND CLOTHES DRYER LINT

    EPA Science Inventory

    Polybrominated diphenyl ether (PBDE) flame retardants are now considered ubiquitous and persistent pollutants. Few studies have examined the concentrations of these chemicals in the home and here we report measurements of PBDEs in house dust samples collected from the Washington...

  9. The flame retardant properties of cyanuric chloride derivatives in cotton textile applications

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cyanuric chloride derivatives are promising flame retardants in cotton textile applications due to their ease of synthesis, high yield, and excellent flame retardant properties as measured by thermogravimetric analyses, limiting oxygen index, and vertical flame testing. Scanning electron microscopic...

  10. Burning To Learn: An Introduction to Flame Retardants.

    ERIC Educational Resources Information Center

    Journal of Chemical Education, 2001

    2001-01-01

    Presents an activity that demonstrates the effectiveness of flame retardants--substances added to combustible materials to slow down or hinder burning--that can be introduced when discussing combustion reactions or during a practical or everyday chemistry unit. (ASK)

  11. Development of Flame Retardants for Engineering Polymers and Polyurethanes

    NASA Astrophysics Data System (ADS)

    Desikan, Anantha

    2013-03-01

    With a broad portfolio of brominated, organophosphorus and inorganic flame retardants, ICL Industrial Products (ICL-IP) is engaged in the development of new flame retardants by exploiting the synergism between bromine based, phosphorus based and other halogen-free flame retardants. ICL-IP is also focusing on the development of polymeric and reactive flame retardants. This presentation will give examples of existing and new polymeric and reactive products for applications in thermoplastics, thermosets and polyurethane foam. This presentation will also show examples of phosphorus-bromine synergism allowing partial or complete elimination of antimony trioxide in many thermoplastics for electronic applications. New synergistic combinations of magnesium hydroxide with phosphorus and other halogen-free FRs will be presented. Work done in collaboration with S. Levchik, ICL-IP America, 430 Saw Mill Rriver Rd., Ardsley, NY, 10502, USA and M. Leifer, ICL-IP, P. O. Box 180, Beer Sheva 84101, Israel.

  12. Environmental monitoring of brominated flame retardants

    NASA Astrophysics Data System (ADS)

    Vagula, Mary C.; Kubeldis, Nathan; Nelatury, Charles F.

    2011-06-01

    Brominated flame retardants (BFRs) are synthetic organobromide compounds which inhibit ignition and combustion processes. Because of their immense ability to retard fire and save life and property, they have been extensively used in many products such as TVs, computers, foam, plastics etc. The five major classes of BFRs are tetrabromobisphenol-A (TBBPA), hexabromocyclododecane (HBCD), pentabromodiphenyl ether, octabromodiphenyl ether, and decabromodiphenyl ether. The last three are also commonly called PBDEs. BDE-85 and BDE-209 are the two prominent congeners of PBDEs and this study reports the adverse effects of these congeners in rodents. Exposure of rat sciatic nerves to 5 μg/mL and 20 μg/mL of BDE-85 and BDE-209 respectively lead to significant, concentration dependent reduction in nerve conduction function. Glucose absorption in the rat intestinal segments exposed to 5 μg/mL of BDE-85 and BDE-209 was significantly reduced for both the compounds tested. Lastly, mice when exposed to 0.25 mg/kg body weight for four days showed a disruption in oxidant and antioxidant equilibrium. The tissues namely liver and brain have shown increase in the levels of lipid hydroperoxides indicating oxidative stress. Moreover, all the protective enzymes namely superoxide dismutase (SOD), glutathione peroxidase (GPx), catalase, and glutathione S transferase (GST) have shown tissue specific alterations indicating the induction of damaging oxidative stress and setting in of lipid peroxidation in exposed animals. The results indicate monitoring of PBDEs in the environment is essential because levels as low as 5 μg/mL and 0.25 mg/kg body weight were able to cause damage to the functions of rodents.

  13. Non-flammable elastomeric fiber from a fluorinated elastomer and containing an halogenated flame retardant

    NASA Technical Reports Server (NTRS)

    Howarth, J. T.; Sheth, S. G.; Sidman, K. R.; Massucco, A. A. (Inventor)

    1976-01-01

    Flame retardant elastomeric compositions are described comprised of either spandex type polyurethane having incorporated into the polymer chain halogen containing polyols, conventional spandex type polyurethanes in physical admixture with flame retardant additives, or fluoroelastomeric resins in physical admixture with flame retardant additives. Methods are described for preparing fibers of the flame retardant elastomeric materials and articles of manufacture comprised of the flame retardant clastomeric materials and non elastic materials such as polybenzimidazoles, fiberglass, nylons, etc.

  14. Flame Retardant Exposure among Collegiate U.S. Gymnasts

    PubMed Central

    Carignan, Courtney C.; Heiger-Bernays, Wendy; McClean, Michael D.; Roberts, Simon C.; Stapleton, Heather M.; Sjödin, Andreas; Webster, Thomas F.

    2013-01-01

    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. PMID:24195753

  15. Cone calorimeter evaluation of two flame retardant cotton fabrics

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Unbleached (grey) cotton needle punched nonwoven (NW) fabrics with 12.5% polypropylene scrim were treated with two phosphate-nitrogen based fire-retardant (FR) formulations, SRRC-1 and SRRC-2. The SRRC-1 formulation contains diammonium phosphate as the flame retardant chemical along with urea and d...

  16. Development of fiber reactive, non-halogenated flame retardant on cotton fabrics and the enhanced flame retardancy by covalent bonding

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The US law requires flame resistant properties on apparel or house hold items to prevent or minimize the fire damage. The objective of this research was to develop a non-halogenated flame retardant for application onto cotton fabrics. These treated fabrics can then be used in clothes or beddings to ...

  17. Measurement of flame retardants and triclosan in municipal sewage sludge and biosolids.

    PubMed

    Davis, Elizabeth F; Klosterhaus, Susan L; Stapleton, Heather M

    2012-04-01

    As polybrominated diphenyl ethers (PBDEs) face increasing restrictions worldwide, several alternate flame retardants are expected to see increased use as replacement compounds in consumer products. Chemical analysis of biosolids collected from wastewater treatment plants (WWTPs) can help determine whether these flame retardants are migrating from the indoor environment to the outdoor environment, where little is known about their ultimate fate and effects. The objective of this study was to measure concentrations of a suite of flame retardants, and the antimicrobial compound triclosan, in opportunistic samples of municipal biosolids and the domestic sludge Standard Reference Material (SRM) 2781. Grab samples of biosolids were collected from two WWTPs in North Carolina and two in California. Biosolids samples were also obtained during three subsequent collection events at one of the North Carolina WWTPs to evaluate fluctuations in contaminant levels within a given facility over a period of three years. The biosolids and SRM 2781 were analyzed for PBDEs, hexabromobenzene (HBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), di(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH), the chlorinated flame retardant Dechlorane Plus (syn- and anti-isomers), and the antimicrobial agent 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan). PBDEs were detected in every sample analyzed, and ΣPBDE concentrations ranged from 1750 to 6358ng/g dry weight. Additionally, the PBDE replacement chemicals TBB and TBPH were detected at concentrations ranging from 120 to 3749 ng/g dry weight and from 206 to 1631 ng/g dry weight, respectively. Triclosan concentrations ranged from 490 to 13,866 ng/g dry weight. The detection of these contaminants of emerging concern in biosolids suggests that these chemicals have the potential to migrate out of consumer products and enter the outdoor environment. PMID:22280921

  18. Exposure to flame retardant chemicals on commercial airplanes

    PubMed Central

    2013-01-01

    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

  19. A Polycarbonate/Magnesium Oxide Nanocomposite with High Flame Retardancy

    PubMed Central

    Dong, Quanxiao; Gao, Chong; Ding, Yanfen; Wang, Feng; Wen, Bin; Zhang, Shimin; Wang, Tongxin; Yang, Mingshu

    2014-01-01

    A new flame retardant polycarbonate/magnesium oxide (PC/MgO) nanocomposite, with high flame retardancy was developed by melt compounding. The effect of MgO to the flame retardancy, thermal property, and thermal degradation kinetics were investigated. Limited oxygen index (LOI) test revealed that a little amount of MgO (2 wt %) led to significant enhancement (LOI = 36.8) in flame retardancy. Thermogravimetric analysis results demonstrated that the onset temperature of degradation and temperature of maximum degradation rate decreased in both air and N2 atmosphere. Apparent activation energy was estimated via Flynn–Wall–Ozawa method. Three steps in the thermal degradation kinetics were observed after incorporation of MgO into the matrix and the additive raised activation energies of the composite in the full range except the initial stage. It was interpreted that the flame retardancy of PC was influenced by MgO through the following two aspects: on the one hand, MgO catalyzed the thermal-oxidative degradation and accelerated a thermal protection/mass loss barrier at burning surface; on the other hand, the filler decreased activation energies in the initial step and improved thermal stability in the final period. PMID:24696526

  20. Brominated flame retardants and organochlorine compounds in duplicate diet samples from a Portuguese academic community.

    PubMed

    Coelho, Sónia D; Sousa, Ana C A; Isobe, Tomohiko; Kunisue, Tatsuya; Nogueira, António J A; Tanabe, Shinsuke

    2016-10-01

    Concentrations of persistent organic pollutants (POPs), including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs), polychlorinated biphenyls (PCBs), hexachlorocyclohexane isomers (HCHs), hexachlorobenzene (HCB), chlordane compounds (CHLs) and dichlorodiphenyltrichloroethane and its metabolites (DDTs), were measured in duplicate diet samples from 21 volunteers at a Portuguese academic community (University of Aveiro). Overall, the levels of the target compounds were low, with detection frequencies varying widely depending on the compounds and with brominated flame retardants (BFRs) registering the lowest detection frequencies. Among PCB congeners, nondioxin-like PCBs were predominant and detected in the majority of the samples. Organochlorine pesticides were also detected in the majority of the samples, with 100% detection for DDTs and HCHs. Estimated daily intakes (EDIs) were calculated using lower and upper bound estimations, and in both cases values were far below the currently established tolerable daily intakes for PCBs and OCs and the reference doses for PBDEs and HBCDDs. PMID:27367176

  1. Phosphorus flame retardants: properties, production, environmental occurrence, toxicity and analysis.

    PubMed

    van der Veen, Ike; de Boer, Jacob

    2012-08-01

    Since the ban on some brominated flame retardants (BFRs), phosphorus flame retardants (PFRs), which were responsible for 20% of the flame retardant (FR) consumption in 2006 in Europe, are often proposed as alternatives for BFRs. PFRs can be divided in three main groups, inorganic, organic and halogen containing PFRs. Most of the PFRs have a mechanism of action in the solid phase of burning materials (char formation), but some may also be active in the gas phase. Some PFRs are reactive FRs, which means they are chemically bound to a polymer, whereas others are additive and mixed into the polymer. The focus of this report is limited to the PFRs mentioned in the literature as potential substitutes for BFRs. The physico-chemical properties, applications and production volumes of PFRs are given. Non-halogenated PFRs are often used as plasticisers as well. Limited information is available on the occurrence of PFRs in the environment. For triphenyl phosphate (TPhP), tricresylphosphate (TCP), tris(2-chloroethyl)phosphate (TCEP), tris(chloropropyl)phosphate (TCPP), tris(1,3-dichloro-2-propyl)phosphate (TDCPP), and tetrekis(2-chlorethyl)dichloroisopentyldiphosphate (V6) a number of studies have been performed on their occurrence in air, water and sediment, but limited data were found on their occurrence in biota. Concentrations found for these PFRs in air were up to 47 μg m(-3), in sediment levels up to 24 mg kg(-1) were found, and in surface water concentrations up to 379 ng L(-1). In all these matrices TCPP was dominant. Concentrations found in dust were up to 67 mg kg(-1), with TDCPP being the dominant PFR. PFR concentrations reported were often higher than polybrominated diphenylether (PBDE) concentrations, and the human exposure due to PFR concentrations in indoor air appears to be higher than exposure due to PBDE concentrations in indoor air. Only the Cl-containing PFRs are carcinogenic. Other negative human health effects were found for Cl-containing PFRs as well as

  2. Determination of brominated flame retardants in Jukskei River catchment area in Gauteng, South Africa.

    PubMed

    Olukunle, O I; Okonkwo, O J; Kefeni, K K; Lupankwa, M

    2012-01-01

    Brominated flame retardants (BFRs) are considered to be environmental pollutants due to their toxicity, persistence and ubiquity in the environment. Little information is known about the presence of brominated flame retardants in South Africa's water systems. Therefore, this study examined and compared different extraction methods (liquid-liquid (LL) vs. solid phase (SP) for water, Soxhlet extraction (SE) vs. ultrasonic for sediment) for extraction efficiencies in the determination of polybrominated diphenyl ethers (PBDEs) and polybrominated biphenyls (PBBs) in water and sediment from Jukskei River. Clean-up of sample extracts was performed using disposable Pasteur pipettes containing neutral, acidified and basic silica gel. Final extracts, after concentration and dilution to 200 μL were analyzed by injecting 1 μL in the GC-ECD and GC-MS. Results obtained showed good recoveries for most of the tested analytes in water; for LLE, values ranged between 80.5 ± 10.22% and 126.6 ± 1.94%; SPE, 70.41 ± 2.01%-124.78 ± 3.78% (n = 3) and for sediment (73-114%, with an RSD <17%) using SE. The ultrasonic extraction method gave less than 50% recovery for most of the congeners. The concentrations of the BFRs in water samples were less than the detection limit while the concentrations in sediment ranged from 1.95 to 36.61 ng g(-1) dry weight for Σ(11) BFRs. Dichloromethane and n-hexane : acetone (2 : 1, v/v) gave optimum value of recovery for water and sediment respectively. PMID:22277235

  3. Process for spinning flame retardant elastomeric compositions. [fabricating synthetic fibers for high oxygen environments

    NASA Technical Reports Server (NTRS)

    Howarth, J. T.; Sheth, S.; Sidman, K. R.; Massucco, A. A. (Inventor)

    1978-01-01

    Flame retardant elastomeric compositions comprised of either spandex type polyurethane having halogen containing polyols incorporated into the polymer chain, conventional spandex type polyurethanes in physical admixture with flame retardant additives, or fluoroelastomeric resins in physical admixture with flame retardant additives were developed. Methods are described for preparing fibers of the flame retardant elastomeric materials and manufactured articles as well as nonelastic materials such as polybenzimidazoles, fiberglass, and nylons, for high oxygen environments.

  4. Spatial distribution of old and emerging flame retardants in Chinese forest soils: sources, trends and processes.

    PubMed

    Zheng, Qian; Nizzetto, Luca; Li, Jun; Mulder, Marie D; Sáňka, Ondřej; Lammel, Gerhard; Bing, Haijian; Liu, Xin; Jiang, Yishan; Luo, Chunling; Zhang, Gan

    2015-03-01

    The levels and distribution of polybrominated diphenylethers (PBDEs), novel brominated flame retardants (NBFRs) and Dechlorane Plus (DP) in soils and their dependence on environmental and anthropological factors were investigated in 159 soil samples from 30 background forested mountain sites across China. Decabromodiphenylethane (DBDPE) was the most abundant flame retardant (25-18,000 pg g(-1) and 5-13,000 pg g(-1) in O-horizon and A-horizon, respectively), followed by BDE 209 (nd-5900 pg g(-1) and nd-2400 pg g(-1) in O-horizon and A-horizon, respectively). FRs distributions were primarily controlled by source distribution. The distributions of most phasing-out PBDEs, DP isomers and TBPH were in fact correlated to a population density-based index used as proxy of areas with elevated usage and waste of FR containing products. High concentrations of some NBFRs were however observed in industrialized regions and FR manufacturing plants. Strongly positive correlations were observed between PBDEs and their replacement products suggesting similar emission pattern and environmental behavior. Exposure of mineral subsoils depended on precipitations driving leaching of FRs into the soil core. This was especially evident for some emerging BFRs (TBE, TBPH, and TBB etc.) possibly indicating potential for diffuse groundwater contamination. PMID:25661400

  5. Flame retardants and organochlorine pollutants in bald eagle plasma from the Great Lakes region.

    PubMed

    Venier, Marta; Wierda, Michael; Bowerman, William W; Hites, Ronald A

    2010-08-01

    We report measurements of polybrominated diphenyl ethers and of emerging flame retardants in the plasma of nestling bald eagles sampled from early May to late June of 2005. Concentrations of total PBDEs ranged from 0.35 ng g(-1) ww to 29.3 ng g(-1) ww (average=5.7+/-1.9 ng g(-1) ww). The most abundant congeners were BDE-47, BDE-99, and BDE-100. The fully brominated congener, BDE-209, was detected in approximately one third of the samples at an average concentration of 1.2+/-0.72 ng g(-1) ww. Several emerging flame retardants, such as pentabromoethylbenzene (PBEB), hexabromocyclododecanes (HBCDs), and Dechlorane Plus (DP), were detected in these samples. Polychlorinated biphenyls (PCBs) and organochlorine pesticides were also detected at levels close to those previously published. A statistically significant relationship was found between total PBDE concentrations and total PCB and p,p'-DDE concentrations, suggesting that these compounds share a common source, which is most likely the eagle's food. PMID:20579684

  6. Acute and developmental behavioral effects of flame retardants and related chemicals in zebrafish

    PubMed Central

    Jarema, Kimberly A.; Hunter, Deborah L.; Shaffer, Rachel M.; Behl, Mamta; Padilla, Stephanie

    2016-01-01

    As polybrominated diphenyl ethers are phased out, numerous compounds are emerging as potential replacement flame retardants for use in consumer and electronic products. Little is known, however, about the neurobehavioral toxicity of these replacements. This study evaluated the neurobehavioral effects of acute or developmental exposure to t-butylphenyl diphenyl phosphate (BPDP), 2-ethylhexyl diphenyl phosphate (EHDP), isodecyl diphenyl phosphate (IDDP), isopropylated phenyl phosphate (IPP), tricresyl phosphate (TMPP; also abbreviated TCP), triphenyl phosphate (TPHP; also abbreviated TPP), tetrabromobisphenol A (TBBPA), tris (2-chloroethyl) phosphate (TCEP), tris (1,3-dichloroisopropyl) phosphate (TDCIPP; also abbreviated TDCPP), tri-o-cresyl phosphate (TOCP), and 2,2-,4,4′-tetrabromodiphenyl ether (BDE-47) in zebrafish (Danio rerio) larvae. Larvae (n ≈ 24 per dose per compound) were exposed to test compounds (0.4–120 µM) at sub-teratogenic concentrations either developmentally or acutely, and locomotor activity was assessed at 6 days post fertilization. When given developmentally, all chemicals except BPDP, IDDP and TBBPA produced behavioral effects. When given acutely, all chemicals produced behavioral effects, with TPHP, TBBPA, EHDP, IPP, and BPDP eliciting the most effects at the most concentrations. The results indicate that these replacement flame retardants may have developmental or pharmacological effects on the vertebrate nervous system. PMID:26348672

  7. Brominated flame retardants in the indoor environment - Comparative study of indoor contamination from three countries.

    PubMed

    Venier, Marta; Audy, Ondřej; Vojta, Šimon; Bečanová, Jitka; Romanak, Kevin; Melymuk, Lisa; Krátká, Martina; Kukučka, Petr; Okeme, Joseph; Saini, Amandeep; Diamond, Miriam L; Klánová, Jana

    2016-09-01

    Concentrations of more than 20 brominated flame retardants (FRs), including polybrominated diphenyl ethers (PBDEs) and emerging FRs, were measured in air, dust and window wipes from 63 homes in Canada, the Czech Republic and the United States in the spring and summer of 2013. Among the PBDEs, the highest concentrations were generally BDE-209 in all three matrices, followed by Penta-BDEs. Among alternative FRs, EHTBB and BEHTBP were detected at the highest concentrations. DBDPE was also a major alternative FR detected in dust and air. Bromobenzenes were detected at lower levels than PBDEs and other alternative FRs; among the bromobenzenes, HBB and PBEB were the most abundant compounds. In general, FR levels were highest in the US and lowest in the Czech Republic - a geographic trend that reflects the flame retardants' market. No statistically significant differences were detected between bedroom and living room FR concentrations in the same house (n=10), suggesting that sources of FRs are widespread indoors and mixing between rooms. The concentrations of FRs in air, dust, and window film were significantly correlated, especially for PBDEs. We found a significant relationship between the concentrations in dust and window film and in the gas phase for FRs with log KOA values <14, suggesting that equilibrium was reached for these but not compounds with log KOA values >14. This hypothesis was confirmed by a large discrepancy between values predicted using a partitioning model and the measured values for FRs with log KOA values >14. PMID:27248661

  8. Spatial Distribution and Air-Water Exchange of Organic Flame Retardants in the Lower Great Lakes.

    PubMed

    McDonough, Carrie A; Puggioni, Gavino; Helm, Paul A; Muir, Derek; Lohmann, Rainer

    2016-09-01

    Organic flame retardants (OFRs) such as polybrominated diphenyl ethers (PBDEs) and novel halogenated flame retardants (NHFRs) are ubiquitous, persistent, and bioaccumulative contaminants that have been used in consumer goods to slow combustion. In this study, polyethylene passive samplers (PEs) were deployed throughout the lower Great Lakes (Lake Erie and Lake Ontario) to measure OFRs in air and water, calculate air-water exchange fluxes, and investigate spatial trends. Dissolved Σ12BDE was greatest in Lake Ontario near Toronto (18 pg/L), whereas gaseous Σ12BDE was greatest on the southern shoreline of Lake Erie (11 pg/m(3)). NHFRs were generally below detection limits. Air-water exchange was dominated by absorption of BDEs 47 and 99, ranging from -964 pg/m(2)/day to -30 pg/m(2)/day. Σ12BDE in air and water was significantly correlated with surrounding population density, suggesting that phased-out PBDEs continued to be emitted from population centers along the Great Lakes shoreline in 2012. Correlation with dissolved Σ12BDE was strongest when considering population within 25 km while correlation with gaseous Σ12BDE was strongest when using population within 3 km to the south of each site. Bayesian kriging was used to predict dissolved Σ12BDE over the lakes, illustrating the utility of relatively highly spatially resolved measurements in identifying potential hot spots for future study. PMID:27458653

  9. Brominated flame retardants in matched serum samples from Swedish first-time mothers and their toddlers.

    PubMed

    Sahlström, Leena M O; Sellström, Ulla; de Wit, Cynthia A; Lignell, Sanna; Darnerud, Per Ola

    2014-07-01

    Tri-decabrominated diphenyl ethers and 21 other flame retardants were determined in matched serum samples from 24 Swedish mothers (Uppsala county) and their toddlers (11-15 months of age). The median concentrations of individual polybrominated diphenyl ethers (PBDEs) ranged from 0.036 to 0.95 ng/g lipid in mothers and from 0.057 to 1.5 ng/g lipid in toddlers. BDE-209 was detected in all but one sample. BDE-153 was the predominant congener in the mothers while in toddlers, BDE-209 was found in the highest concentrations. The levels of BDE-47, -100, -207, -208, and -209 in toddlers were significantly higher (p < 0.05) than those in their mothers. Dechlorane Plus (anti- and syn-) and α- and β-tetrabromoethylcyclohexane were detected in a few (2-4) serum samples from both mothers and toddlers. This study also reports concentrations of α-HBCD and eight emerging brominated flame retardants (EBFRs) in the standard reference material serum (SRM 1958, NIST). Lack of correlations between the matched serum samples indicate different exposure routes for octa-decaBDEs in mothers versus toddlers. Congener-to-congener correlations within the mother or toddler cohorts suggest diet as an important exposure pathway for tetra-nonaBDEs for mothers, breastfeeding as a predominant exposure pathway for tetra-hexaBDEs, and dust for octa-decaBDEs for toddlers. PMID:24927135

  10. Innovative green technique for preparing of flame retardant cotton

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Due to its environmentally benign character, microwave-assisted or supercritical carbon dioxide high pressure reactors are considered in green chemistry as a substitute for organic solvents in chemical reactions. In this paper, an innovative approach for preparation of flame retardant cotton fabric ...

  11. Phosphorus Containing Flame Retardants and Their Textile Applications

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this paper, we discuss the new challenge phosphorus containing flame retardant compounds and the properties for covalently bonded cotton’s surface. We showed the design, synthesis, and characterization of (2-methyl-oxiranylmethyl)-phosphonic acid dimethyl ester and [2-(dimethoxy-phosphorylmethyl)...

  12. Green Flame Retardant Cotton Highlofts for Mattresses and Upholstered Furniture

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Green flame retardant (FR) barrier fabric is environmentally-friendly because it is from a natural renewable resource, biodegradable, economical, employing greige cotton that is soft to touch. Greige unbleached cotton is cheaper and softer than bleached cotton, thus, increasing its marketability par...

  13. NOVEL 'GREENER' ROUTES TO HALOGEN-FREE FLAME RETARDANT MATERIALS

    EPA Science Inventory

    The increased use of polymeric materials in numerous applications over the past decade has prompted a surge in the need for additives in the polymer industry. Flame retardant (FR) materials are additives that are used to control or reduce/eliminate the risk of fire in flammabl...

  14. Mimicking of Estradiol Binding by Flame Retardants and Their Metabolites: A Crystallographic Analysis

    PubMed Central

    Gosavi, Rajendrakumar A.; Knudsen, Gabriel A.; Birnbaum, Linda S.

    2013-01-01

    Background: Brominated flame retardants (BFRs), used in many types of consumer goods, are being studied because of concerns about possible health effects related to endocrine disruption, immunotoxicity, reproductive toxicity, and neurotoxicity. Tetrabromobisphenol A (TBBPA), the most widely used BFR, and human metabolites of certain congeners of polybrominated diphenyl ether (e.g., 3-OH-BDE-47) have been suggested to inhibit estrogen sulfotransferase, potentially affecting estrogen metabolism. Objectives: Our primary goal was to understand the structural mechanism for inhibition of the hormone-metabolizing enzyme estrogen sulfotransferase by certain BFRs. We also sought to understand various factors that facilitate the binding of flame retardants in the enzyme binding pocket. Methods: We used X-ray crystallography to obtain atomic detail of the binding modes of TBBPA and 3-OH-BDE-47 to estrogen sulfotransferase for comparison with binding of the endogenous substrate estradiol. Results: The crystal structures reveal how BFRs mimic estradiol binding as well as the various interactions between the compounds and protein residues that facilitate its binding. In addition, the structures provide insights into the ability of the sulfotransferase substrate binding pocket to accommodate a range of halogenated compounds that satisfy minimal structural criteria. Conclusions: Our results show how BFRs or their metabolites can bind to and inhibit a key hormone-metabolizing enzyme, potentially causing endocrine disruption. Citation: Gosavi RA, Knudsen GA, Birnbaum LS, Pedersen LC. 2013. Mimicking of estradiol binding by flame retardants and their metabolites: a crystallographic analysis. Environ Health Perspect 121:1194–1199; http://dx.doi.org/10.1289/ehp.1306902 PMID:23959441

  15. Multi-residue method for the determination of brominated and organophosphate flame retardants in indoor dust.

    PubMed

    Van den Eede, Nele; Dirtu, Alin C; Ali, Nadeem; Neels, Hugo; Covaci, Adrian

    2012-01-30

    A new method was optimized for the simultaneous determination of several flame retardants (FRs) in indoor dust, namely polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), novel brominated flame retardants (NBFRs) and organophosphate ester flame retardants (OPFRs). The method was based on two previously validated analytical methods for NBFRs and OPFRs, which were combined in order to include even a large number of FRs. An ultrasonic extraction method and two-stage clean-up by adsorption chromatography was optimized using an indoor dust standard reference material (SRM 2584). The 1st cleanup step was essential for fractionation of analytes in the dust extracts, while the 2nd step was important for the further removal of interferences. Analysis of cleaned dust extracts was performed with gas chromatography electron impact ionization mass spectrometry for OPFRs, gas chromatography electron capture negative ionization mass spectrometry for PBDEs and NBFRs and liquid chromatography electrospray ionization tandem mass spectrometry for HBCDs. Method validation by matrix spiking demonstrated good accuracy ranging from 81 to 130%. Matrix effects were investigated by spiking sodium sulfate and dust with analyte standards. Typical recoveries ranged between 80 and 110% at both spiking levels, though occasional deviations were observed at low spiking concentrations. Precision between different days was generally below 24% relative standard deviation (RSD) at low concentrations and below 11% RSD at high concentrations. Method limits of quantification for BFRs ranged between 0.04 (BDE 28) and 17 ng/g (BDE 209), 6 ng/g for sum HBCDs, and for OPFRs between 10 (triphenyl phosphate) and 370 ng/g (tri-isobutyl phosphate). The method was applied to SRM 2585 and to a set of indoor dust samples from various countries. The newly developed method will be employed for the monitoring of human exposure via dust ingestion to phased-out and alternate FRs. PMID:22284495

  16. Associations between brominated flame retardants in house dust and hormone levels in men.

    PubMed

    Johnson, Paula I; Stapleton, Heather M; Mukherjee, Bhramar; Hauser, Russ; Meeker, John D

    2013-02-15

    Brominated flame retardants (BFRs) are used in the manufacture of a variety of materials and consumer products in order to meet fire safety standards. BFRs may persist in the environment and have been detected in wildlife, humans and indoor dust and air. Some BFRs have demonstrated endocrine and reproductive effects in animals, but human studies are limited. In this exploratory study, we measured serum hormone levels and flame retardant concentrations [31 polybrominated diphenyl ether (PBDE) congeners and 6 alternate flame retardants] in house dust from men recruited through a US infertility clinic. PBDE congeners in dust were grouped by commercial mixtures (i.e. penta-, octa- and deca-BDE). In multivariable linear regression models adjusted by age and body mass index (BMI), significant positive associations were found between house dust concentrations of pentaBDEs and serum levels of free T4, total T3, estradiol, and sex hormone binding globulin (SHBG), along with an inverse association with follicle stimulating hormone (FSH). There were also positive associations of octaBDE concentrations with serum free T4, thyroid stimulating hormone (TSH), luteinizing hormone (LH) and testosterone and an inverse association of decaBDE concentrations with testosterone. Hexabromocyclododecane (HBCD) was associated with decreased SHBG and increased free androgen index. Dust concentrations of bis-tribromophenoxyethane (BTBPE) and tetrabromo-diethylhexylphthalate (TBPH) were positively associated with total T3. These findings are consistent with our previous report of associations between PBDEs (BDE 47, 99 and 100) in house dust and hormone levels in men, and further suggest that exposure to contaminants in indoor dust may be leading to endocrine disruption in men. PMID:23333513

  17. DEVELOPMENTAL EXPOSURES TO POLYBROMINATED DIPHENYLETHERS: DISRUPTION OF THYROID HORMONES, HEPATIC METABOLISM AND NEUROBEHAVIORAL DEVELOPMENT.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs), produced commercially as mixtures, are used as flame-retardants in numerous consumer products. Previous work has demonstrated that the DE-71 induces hypothyroxinemia in various animal models. In a series of studies, primiparous dams were...

  18. STIMULATION OF [3H] ARACHIDONIC ACID RELEASE IN RAT CEREBELLAR GRANULE NEURONS BY POLYBROMINATED DIPHENYL.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants in electronic equipment, plastics, textiles, and building materials. While the presence of other persistent organic pollutants, such as polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxin...

  19. DEVELOPMENTAL EXPOSURE TO POLYBROMINATED DIPHENYL ETHERS DOES NOT ALTER SYNAPTIC TRANSMISSION AND LTP IN HIPPOCAMPUS.

    EPA Science Inventory

    Polybrominated diphenyl ether (PDE) flame retardants bioaccumulate in the environment, in wildlife, and in humans. Concern has been raised over potential thyrotoxic effects of this class of xenobiotics. Severe hypothyroidism during critical periods of brain development leads to...

  20. Investigation of Reagent Gases for the Positive Chemical Ionization of Select Polybrominated Diphenyl Ethers

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) fall into the class of compounds known as brominated flame retardants and their incorporation in a multitude of products is responsible for saving numerous lives. However, toxicology studies have alerted researchers to the potential adverse...

  1. Neurotoxicity and risk assessment of brominated and alternative flame retardants.

    PubMed

    Hendriks, Hester S; Westerink, Remco H S

    2015-01-01

    Brominated flame retardants (BFRs) are widely used chemicals that prevent or slow the onset and spreading of fire. Unfortunately, many of these compounds pose serious threats for human health and the environment, indicating an urgent need for safe(r) and less persistent alternative flame retardants (AFRs). As previous research identified the nervous system as a sensitive target organ, the neurotoxicity of past and present flame retardants is reviewed. First, an overview of the neurotoxicity of BFRs in humans and experimental animals is provided, and some common in vitro neurotoxic mechanisms of action are discussed. The combined epidemiological and toxicological studies clearly underline the need for replacing BFRs. Many potentially suitable AFRs are already in use, despite the absence of a full profile of their environmental behavior and toxicological properties. To prioritize the suitability of some selected halogenated and non-halogenated organophosphorous flame retardants and inorganic halogen-free flame retardants, the available neurotoxic data of these AFRs are discussed. The suitability of the AFRs is rank-ordered and combined with human exposure data (serum concentrations, breast milk concentrations and house dust concentrations) and physicochemical properties (useful to predict e.g. bioavailability and persistence in the environment) for a first semi-quantitative risk assessment of the AFRs. As can be concluded from the reviewed data, several BFRs and AFRs share some neurotoxic effects and modes of action. Moreover, the available neurotoxicity data indicate that some AFRs may be suitable substitutes for BFRs. However, proper risk assessment is hampered by an overall scarcity of data, particularly regarding environmental persistence, human exposure levels, and the formation of breakdown products and possible metabolites as well as their toxicity. Until these data gaps in environmental behavioral and toxicological profiles are filled, large scale use of

  2. Temporal trends and spatial distributions of brominated flame retardants in archived fishes from the Great Lakes.

    PubMed

    Zhu, Ling Yan; Hites, Ronald A

    2004-05-15

    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. PMID:15212250

  3. Monitoring of WEEE plastics in regards to brominated flame retardants using handheld XRF.

    PubMed

    Aldrian, Alexia; Ledersteger, Alfred; Pomberger, Roland

    2015-02-01

    This contribution is focused on the on-site determination of the bromine content in waste electrical and electronic equipment (WEEE), in particular waste plastics from television sets (TV) and personal computer monitors (PC) using a handheld X-ray fluorescence (XRF) device. The described approach allows the examination of samples in regards to the compliance with legal specifications for polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) directly after disassembling and facilitates the sorting out of plastics with high contents of brominated flame retardants (BFRs). In all, over 3000 pieces of black (TV) and 1600 pieces of grey (PC) plastic waste were analysed with handheld XRF technique for this study. Especially noticeable was the high percentage of pieces with a bromine content of over 50,000ppm for TV (7%) and PC (39%) waste plastics. The applied method was validated by comparing the data of handheld XRF with results obtained by GC-MS. The results showed the expected and sufficiently accurate correlation between these two methods. It is shown that handheld XRF technique is an effective tool for fast monitoring of large volumes of WEEE plastics in regards to BFRs for on-site measurements. PMID:25464945

  4. Phosphate flame retardants and novel brominated flame retardants in home-produced eggs from an e-waste recycling region in China.

    PubMed

    Zheng, Xiaobo; Xu, Fuchao; Luo, Xiaojun; Mai, Bixian; Covaci, Adrian

    2016-05-01

    Phosphate flame retardants (PFRs) and novel brominated flame retardants (NBFRs) (2-ethylhexyl-2,3,4,5-tetrabromo-benzoate (EH-TBB) and bis-(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEH-TEBP)) were measured in free-range chicken eggs from three e-waste recycling sites and a negative control site located in Guangdong province, Southern China. BEH-TEBP, tris-(chloroethyl)-phosphate (TCEP), tris-(chloropropyl)-phosphate (∑TCPP, two isomers) and tris-(1,3-dichloroisopropyl)-phosphate (TDCIPP) were detected in more than 50% of eggs samples with low concentrations. The median values of BEH-TEBP and total PFRs were 0.17-0.46 ng/g ww (wet weight) and 1.62-2.59 ng/g ww in eggs from the e-waste sites, respectively. The results indicate that EH-TBB, BEH-TEBP and PFRs are less persistent and bioaccumulative than polybrominated diphenyl ethers (PBDEs) in chicken eggs, and possibly also in other bio-matrices. Triphenyl phosphate (TPHP) were identified in albumen with higher frequencies, but at similar concentrations compared to yolk, while BEH-TEBP was mainly detected in yolk. The estimated daily intake (EDI) of BEH-TEBP and total PFRs from consumption of chicken eggs ranged from 0.03 to 0.09 and 0.32-0.52 ng/kg bw/day for adults, and 0.20-0.54 and 1.89-3.02 ng/kg bw/day for children in e-waste sites, respectively. Indoor dust ingestion seems to be a more important pathway for the intake of these FRs, while egg consumption is probably a more important exposure pathway for PBDEs. PMID:26460270

  5. Part I. improve flame retardant textile. Part II. novel approach layer-by-layer processing for flame retardant textile.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this presentation, new approaches for flame retardant textile by using supercritical carbon dioxide (scCO2) and layer-by-layer processing will be discussed. Due to its environmentally benign character, the scCO2 is considered in green chemistry as a substitute for organic solvents in chemical rea...

  6. Part I. Improved flame retardant textiles. Part II. Novel approach to layer-by-layer processing for flame retardant textiles.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this presentation, new approaches for flame retardant textile by using supercritical carbon dioxide (scCO2) and layer-by-layer processing will be discussed. Due to its environmentally benign character, the scCO2 is considered in green chemistry as a substitute for organic solvents in chemical re...

  7. Effects of TiO₂ and curing temperatures on flame retardant finishing of cotton.

    PubMed

    Poon, Chin-Kuen; Kan, Chi-Wai

    2015-05-01

    The performance of flame retardancy of cotton cellulose can be influenced by curing conditions. In this study, cotton cellulose was imparted durable flame retardant properties by a reaction between a flame retardant agent (Pyrovatex CP New) and a cross linking agent (Knittex CHN), in the presence of catalysts phosphoric acid and titanium dioxide (TiO2). After treating cotton fabrics at different curing temperatures for different curing time, its flame retardant performance was evaluated by 45° fabric flammability standard test method. For cotton fabrics cured at 150 and 170°C, good flame retardant characteristics were retained even after three home laundering cycles. The use of TiO2 as a co-catalyst in the treatment improved the flame retardant properties and reduced the loss of tearing strength of cotton fabrics. No significant negative effect in the whiteness index was observed, as compared with conventional flame retardant treatment. PMID:25659721

  8. Halogenated flame retardants during egg formation and chicken embryo development: maternal transfer, possible biotransformation, and tissue distribution.

    PubMed

    Zheng, Xiao-Bo; Luo, Xiao-Jun; Zeng, Yan-Hong; Wu, Jiang-Ping; Chen, She-Jun; Mai, Bi-Xian

    2014-08-01

    Hen muscle, eggs, and newborn chick tissues (muscle and liver) were collected from an electronic waste recycling site in southern China. The authors examined the maternal transfer, potential metabolism, and tissue distribution of several halogenated flame retardants (HFRs) during egg formation and chicken embryo development. The pollutant composition changes significantly from hen muscle to eggs and from eggs to tissues of newborn chicks. Higher-halogenated chemicals, such as octa- to deca-polybrominated diphenyl ether (PBDE) congeners, deca-polybrominated biphenyl (PBB209), and dechlorane plus (DP), are less readily transferred to eggs compared with lower-halogenated chemicals. During embryo development, PBDEs are the most likely to be metabolized, whereas decabromodiphenyl ethane (DBDPE) is the least. The authors also observed selective maternal transfer of anti-DP and stereoselective metabolism of syn-DP during chicken embryo development. During tissue development, liver has greater affinity than the muscle for chemcials with a high log octanol-water partition coefficient, with the exception of DBDPE. The differences in metabolism potential of different chemicals in chicken embryos cause pollutant composition alterations. Halogenated flame retardant from maternal transfer and tissue distribution also exhibited chemical specificity, especially for DBDPE. Levels of DBDPE were elevated along with the full process from hen muscle to eggs and from eggs to chick tissues. More attention should be paid to the selective accumulation and biotransformation of HFRs in the early development stage of birds. PMID:24888473

  9. Plasma-enhanced synthesis of green flame retardant cellulosic materials

    NASA Astrophysics Data System (ADS)

    Totolin, Vladimir

    The natural fiber-containing fabrics and composites are more environmentally friendly, and are used in transportation (automobiles, aerospace), military applications, construction industries (ceiling paneling, partition boards), consumer products, etc. Therefore, the flammability characteristics of the composites based on polymers and natural fibers play an important role. This dissertation presents the development of plasma assisted - green flame retardant coatings for cellulosic substrates. The overall objective of this work was to generate durable flame retardant treatment on cellulosic materials. In the first approach sodium silicate layers were pre-deposited onto clean cotton substrates and cross linked using low pressure, non-equilibrium oxygen plasma. A statistical design of experiments was used to optimize the plasma parameters. The modified cotton samples were tested for flammability using an automatic 45° angle flammability test chamber. Aging tests were conducted to evaluate the coating resistance during the accelerated laundry technique. The samples revealed a high flame retardant behavior and good thermal stability proved by thermo-gravimetric analysis. In the second approach flame retardant cellulosic materials have been produced using a silicon dioxide (SiO2) network coating. SiO 2 network armor was prepared through hydrolysis and condensation of the precursor tetraethyl orthosilicate (TEOS), prior coating the substrates, and was cross linked on the surface of the substrates using atmospheric pressure plasma (APP) technique. Due to protection effects of the SiO2 network armor, the cellulosic based fibers exhibit enhanced thermal properties and improved flame retardancy. In the third approach, the TEOS/APP treatments were extended to linen fabrics. The thermal analysis showed a higher char content and a strong endothermic process of the treated samples compared with control ones, indicating a good thermal stability. Also, the surface analysis proved

  10. Comprehensive characterisation of flame retardants in textile furnishings by ambient high resolution mass spectrometry, gas chromatography-mass spectrometry and environmental forensic microscopy.

    PubMed

    Ionas, Alin C; Ballesteros Gómez, Ana; Uchida, Natsuyo; Suzuki, Go; Kajiwara, Natsuko; Takata, Kyoko; Takigami, Hidetaka; Leonards, Pim E G; Covaci, Adrian

    2015-10-01

    The presence and levels of flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs) and organophosphate flame retardants (PFRs), was determined in textile home furnishings, such as carpets and curtains from stores in Belgium. A comprehensive characterisation of FRs in textile was done by ambient high resolution mass spectrometry (qualitative screening), gas chromatography-mass spectrometry (GC-MS) (quantitation), and environmental forensic microscopy (surface distribution). Ambient ionisation coupled to a time-of-flight (TOF) high resolution mass spectrometer (direct probe-TOF-MS) was investigated for the rapid screening of FRs. Direct probe-TOF-MS proved to be useful for a first screening step of textiles to detect FRs below the levels required to impart flame retardancy and to reduce, in this way, the number of samples for further quantitative analysis. Samples were analysed by GC-MS to confirm the results obtained by ambient mass spectrometry and to obtain quantitative information. The levels of PBDEs and PFRs were typically too low to impart flame retardancy. Only high levels of BDE-209 (11-18% by weight) were discovered and investigated in localised hotspots by employing forensic microscopy techniques. Most of the samples were made of polymeric materials known to be inherently flame retarded to some extent, so it is likely that other alternative and halogen-free FR treatments/solutions are preferred for the textiles on the Belgian market. PMID:26398896

  11. Environmental Impact of Flame Retardants (Persistence and Biodegradability)

    PubMed Central

    Segev, Osnat; Kushmaro, Ariel; Brenner, Asher

    2009-01-01

    Flame-retardants (FR) are a group of anthropogenic environmental contaminants used at relatively high concentrations in many applications. Currently, the largest market group of FRs is the brominated flame retardants (BFRs). Many of the BFRs are considered toxic, persistent and bioaccumulative. Bioremediation of contaminated water, soil and sediments is a possible solution for the problem. However, the main problem with this approach is the lack of knowledge concerning appropriate microorganisms, biochemical pathways and operational conditions facilitating degradation of these chemicals at an acceptable rate. This paper reviews and discusses current knowledge and recent developments related to the environmental fate and impact of FRs in natural systems and in engineered treatment processes. PMID:19440395

  12. Graphene phosphonic acid as an efficient flame retardant.

    PubMed

    Kim, Min-Jung; Jeon, In-Yup; Seo, Jeong-Min; Dai, Liming; Baek, Jong-Beom

    2014-03-25

    We report the preparation of graphene phosphonic acid (GPA) via a simple and versatile method and its use as an efficient flame retardant. In order to covalently attach phosphorus to the edges of graphene nanoplatelets, graphite was ball-milled with red phosphorus. The cleavage of graphitic C-C bonds during mechanochemical ball-milling generates reactive carbon species, which react with phosphorus in a sealed ball-mill crusher to form graphene phosphorus. Subsequent opening of the crusher in air moisture leads to violent oxidation of graphene phosphorus into GPA (highest oxidation state). The GPA is readily dispersible in many polar solvents, including neutral water, allowing for solution (spray) coating for high-performance, nontoxic flame-retardant applications. PMID:24575902

  13. Fabrication of cotton fabric with superhydrophobicity and flame retardancy.

    PubMed

    Zhang, Ming; Wang, Chengyu

    2013-07-25

    A simple and facile method for fabricating the cotton fabric with superhydrophobicity and flame retardancy is described in the present work. The cotton fabric with the maximal WCA of 160° has been prepared by the covalent deposition of amino-silica nanospheres and the further graft with (heptadecafluoro-1,1,2,2-tetradecyl) trimethoxysilane. The geometric microstructure of silica spheres was measured by transmission electron microscopy (TEM). The cotton textiles before and after treatment were characterized by using scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS). The wetting behavior of cotton samples was investigated by water contact angle measurement. Moreover, diverse performances of superhydrophobic cotton textiles have been evaluated as well. The results exhibited the outstanding superhydrophobicity, excellent waterproofing durability and flame retardancy of the cotton fabric after treatment, offering a good opportunity to accelerate the large-scale production of superhydrophobic textiles materials for new industrial applications. PMID:23768579

  14. Fate of flame retardants and the antimicrobial agent triclosan in planted and unplanted biosolid-amended soils.

    PubMed

    Davis, Elizabeth F; Gunsch, Claudia K; Stapleton, Heather M

    2015-05-01

    A comprehensive understanding of the fate of contaminant-laden biosolids is needed to fully evaluate the environmental impacts of biosolid land application. The present study examined the fate of several flame retardants and triclosan in biosolid-amended soil in a 90-d greenhouse experiment. Objectives included evaluating the persistence of these compounds in soil, their phytoaccumulation potential by alfalfa (Medicago sativa), and potential degradation reactions. Concentrations of the polybrominated diphenyl ether (PBDE) congeners BDE-47 and BDE-209 and the antimicrobial triclosan declined significantly over time in biosolid-amended soil planted with alfalfa and then reached a steady state by day 28. In contrast, no significant losses of those analytes were observed from soil in nonvegetated pots. The amount of an analyte lost from vegetated soil ranged from 43% for the flame retardant di(2-ethylhexyl)-2,3,4,5-tetrabromophthalate to 61% for triclosan and was significantly and negatively related to the log octanol-water partition coefficient. Alfalfa roots and shoots were monitored for the compounds, but no clear evidence of phytoaccumulation was observed. Methyl triclosan formation was observed in the biosolid-amended soils during the study period, indicating in situ biotransformation of triclosan. The present study demonstrates that, although they are highly recalcitrant, PBDEs, selected alternate brominated flame retardants, and triclosan are capable of undergoing dissipation from biosolid-amended soils in the presence of plants. PMID:25546022

  15. Occurrence and sources of brominated and organophosphorus flame retardants in dust from different indoor environments in Barcelona, Spain.

    PubMed

    Cristale, Joyce; Hurtado, Alba; Gómez-Canela, Cristian; Lacorte, Silvia

    2016-08-01

    In this study, the simultaneous presence of eight polybrominated diphenyl ethers (PBDEs), nine new brominated flame retardants (NBFRs) and ten organophosphorus flame retardants (OPFRs) was investigated in dust samples collected from different indoor environments (homes, schools, theatres, a university and a Research Institute) in Barcelona, Spain. OPFRs were detected at the highest concentrations followed by PBDEs. ∑OPFRs ranged from 2053 to 72,090ngg(-1) and tris(2-chloroisopropyl) phosphate (TCIPP) was the most abundant compound. BDE-209 was the main PBDE congener detected (up to 14,990ngg(-1)), while other PBDEs ranged from 2.6 to 118ngg(-1). Among the studied NBFRs, decabromodiphenyl ethane (DBDPE - up to 4432ngg(-1)) followed by bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP - up to 508ngg(-1)) were detected at the highest concentration, whereas a lower detection frequency was observed for 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EH-TBB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), pentabromotoluene (PBT) and hexabromobenzene (HBB). The levels and profile of flame retardants (FRs) were characteristic of each environment, where theatres followed by homes presented the highest concentrations and schools had the lowest levels. Principal Component Analysis permitted to identify the main sources and distribution of all FRs, according to specific uses in each environment. The simultaneous presence of all FR families in indoor dust points to the need to monitor these compounds to minimize human exposure. PMID:27179204

  16. A review of chamber experiments for determining specific emission rates and investigating migration pathways of flame retardants

    NASA Astrophysics Data System (ADS)

    Rauert, Cassandra; Lazarov, Borislav; Harrad, Stuart; Covaci, Adrian; Stranger, Marianne

    2014-01-01

    The widespread use of flame retardants (FRs) in indoor products has led to their ubiquitous distribution within indoor microenvironments with many studies reporting concentrations in indoor air and dust. Little information is available however on emission of these compounds to air, particularly the measurement of specific emission rates (SERs), or the migration pathways leading to dust contamination. Such knowledge gaps hamper efforts to develop understanding of human exposure. This review summarizes published data on SERs of the following FRs released from treated products: polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), tetrabromobisphenol-A (TBBPA), novel brominated flame retardants (NBFRs) and organophosphate flame retardants (PFRs), including a brief discussion of the methods used to derive these SERs. Also reviewed are published studies that utilize emission chambers for investigations/measurements of mass transfer of FRs to dust, discussing the chamber configurations and methods used for these experiments. A brief review of studies investigating correlations between concentrations detected in indoor air/dust and possible sources in the microenvironment is included along with efforts to model contamination of indoor environments. Critical analysis of the literature reveals that the major limitations with utilizing chambers to derive SERs for FRs arise due to the physicochemical properties of FRs. In particular, increased partitioning to chamber surfaces, airborne particles and dust, causes loss through “sink” effects and results in long times to reach steady state conditions inside the chamber. The limitations of chamber experiments are discussed as well as their potential for filling gaps in knowledge in this area.

  17. Chemical regulation on fire: rapid policy advances on flame retardants.

    PubMed

    Cordner, Alissa; Mulcahy, Margaret; Brown, Phil

    2013-07-01

    Chemicals that are widely used in consumer products offer challenges to product manufacturers, risk managers, environmental regulators, environmental scientists, and the interested public. However, the factors that cause specific chemicals to rise to the level of regulatory, scientific, and social movement concern and scrutiny are not well documented, and scientists are frequently unclear about exactly how their research impacts policy. Through a case study of advocacy around flame retardant chemicals, this paper traces the pathways through which scientific evidence and concern is marshaled by both advocacy groups and media sources to affect policy change. We focus our analysis around a broad coalition of environmental and public health advocacy organizations and an investigative journalism series published in 2012 in the Chicago Tribune. We demonstrate that the Tribune series both brought the issue to a wider public audience and precipitated government action, including state policy revisions and federal Senate hearings. We also show how a broad and successful flame retardant coalition developed, leveraged a media event, and influenced policy at multiple institutional levels. The analysis draws on over 110 in-depth interviews, literature and Web site reviews, and observations at a flame retardant manufacturing company, government offices, and scientific and advocacy conferences. PMID:23713659

  18. Non-halogen Flame retardant High Impact Polystyrene Composites

    NASA Astrophysics Data System (ADS)

    Rafailovich, Miriam; Si, Mayu; Sokolov, Jonathan; Otaigbe, Joshia; Yudin, Vladimir E.

    2006-03-01

    In recent years, driven by the health issues and the incurred banning policy of bromine compounds, it is a great demand to find an alternate to replace brominated compounds in polymer flame retardant industry. High impact polystyrene (HIPS), a popular materials widely used for electrical appliances and electronic instruments, attracts extensive attention for its dominant flame retardant agent, decabromodiphenyl ether. Here we propose a novel idea to prepare non-halogen HIPS self-extinguishing composites based on the combination of phosphorus compounds and clay. The combustion behavior was thoroughly investigated by UL 94 V-0, LOI, and cone calorimeter measurements. The addition of Cloisite 20A dramatically decreases the value of LOI and the resulted HIPS composites could not pass UL 94 V-0. On the other hand, the introduction of thermal stable clay significantly increases the value of LOI and the corresponding HIPS composites can successfully self-extinguish. These results strongly demonstrate that the thermal stability of clay is the key factor to determine the final flame retardant performance. The synergy between the clay and phosphorus compounds is further studied.

  19. Toxicity of new generation flame retardants to Daphnia magna.

    PubMed

    Waaijers, Susanne L; Hartmann, Julia; Soeter, A Marieke; Helmus, Rick; Kools, Stefan A E; de Voogt, Pim; Admiraal, Wim; Parsons, John R; Kraak, Michiel H S

    2013-10-01

    There is a tendency to substitute frequently used, but relatively hazardous brominated flame retardants (BFRs) with halogen-free flame retardants (HFFRs). Consequently, information on the persistence, bioaccumulation and toxicity (PBT) of these HFFRs is urgently needed, but large data gaps and inconsistencies exist. Therefore, in the present study the toxicity of a wide range of HFFRs to the water flea Daphnia magna was investigated. Our results revealed that four HFFRs were showing no effect at their Sw (saturated water concentration) and three had a low toxicity (EC50>10 mg L(-1)), suggesting that these compounds are not hazardous. Antimony trioxide had a moderate toxicity (EC50=3.01 mg L(-1), 95% CL: 2.76-3.25) and triphenyl phosphate and the brominated reference compound tetra bromobisphenol A were highly toxic to D. magna (EC50=0.55 mg L(-1), 95% CL: 0.53-0.55 and EC50=0.60 mg L(-1), 95% CL: 0.24-0.97 respectively). Aluminum trihydroxide and bisphenol A bis(diphenyl phosphate) caused limited mortality at Sw (26 and 25% respectively) and have a low solubility (<10 mg L(-1)). Hence, increased toxicity of these compounds may be observed when for instance decreasing pH could increase solubility. By testing all compounds under identical conditions we provided missing insights in the environmental hazards of new generation flame retardants and propose as best candidates for BFR replacements: APP, ALPI, DOPO, MHO, MPP, ZHS and ZS. PMID:23886749

  20. PERINATAL EXPOSURE TO A POLYBROMINATED DIPHENYL ETHER MIXTURE (DE-71) DISRUPTS THYROID HORMONES BUT NOT NEUROBEHAVIORAL DEVELOPMENT.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs), produced commercially as mixtures, are used as flame-retardants for numerous consumer products. Because of their lipophilicity and persistence, PBDEs have become ubiquitous environmental contaminants. Previous work in our lab has demonstra...

  1. PERINATAL EXPOSURE TO A POLYBROMINATED DIPHENYL ETHER MIXTURE (DE-71): DISRUPTION OF THYROID HOMEOSTASIS AND NEUROBEHAVIORAL DEVELOPMENT.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs), produced commercially as mixtures, are used as flame-retardants in numerous consumer products. Previous work has demonstrated that the DE-71 induces hypothyroxinemia in both adults and developing rats. In these studies, primiparous rats w...

  2. Polybrominated diphenyl ether serum concentrations in a Californian population of children, their parents, and older adults: an exposure assessment study

    EPA Science Inventory

    BackgroundPolybrominated diphenyl ethers (PBDEs) are used as flame retardants in many household items. Given concerns over their potential adverse health effects, we identified predictors and evaluated temporal changes of PBDE serum concentrations.MethodsPBDE serum concentrations...

  3. Use of nanoclay as an environmentally friendly flame retardant synergist in polyamide-6.

    PubMed

    Kaynak, Cevdet; Gunduz, Huseyin Ozgur; Isitman, Nihat Ali

    2010-11-01

    Due to their very high levels of flame retardancy, chlorinated and brominated flame retardants had been the most widely used flame retardant additives in plastics industry. However, these flame retardants lead to formation of very toxic volatiles and by-products during fire. Therefore, the recent trend is to replace all of them with non-halogenated flame retardants. In this respect, the use of nanoclays as a synergist flame retardant is becoming more and more important. Thus, the main aim of this work was to investigate the synergistic flame retardant effect of nanoclays with phosphorous compounds in polyamide-6 composites. For this purpose, exfoliated clay nanocomposites of flame retarded/glass fiber reinforced polyamide-6 were prepared by melt compounding. A flame retardant based on phosphorus compounds was used at various levels in glass fiber reinforced polyamide-6 and nanocomposites. Flammability and fire behaviors were evaluated by limiting oxygen index, UL94 and cone calorimeter tests. Substitution of a certain fraction of the flame retardant with nanoclays was found to significantly reduce the peak heat release rate and delay the ignition in cone calorimeter. Moreover, remarkable improvements were obtained in limiting oxygen index along with maintained UL94 ratings. PMID:21137938

  4. POLYBROMINATED DIPHENYL ETHERS IN SOUTHERN MISSISSIPPI CATFISH

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in a wide variety of consumer products. Concerns surrounding these compounds are primarily due do their ubiquitous presence in the environment as well as in human tissue, such as milk, coupled with evidence indi...

  5. Chicago's Sanitary and Ship Canal sediment: Polycyclic aromatic hydrocarbons, polychlorinated biphenyls, brominated flame retardants, and organophosphate esters.

    PubMed

    Peverly, Angela A; O'Sullivan, Colin; Liu, Liang-Ying; Venier, Marta; Martinez, Andres; Hornbuckle, Keri C; Hites, Ronald A

    2015-09-01

    The Chicago Sanitary and Ship Canal (CSSC) links the Great Lakes to the Mississippi River starting in downtown Chicago. In addition to storm water, the CSSC receives water from Chicago's wastewater treatment plants (WWTP). Such effluents are known to be sources of organic pollutants to water and sediment. Therefore in 2013, we collected 10 sediment samples from the CSSC and measured the concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), brominated flame retardants, and organophosphate esters (OPEs). Geometric mean concentrations of the summed concentrations of 16 PAHs ranged from 11,000 to 420,000 ng/g dw, with the highest concentrations located at each end of the canal. Total PCB concentrations had a geometric mean of 1,400 ± 500 ng/g dw. Brominated flame retardants were separated into two groups: polybrominated diphenyl ethers (PBDEs) and non-PBDEs. Concentrations of PBDEs and those of the non-PBDE flame retardants had a geometric average of 83 ± 19 and 7.0 ± 5.8 ng/g dw, respectively. The summed concentrations of 8 OPEs ranged from 470 to 2,800 ng/g dw, with the highest concentration detected at a site located downstream of the Stickney water reclamation plant. Using ANOVA results, some hypotheses on sources to the CSSC could be formulated: downtown Chicago is probably a source of PAHs, the Cal-Sag Channel may be a source of PCBs, and neither the WWTP nor the Cal-Sag Channel seem to be significant sources of brominated flame retardants or OPEs. PMID:25981316

  6. Engineering Biodegradable Flame Retardant Wood-Plastic Composites

    NASA Astrophysics Data System (ADS)

    Zhang, Linxi

    Wood-plastic composites (WPCs), which are produced by blending wood and polymer materials, have attracted increasing attentions in market and industry due to the low cost and excellent performance. In this research, we have successfully engineered WPC by melt blending Polylactic Acid (PLA) and Poly(butylene adipate-co-terphthalate) (PBAT) with recycled wood flour. The thermal property and flammability of the composite are significantly improved by introducing flame retardant agent resorcinol bis(biphenyl phosphate) (RDP). The mechanical and morphological properties are also investigated via multiple techniques. The results show that wood material has increased toughness and impact resistance of the PLA/PBAT polymer matrix. SEM images have confirmed that PLA and PBAT are immiscible, but the incompatibility is reduced by the addition of wood. RDP is initially dispersed in the blends evenly. It migrates to the surface of the sample after flame application, and serves as a barrier between the fire and underlying polymers and wood mixture. It is well proved in the research that RDP is an efficient flame retardant agent in the WPC system.

  7. Concentrations in air of organobromine, organochlorine and organophosphate flame retardants in Toronto, Canada

    NASA Astrophysics Data System (ADS)

    Shoeib, Mahiba; Ahrens, Lutz; Jantunen, Liisa; Harner, Tom

    2014-12-01

    Concentrations of organobromine (BFRs), organochlorine (CFRs) and organophosphate esters flame retardants and plasticizers (PFRs) in air were monitored for over one year at an urban site in Toronto, Canada during 2010-2011. The mean value for polybrominated diphenyl ethers (BDEs) (gas + particle phase) was 38 pg/m3 with BDE-47 and BDE-99 as the dominant congeners. The mean concentrations in air for ∑non-BDE (BFRs and CFRs), was 9.6 pg/m3 - about four times lower than the BDEs. The brominated FRs: TBP-AE, BTBPE, EH-TBB, BEH-TEBP and the chlorinated syn- and anti-DP were detected frequently, ranging from 87% to 96%. Highest concentrations in air among all flame retardant classes were observed for the Σ-PFRs. The yearly mean concentration in air for ΣPFRs was 2643 pg/m3 with detection frequency higher than 80%. Except for TBP-AE and b- DBE-DBCH, non-BDEs (BFRs, CFRs and PFRs) were mainly associated with the particle phase. BDE concentrations in air were positively correlated with temperature indicating that volatilization from local sources was an important factor controlling levels in air. This correlation did not hold for most BFRs, CFRs and PFRs which were mainly on particles. For these compounds, air concentrations in Toronto are likely related to emissions from point sources and advective inputs. This study highlights the importance of urban air monitoring for FRs. Urban air can be considered a sentinel for detecting changes in the use and application of FRs in commercial products.

  8. Brominated flame retardants and Dechloranes in European and American eels from glass to silver life stages.

    PubMed

    Sühring, Roxana; Byer, Jonathan; Freese, Marko; Pohlmann, Jan-Dag; Wolschke, Hendrik; Möller, Axel; Hodson, Peter V; Alaee, Mehran; Hanel, Reinhold; Ebinghaus, Ralf

    2014-12-01

    The populations of American (Anguilla rostrata) and European eels (Anguilla anguilla) have been declining rapidly in the last decades. Organic contaminants are suspected to be one of the possible causes for the decline; however, so far there have been few investigations of the uptake of specific compounds by different life cycle stages (e.g. freshwater or marine stage) and how the contamination patterns develop throughout the eel's life cycle. In the present study we measured concentrations of polybrominated diphenylethers (PBDEs), alternate brominated flame retardants (alternate BFRs) and Dechloranes (Decs) in different life stages of European and American eels to compare the contamination patterns and their development throughout the eel's life cycle. In general, concentrations of flame retardants (FRs) were similar to or higher in American than in European eels, and a greater number of FRs were detected. PBDE congeners that are characteristic of the Penta-PBDE formulation were the most abundant FRs in all adult eels as well as American glass eels. In European glass eels the alternate BFR 2,3-dibromopropyl-2,4,6-tribromophenylether (DPTE) and Dechlorane Plus were the dominating FRs, with average concentrations of 1.1±0.31 ng g(-1) ww and up to 0.32 ng g(-1) ww respectively. Of the PBDEs BDE-183 was the most abundant congener in European glass eels. Low concentrations (less than 10% of the total contamination) of Tetra and Penta-PBDEs in juvenile European eels indicated that bans of technical Penta-PBDE in the European Union are effective. Enrichment of PBDEs was observed over the life stages of both European and American eels. However, a greater relative contribution of PBDEs to the sum FR contamination in American eels indicated an on-going exposure to these substances. High contributions of alternate BFRs in juvenile eels indicated an increased use of these substances in recent years. Concentrations seemed to be driven primarily by location, rather than life

  9. Monitoring of WEEE plastics in regards to brominated flame retardants using handheld XRF

    SciTech Connect

    Aldrian, Alexia; Ledersteger, Alfred; Pomberger, Roland

    2015-02-15

    Highlights: • Specification of an empirical factor for conversion from bromine to PBB and PBDE. • The handheld XRF device was validated for this particular application. • A very large number of over 4600 pieces of monitor housings was analysed. • The recyclable fraction mounts up to 85% for TV but only 53% of PC waste plastics. • A high percentage of pieces with bromine contents of over 50,000 ppm was obtained. - Abstract: This contribution is focused on the on-site determination of the bromine content in waste electrical and electronic equipment (WEEE), in particular waste plastics from television sets (TV) and personal computer monitors (PC) using a handheld X-ray fluorescence (XRF) device. The described approach allows the examination of samples in regards to the compliance with legal specifications for polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) directly after disassembling and facilitates the sorting out of plastics with high contents of brominated flame retardants (BFRs). In all, over 3000 pieces of black (TV) and 1600 pieces of grey (PC) plastic waste were analysed with handheld XRF technique for this study. Especially noticeable was the high percentage of pieces with a bromine content of over 50,000 ppm for TV (7%) and PC (39%) waste plastics. The applied method was validated by comparing the data of handheld XRF with results obtained by GC–MS. The results showed the expected and sufficiently accurate correlation between these two methods. It is shown that handheld XRF technique is an effective tool for fast monitoring of large volumes of WEEE plastics in regards to BFRs for on-site measurements.

  10. Inhalation a significant exposure route for chlorinated organophosphate flame retardants.

    PubMed

    Schreder, Erika D; Uding, Nancy; La Guardia, Mark J

    2016-05-01

    Chlorinated organophosphate flame retardants (ClOPFRs) are widely used as additive flame retardants in consumer products including furniture, children's products, building materials, and textiles. Tests of indoor media in homes, offices, and other environments have shown these compounds are released from products and have become ubiquitous indoor pollutants. In house dust samples from Washington State, U.S.A., ClOPFRs were the flame retardants detected in the highest concentrations. Two ClOPFRs, tris(1,3-dichloro-2-propyl)phosphate (TDCPP or TDCIPP) and tris(2-chloroethyl)phosphate (TCEP), have been designated as carcinogens, and there is growing concern about the toxicity of the homologue tris(1-chloro-2-propyl)phosphate (TCPP or TCIPP). In response to concerns about exposure to these compounds, the European Union and a number of U.S. states have taken regulatory action to restrict their use in certain product categories. To better characterize exposure to ClOPFRs, inhalation exposure was assessed using active personal air samplers in Washington State with both respirable and inhalable particulate fractions collected to assess the likelihood particles penetrate deep into the lungs. Concentrations of ∑ClOPFRs (respirable and inhalable) ranged from 97.1 to 1190 ng m(-3) (mean 426 ng m(-3)), with TCPP detected at the highest concentrations. In general, higher levels were detected in the inhalable particulate fraction. Total intake of ClOPFRs via the inhalation exposure route was estimated to exceed intake via dust ingestion, indicating that inhalation is an important route that should be taken into consideration in assessments of these compounds. PMID:26775187

  11. Persistence, bioaccumulation, and toxicity of halogen-free flame retardants.

    PubMed

    Waaijers, Susanne L; Kong, Deguo; Hendriks, Hester S; de Wit, Cynthia A; Cousins, Ian T; Westerink, Remco H S; Leonards, Pim E G; Kraak, Michiel H S; Admiraal, Wim; de Voogt, Pim; Parsons, John R

    2013-01-01

    Polymers are synthetic organic materials having a high carbon and hydrogen content, which make them readily combustible. Polymers have many indoor uses and their flammability makes them a fire hazard. Therefore, flame retardants (FRs) are incorporated into these materials as a safety measure. Brominated flame retardants (BFRs), which accounted for about 21% of the total world market of FRs, have several unintended negative effects on the environment and human health. Hence, there is growing interest in finding appropriate alternative halogen-free flame retardants (HFFRs). Many of these HFFRs are marketed already, although their environ- mental behavior and toxicological properties are often only known to a limited extent, and their potential impact on the environment cannot yet be properly assessed. Therefore, we undertook this review to make an inventory of the available data that exists (up to September 2011) on the physical-chemical properties, pro- duction volumes, persistence, bioaccumulation, and toxicity (PBT) of a selection of HFFRs that are potential replacements for BFRs in polymers. Large data gaps were identified for the physical-chemical and the PBT properties of the reviewed HFFRs. Because these HFFRs are currently on the market, there is an urgent need to fill these data gaps. Enhanced transparency of methodology and data are needed to reevaluate certain test results that appear contradictory, and, if this does not provide new insights, further research should be performed. TPP has been studied quite extensively and it is clearly persistent, bioaccumulative, and toxic. So far, RDP and BDP have demonstrated low to high ecotoxicity and persistence. The compounds ATH and ZB exerted high toxicity to some species and ALPI appeared to be persistent and has low to moderate reported ecotoxicity. DOPO and MPP may be persistent, but this view is based merely on one or two studies, clearly indicating a lack of information. Many degradation studies have been

  12. LACK OF EFFECT OF PERINATAL EXPOSURE TO A POLYBROMINATED DEPHENYL OTHER MIXTURE (DE-71) ON THE HABITUATION OF MOTOR ACTIVITY IN ADULT RATS.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants and are becoming increasingly evident in environmental media, wildlife and human breast milk. Published research in mice has shown that early postnatal exposure to some PBDEs attenuates the habituation of motor ...

  13. Catalytic degradation of brominated flame retardants by copper oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Dror, I.; Yecheskel, Y.; Berkowitz, B.

    2013-12-01

    Brominated flame retardants (BFRs) have been added to various products like plastic, textile, electronics and synthetic polymers at growing rates. In spite of the clear advantages of reducing fire damages, many of these BFRs may be released to the environment after their beneficial use which may lead to contamination of water resources. In this work we present the catalytic degradation of two brominated flame retardants (BFRs), tribromoneopentyl alcohol (TBNPA) and 2,4 dibromophenol (2,4-DBP) by copper oxide nanoparticles (nCuO) in aqueous solution. The degradation kinetics, the debromination, and the formation of intermediates by nCuO catalysis are compared to Fenton oxidation and to reduction by nano zero-valent iron (nZVI). The two studied BFRs are shown to degrade fully by the nCuO system within hours to days. Shorter reaction times showed differences in reaction pathways and kinetics for the two compounds. The 2,4-DBP showed faster degradation than TBNPA, by nCuO catalysis. Relatively high resistance to degradation was recorded for 2,4-DBP with nZVI, yielding 20% degradation after 24 h, while the TBNPA was degraded by 85% within 12 hours. A catalytic mechanism for radical generation and BFR degradation by nCuO is proposed. It is further suggested that H2O2 plays an essential role in the activation of the catalyst.

  14. Daphnid life cycle responses to new generation flame retardants.

    PubMed

    Waaijers, Susanne L; Bleyenberg, Tanja E; Dits, Arne; Schoorl, Marian; Schütt, Jeroen; Kools, Stefan A E; de Voogt, Pim; Admiraal, Wim; Parsons, John R; Kraak, Michiel H S

    2013-12-01

    Relatively hazardous brominated flame retardants (BFRs) are currently substituted with halogen-free flame retardants (HFFRs). Consequently, information on their persistence, bioaccumulation and toxicity (PBT) is urgently needed. Therefore, we investigated the chronic toxicity to the water flea Daphnia magna of two HFFRs, aluminum diethylphosphinate (ALPI) and 9,10-dihyro-9-oxa-10-phosphaphenanthrene-oxide (DOPO). The toxicity of ALPI increased from a 48 h LC50 of 18 mg L(-1) to a 21 day LC50 value of 3.2 mg L(-1), resulting in an acute-to-chronic ratio of 5.6. This may imply a change in classification from low to moderate toxicity. ALPI also affected sublethal life cycle parameters, with an EC50 of 2.8 mg L(-1) for cumulative reproductive output and of 3.4 mg L(-1) for population growth rate, revealing a nonspecific mode of action. DOPO showed only sublethal effects with an EC50 value of 48 mg L(-1) for cumulative reproductive output and an EC50 value of 73 mg L(-1) for population growth rate. The toxicity of DOPO to D. magna was classified as low and likely occurred above environmentally relevant concentrations, but we identified specific effects on reproduction. Given the low chronic toxicity of DOPO and the moderate toxicity of ALPI, based on this study only, DOPO seems to be more suitable than ALPI for BFR replacement in polymers. PMID:24180581

  15. Brominated flame retardants (BFRs): A review on environmental contamination in China.

    PubMed

    Yu, Gang; Bu, Qingwei; Cao, Zhiguo; Du, Xinming; Xia, Jing; Wu, Min; Huang, Jun

    2016-05-01

    Brominated flame retardants (BFRs) which were detected extensively in environmental and biota samples worldwide, have raised significant concerns during past decades for their persistence, bioaccumulation and potential toxicity to ecological environment and human health. In this paper, we have compiled and reviewed existing literature on the contamination status of BFRs in abiotic and biotic environments in China, including polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane, tetrabromobisphenol A and new BFRs. Temporal trends were also summarized and evaluated. Based on this review, it has been concluded that (1) high concentrations of PBDEs were generally related to the e-waste disposal processing, while the spatial distribution pattern of other BFRs was not necessarily in accordance with this; (2) extremely high concentrations of BFRs in indoor dust emphasized the importance of indoor contamination to human body burdens, while more work need to be done to confirm its contribution; (3) PBDEs in electronics dismantling workers were higher compared to the general population, indicating the occupational exposure should be of particular concern; (4) more data are now becoming available for BFRs in aquatic and terrestrial organisms not previously studied, while studies that consider the occurrence of BFRs in organisms of different trophic levels are still of urgent need for evaluating the fate of BFRs in the food web; and (5) limited data showed a decreasing trend for PBDEs, while more data on time trends of BFR contamination in various matrices and locations are still needed before the impact of regulation of BFRs can be assessed. PMID:26725304

  16. Particle size distribution of halogenated flame retardants and implications for atmospheric deposition and transport.

    PubMed

    Okonski, Krzysztof; Degrendele, Céline; Melymuk, Lisa; Landlová, Linda; Kukučka, Petr; Vojta, Šimon; Kohoutek, Jiří; Čupr, Pavel; Klánová, Jana

    2014-12-16

    This study investigates the distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and a group of novel flame retardants (NFRs) on atmospheric aerosols. Two high volume cascade impactors were used to collect particulate fractions of ambient air over a one year period at urban and rural sites. The majority of FRs were found on the finest aerosols (<0.95 μm). Concentrations of HBCD were higher than those of ΣPBDEs. Moreover, we noted seasonality and spatial differences in particle size distributions, yet a large portion of the observed differences were due to differences in particulate matter (PM) itself. When normalized by PM, the size distributions of the FRs exhibited much greater heterogeneity. Differences existed between the FR distributions by molecular weight, with the higher molecular weight FRs (e.g., BDE-209, Dechlorane Plus) distributed more uniformly across all particulate size fractions. The seasonal, spatial, and compound-specific differences are of crucial importance when estimating dry and wet deposition of FRs as smaller aerosols have longer atmospheric residence times. Estimated wet and dry deposition of four representative FRs (BDE-47, BDE-209, HBCD, and Dechlorane Plus) using size-segregated aerosol data resulted in lower deposition estimates than when bulk aerosol data were used. This has implications for estimates of long-range atmospheric transport and atmospheric residence times, as it suggests that without size-specific distributions, these parameters could be underestimated for FRs. PMID:25380095

  17. Five-year trends of selected halogenated flame retardants in the atmosphere of Northeast China.

    PubMed

    Li, Wen-Long; Liu, Li-Yan; Song, Wei-Wei; Zhang, Zi-Feng; Qiao, Li-Na; Ma, Wan-Li; Li, Yi-Fan

    2016-01-01

    This study collected 227 pairs of gas phase and particle phase air samples in a typical urban city of Northeast China from 2008 to 2013. Four alternative halogenated flame retardants for polybrominated diphenyl ethers (PBDEs) were analyzed, namely 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EHTBB), bis (2-ethylhexyl) tetrabromophthalate (BEHTBP), syn-dechlorane plus (syn-DP) and anti-dechlorane plus (anti-DP). The average concentrations for EHTBB and BEHTBP were 5.2 ± 20 and 30 ± 200 pg/m3, respectively, while for syn-DP and anti-DPwere 1.9±5.1 and 5.8±18 pg/m3, respectively. Generally, they were frequently detected in the particle phase, and the gas/particle partitioning suggested they were the maximum partition chemicals. The fractional abundance of EHTBB (fEHTBB) and syn-DP (fsyn)were comparablewith those in other studies. Strong local sources were identified based on the air parcel backward trajectories and the potential source contribution function. The concentrations of these chemicals were significantly increased during this sampling campaign, possibly suggesting their increasing usages from 2008 to 2013 in China. PMID:26363723

  18. DNA aptamers for selective identification and separation of flame retardant chemicals.

    PubMed

    Kim, Un-Jung; Kim, Byoung Chan

    2016-09-14

    Polybrominated diphenyl ethers (PBDEs) are group of chemicals which are representative persistent organic pollutants (POPs) and used as brominated flame retardants for many consumer products. PBDEs were phased out since 2009 but are still frequently observed in various environmental matrices and human body. Here, we report ssDNA aptamers which bind to BDE47, one of the PBDE congeners commonly found in various environmental matrices, and show affinity to other major tri-to hepta- BDE congeners. The PBDE specific aptamers were isolated from random library of ssDNA using Mag-SELEX. Two out of 15 sequences, based on their alignment and hairpin loop structures, were chosen to determine dissociation constant with BDE47 and showed from picomolar to nanomolar affinities (200 pM and 1.53 nM). The aptamers displayed high selectivity to the original target, BDE47, and implying general specificity to PBDE backbone with varying affinities to other congeners. Further, we showed that the use of two aptamers together could enhance the separation efficiency of BDE47 and other BDE congeners when dissolved in a solvent compared to use of single aptamer. These aptamers are expected to provide a tool for preliminary screening or quick separation of PBDEs in environmental samples prior to trace quantitative analysis. PMID:27566357

  19. Does Exposure to Flame Retardants Increase the Risk for Preterm Birth?

    PubMed Central

    Peltier, Morgan R.; Koo, Hschi-Chi; Getahun, Darios; Menon, Ramkumar

    2015-01-01

    During the past 40 years, polybrominated diphenyl ethers (PBDEs) have been widely used as flame retardants and nearly all women have some level of exposure. PBDEs have been isolated from amniotic fluid and cord plasma indicating vertical transmission; however, their effects on pregnancy outcome are largely unknown. Therefore, we quantified PBDE-47, the most common conger in maternal plasma samples collected at the time of labor from women who subsequently had term or preterm birth (PTB). Women were then scored based on whether or not they had very low, low, medium, high or very high peripheral plasma concentrations of PBDE-47. Probit regression analysis suggested that women in the PTB group had a greater chance of scoring higher on this scale (P < 0.001). Women with high (OR = 3.8, CI: 1.6, 9.7; P = 0.003) or very high PBDE-47 concentrations were at greater odds (OR = 5.6, CI: 2.2, 15.2; P < 0.001) for PTB than women with very low levels of PBDE-47. Results became even more significant after adjustment for maternal race, age, and marital status. These findings suggest that high levels of maternal exposure to PBDEs might increase the risk for PTB. PMID:25542760

  20. In vitro assessment of mutagenicity and clastogenicity of BDE-99, a pentabrominated diphenyl ether flame retardant.

    PubMed

    Evandri, Maria G; Mastrangelo, Sabina; Costa, Lucio G; Bolle, Paola

    2003-01-01

    Polybrominated diphenyl ethers (PBDEs), which are widely used as flame retardants, are considered persistent organic pollutants. To date, the available toxicological data on PBDEs are limited and were primarily obtained by studying technical blends. The present study was undertaken to investigate the genotoxicity of the pure congener 2,2',4,4',5-brominated diphenyl ether (BDE-99), one of the major isomers present in penta-commercial products. Bacterial reverse mutation assays in Salmonella typhimurium strains TA98 and TA100 and in Escherichia coli WP2 uvrA, and the Allium cepa chromosome aberration test were carried out to evaluate mutagenicity and clastogenicity. The experimental design also involved testing a well-known polychlorinated biphenyl (PCB) mixture, Aroclor(R) 1254, which is structurally related to PBDEs. BDE-99 was negative in the bacterial mutagenicity assays, with and without S9 mix. Also, the frequency of structural chromosome aberrations was not significantly higher than the control and no signs of cytotoxicity were observed in BDE-99-treated A. cepa. Aroclor(R) 1254 was not mutagenic, but it induced a significant increase in chromosomal aberrations in A. cepa. In conclusion, BDE-99 was not mutagenic in S. typhimurium or E. coli, or clastogenic in A. cepa; however, the possibility that PBDEs might act through an epigenetic mechanism cannot be excluded. PMID:12929120

  1. Toxicity of brominated flame retardants, BDE-47 and BDE-99 stems from impaired mitochondrial bioenergetics.

    PubMed

    Pazin, Murilo; Pereira, Lilian Cristina; Dorta, Daniel Junqueira

    2015-01-01

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants, and they have been detected in human blood, adipose tissue and breast milk, a consequence of their physicochemical and bioaccumulative properties, as well as their high environmental persistence. Many studies report liver toxicity related to exposure to PBDEs. In the present study, we investigated the toxicity of BDE-47 and BDE-99 at concentrations ranging from 0.1 to 50 µM in isolated rat liver mitochondria. We evaluated how incubation of a mitochondrial suspension with the PBDEs affected the mitochondrial inner membrane, membrane potential, oxygen consumption, calcium release, mitochondrial swelling, and ATP levels to find out whether the tested compound interfered with the bioenergetics of this organelle. Both PBDEs were toxic to mitochondria: BDE-47 and BDE-99 concentrations equal to or higher than 25 and 50 µM, respectively, modified all the parameters used to assess mitochondrial bioenergetics, which culminated in ATP depletion. These effects stemmed from the ability of both PBDEs to cause Membrane Permeability Transition (MPT) in mitochondria, which impaired mitochondrial bioenergetics. In particular, BDE-47, which has fewer bromine atoms in the molecule, can easily overcome biological membranes what would be responsible for the major negative effects exerted by this congener when compared with BDE-99. PMID:25299509

  2. Determinants of brominated flame retardants in breast milk from a large scale Norwegian study.

    PubMed

    Thomsen, Cathrine; Stigum, Hein; Frøshaug, May; Broadwell, Sharon L; Becher, Georg; Eggesbø, Merete

    2010-01-01

    Brominated flame retardants (BFRs), particularly polybrominated diphenyl ethers (PBDEs), are widely present in human populations. In order to investigate human exposure pathways and associations with socioeconomic and lifestyle factors, 393 breast milk samples from mothers living in various regions throughout Norway were analyzed. Up to ten PBDE congeners were measured in all the samples, hexabromocyclododecane (HBCD) and BDE-209 in subsets of 310 and 46, respectively. The median concentrations of the sum of the seven most prominent PBDEs (BDE-28, 47, 99, 100, 153, 154 and 183), BDE-209 and HBCD were 2.1, 0.32 and 0.86ng/g lipids, respectively. These concentrations are comparable to the levels generally observed in human populations in Europe. The frequency distributions were quite skewed with long tails towards higher concentrations. Maternal age, parity, education, having a cohabitant employed as electrician, and ventilation were factors significantly associated with some of the BFRs, although these factors only explained a small amount of the variability (R(2) 0.04-0.16). The mothers' diet was not found to influence the breast milk PBDE and HBCD levels. Our results show that sources other than the diet are important for the variability seen in breast milk BFR concentrations and that exposure from the indoor atmosphere should be emphasized in future studies. PMID:19889457

  3. Brominated flame retardants and the formation of dioxins and furans in fires and combustion.

    PubMed

    Zhang, Mengmei; Buekens, Alfons; Li, Xiaodong

    2016-03-01

    The widespread use and increasing inventory of brominated flame retardants (BFRs) have caused considerable concern, as a result of BFRs emissions to the environment and of the formation of both polybrominated dibenzo-p-dioxins and dibenzofurans (PBDD/Fs) and mixed polybromochloro-dibenzo-p-dioxins and dibenzofurans (PBCDD/Fs or PXDD/Fs). Structural similarities between PBDD/Fs and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) suggest the existence of comparable formation pathways of both PBDD/Fs and PCDD/Fs, yet BFRs also act as specific precursors to form additional PBDD/Fs. Moreover, elementary bromine (Br2) seems to facilitate chlorination by bromination of organics, followed by Br/Cl-exchange based on displacement through the more reactive halogen. Overall, PBDD/Fs form through three possible pathways: precursor formation, de novo formation, and dispersion of parts containing BFRs as impurities and surviving a fire or other events. The present review summarises the formation mechanisms of both brominated (PBDD/Fs) and mixed dioxins (PXDD/Fs with X=Br or Cl) from BFRs, recaps available emissions data of PBDD/Fs and mixed PXDD/Fs from controlled waste incineration, uncontrolled combustion sources and accidental fires, and identifies and analyses the effects of several local factors of influence, affecting the formation of PBDD/Fs and mixed PXDD/Fs during BFRs combustion. PMID:26546701

  4. Bioavailability of classical and novel flame retardants: Effect of fullerene presence.

    PubMed

    Santín, Giselle; Eljarrat, Ethel; Barceló, Damià

    2016-09-15

    To understand the behavior of some emerging flame retardants (FRs) in the environment, a nonexhaustive extraction using Tenax was applied to study their behavior in aquatic ecosystems. Desorption of 8 polybrominated diphenyl ethers (PBDEs), 8 methoxylated PBDEs, 3 emerging brominated FRs and 6 halogenated norbornenes from sediments spiked in the laboratory was studied. Results showed that emerging FRs have a similar bioavailability than that of legacy FRs, already banned. In addition, some parameters such as sediment total organic carbon (TOC), aging or nanomaterial (NMs) presence in the sediment were modified in order to study their effects on the bioavailability of FRs. Bioavailability increases with a diminution of sediment TOC, while diminishes with an increase of aging. The study of effect of NM presence was performed at three different pH (acidic, neutral and basic), and for the three scenarios, FR bioavailability decreased with NM presence. The retention of pollutants in the sediment seems to be favoured by NM presence, minimizing their impact on living organisms. PMID:27177136

  5. Breast cancer among women in Michigan following exposure to brominated flame retardants.

    PubMed

    Terrell, Metrecia L; Rosenblatt, Karin A; Wirth, Julie; Cameron, Lorraine L; Marcus, Michele

    2016-08-01

    In this updated follow-up, we investigated the breast cancer experience among women in Michigan exposed to brominated flame retardants, some 30 years following exposure. Michigan residents were enrolled in a study cohort after exposure to polybrominated biphenyls (PBBs) through the consumption of contaminated food products. PBB concentrations were measured in serum at the time of enrolment. Cancer experience was determined by linkage to the Michigan Cancer Registry. We conducted a nested case-control study that included 51 women diagnosed with breast cancer during 1974-2004 and 202 age-matched controls. While the data suggest an increase in breast cancer risk with higher PBB exposure, this did not reach statistical significance. The OR of having breast cancer among women with PBB concentrations ≥10 ng/mL compared to women with PBB concentrations at or below the limit of detection of 1 ng/mL was 2.60, 95% CI 0.93 to 7.27, (p=0.07), when adjusted for age and family history of cancer in a first-degree female relative. It remains important to examine exposure to brominated chemicals and possible health effects, and to continue following the cancer experience of participants in this study. PMID:27312402

  6. A method for the analysis of multiple novel halogenated flame retardants in cow's milk.

    PubMed

    Rawn, Dorothea F K; Corrigan, Catherine; Ménard, Cathie; Breton, François; Sun, Wing-Fung

    2016-07-01

    A method was developed for the extraction and analysis of cow's milk to measure 21 halogenated flame retardants (FRs), including individual isomers plus eight methoxy-polybrominated diphenyl ethers (MeO-PBDEs). Extraction was performed using homogenisation with acetone:hexane with size exclusion chromatography followed by adsorption chromatography clean-up. Analysis was undertaken using gas chromatography high-resolution mass spectrometry. The method was validated in fortified cow's milk with FRs and 2-methoxy-PBDE 68 at three levels (low [12.5-1250 pg g(-)(1)], mid [37.5-5000 pg g(-)(1)] and high [400-10 000 pg g(-)(1)]). Additional methoxy-PBDEs were tested at two fortification levels. Isotope dilution was used to correct for losses during sample preparation and average recoveries ranged from 58% (allyl 2,4,6-tribromophenyl ether [ATE]) to 121% (γ-tetrabromoethylcyclohexane (γ-TBECH)). Limits of detection ranged from 0.055 pg g(-)(1) (6-methoxy-PBDE 47) to 38.9 pg g(-)(1) (decabromodiphenylethane (DBDPE)). Matrix effects were overcome through the use of surrogate and performance standards. A single FR (1-bromomethyl-2,3,4,5,6-pentabromobenzene [PBBB]) and two methoxy-PBDEs were detected in commercially available cow's milk collected from local supermarkets in Ottawa, ON, Canada. Detection frequency was < 25% for these compounds and, where present, concentrations were low. PMID:27264991

  7. Photochemical transformation of five novel brominated flame retardants: Kinetics and photoproducts.

    PubMed

    Zhang, Ya-Nan; Chen, Jingwen; Xie, Qing; Li, Yingjie; Zhou, Chengzhi

    2016-05-01

    Many novel brominated flame retardants (NBFRs) are used as substitutes of polybrominated diphenyl ethers (PBDEs) in recent years. However, little is known about their phototransformation behavior, which may influence the environmental fate of these chemicals. In this study, photochemical behavior of five NBFRs, allyl-2,4,6-tribromophenyl ether (ATE), 2-bromoallyl-2,4,6-tribromophenyl ether (BATE), 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), and 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) was investigated. Results show all the five NBFRs can undergo photochemical transformation under simulated sunlight irradiation. Quantum yields (Φ) of the five NBFRs varied from 0.012 of TTBP-TAZ in hexane to 0.091 of BTBPE in methanol. Half-lives (t1/2) relevant with solar irradiation of these NBFRs were estimated using the determined Φ, and the values are 1.5-12.0 d in summer and 17.1-165.0 d in winter. Debrominated and ether bond cleavage products were identified in the phototransformation of DPTE and BTBPE. Debromination on the phenyl is a main phototransformation pathway for DPTE, and both debromination and ether bond cleavage are main phototransformation pathways for BTBPE. This study is helpful to better understand the phototransformation behavior of the NBFRs. PMID:26796587

  8. Novel brominated flame retardants and dechlorane plus in Greenland air and biota.

    PubMed

    Vorkamp, Katrin; Bossi, Rossana; Riget, Frank F; Skov, Henrik; Sonne, Christian; Dietz, Rune

    2015-01-01

    Following the ban of polybrominated diphenyl ethers, other halogenated flame retardants (FRs) might be used increasingly. This study has analyzed hexabromocyclododecane (HBCD), 1,2-bis(2,4,6-tribromophenoxy)-ethane (BTBPE), 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and dechloraneplus (DP) in Greenland air over the course of a year. Moreover, BTBPE, DPTE, DP, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), bis(2-ethylhexyl) tetrabromophthalate (TBPH) and decabromodiphenylethane (DBDPE) were analyzed in samples of polar bear, ringed seal, black guillemot and glaucous gull from Greenland. HBCD in air appeared low, while mean concentrations of syn- and anti-DP were 2.3 and 5.2 pg/m(3), respectively. BTBPE and DPTE were undetectable in air. Detection frequencies in biota were <50% for BTBPE, TBPH and DBDPE, but near 100% for the remaining compounds. Ringed seals from East Greenland had highest mean concentrations of TBB, DPTE, syn- and anti-DP (1.02, 0.078, 0.096 and 0.42 ng/g wet weight, respectively). Our study documents the long-range transport and, to some extent, bioaccumulation of these novel FRs. PMID:25463724

  9. Novel brominated flame retardants: a review of their analysis, environmental fate and behaviour.

    PubMed

    Covaci, Adrian; Harrad, Stuart; Abdallah, Mohamed A-E; Ali, Nadeem; Law, Robin J; Herzke, Dorte; de Wit, Cynthia A

    2011-02-01

    This review summarises current knowledge about production volumes, physico-chemical properties, analysis, environmental occurrence, fate and behaviour and human exposure to the "novel" brominated flame retardants (NBFRs). We define the term NBFRs as relating to BFRs which are new to the market or newly/recently observed in the environment. Restrictions and bans on the use of some polybrominated diphenyl ether (PBDE) formulations, in many jurisdictions, have created a market for the use of NBFRs. To date, most data on NBFRs have arisen as additional information generated by research designed principally to study more "traditional" BFRs, such as PBDEs. This has led to a wide variety of analytical approaches for sample extraction, extract purification and instrumental analysis of NBFRs. An overview of environmental occurrence in abiotic matrices, aquatic biota, terrestrial biota and birds is presented. Evidence concerning the metabolism and absorption of different NBFRs is reviewed. Human exposure to NBFRs via different exposure pathways is discussed, and research gaps related to analysis, environmental sources, fate, and behaviour and human exposure are identified. PMID:21168217

  10. Occurrence of brominated flame retardants in household and car dust from the Czech Republic.

    PubMed

    Kalachova, K; Hradkova, P; Lankova, D; Hajslova, J; Pulkrabova, J

    2012-12-15

    The levels and profiles of 16 polybrominated diphenyl ethers congeners (PBDEs), three isomers of hexabromocyclododecane (HBCD) and other six "alternative" brominated flame retardants (BFRs) in dust collected in 25 Czech households and 27 car interiors were investigated. The Σ16 PBDEs contents varied widely with maximum concentrations reaching up to 5896 and 33728 μg/kg in house and car dust, respectively. The highest concentrations of PBDEs were observed for BDE 209, which was found almost in all samples and exceeded concentrations of other PBDEs even by one order of magnitude. The profile and levels of Penta-, Octa-, and DecaBDE obtained within this study were comparable to those presented in other studies worldwide and confirmed lower contamination of dust from Europe compared to North America. From the group of "alternative" BFRs, suitable for commercial applications as an alternative to banned PBDEs, mainly decabromodiphenyl ethane (DBDPE) and HBCD were detected in the concentration ranges <20-3567 and <0.3-950 μg/kg, respectively. γ-HBCD was dominating, forming up to 70% of ΣHBCD. Using the measured concentrations and estimates of dust ingestion rates it was estimated that toddlers had a higher exposure than adults for all compounds investigated. PMID:23137984

  11. The toxic effects of flame retardants: a gene expression study in elucidating their carcinogenicity

    NASA Astrophysics Data System (ADS)

    Vagula, Mary; Al-Dhumani, Ali; Al-Dhumani, Sajaad; Mastro, Alexandra

    2013-05-01

    Polybrominated Diphenyl Ethers (PBDEs) are flame retardants widely used in many commercial products, including building materials, electronics, furnishings, motor vehicles, airplanes, plastics, polyurethane foams, and textiles. Although the specific toxic action of these chemicals is not clear, it is reported that they can cause serious damage to the nervous, reproductive, and endocrine systems. These chemicals are branded as "probable carcinogens" by Environmental Protection Agency (EPA). Therefore, this study is taken up to investigate the expression of genes namely, TP-53, RAD1, CRADD, and ATM, which are involved in apoptosis, DNA repair and cell cycle regulation. For this study human umbilical vein endothelial cells (HUVEC) are exposed to 5 μM of BDE-85 (a penta-BDE) and BDE-209 (deca-BDE). The results of this report reveal significant alteration in all the genes under investigation in BDE-85 and BDE-209 exposed cells. The BDE-85 induced responses are significantly more than BDE-209. These results emphasize the congener specific action of PBDEs on the expression of genes relevant to DNA repair and cell division of HUVEC cells.

  12. Multiyear Measurements of Flame Retardants and Organochlorine Pesticides in Air in Canada's Western Sub-Arctic.

    PubMed

    Yu, Yong; Hung, Hayley; Alexandrou, Nick; Roach, Pat; Nordin, Ken

    2015-07-21

    Fourteen polybrominated diphenyl ethers (PBDEs), 14 non-BDE flame retardants (FRs), and 25 organochlorine pesticides (OCPs) were analyzed in air samples collected at Little Fox Lake (LFL) in Canada's Yukon Territory from August 2011 to December 2014. LFL is a long-term monitoring station operated under the Northern Contaminants Program (NCP) and one of only a few stations that contribute to the assessment of air pollution levels and pathways to the sub-Arctic region. BDE-47 was the most abundant congener among the 14 PBDEs, followed by BDE-99. Non-BDE FRs pentabromotoluene (PBT) and dechlorane plus (DP) were detected in all the samples. Dechlorane 602, 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), hexabromobenzene (HBB), and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) were also detected in >75% of all samples. PBDEs have shown a decreasing tendency as of 2013, which may reflect the phase-out of penta- and octa-BDE mixtures has led to significant decline in the atmosphere. The highest concentrations of OCPs were observed for hexachlorobenzene (HCB), with a median concentration of 61 pg/m(3), followed by α-hexachlorocyclohexane (α-HCH) and α-endosulfan. Potential source contribution function (PSCF) highlights Northern Canada, Pacific, and East Asia as potential sources in warm seasons; whereas in cold seasons, the chemicals mainly came from the Pacific Rim. PMID:26098022

  13. Understanding the mechanism of action of triazine-phosphonate derivatives as flame retardants for cotton fabrics

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Countless hours of research and studies on triazine, phosphonate and their combination have provided insightful information into their flame retardant properties on polymeric systems. However, only limited number of studies shed light on the mechanism of flame retardant cotton fabrics. The purpose...

  14. Effect of urea additive on the thermal decomposition kinetics of flame retardant greige cotton nonwoven fabric

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Urea is well known to have a synergistic action with phosphorus-based flame retardants such as diammonium phosphate (DAP) in enhancing the flame retardant performance of cellulosic materials, but its effect on their thermal decomposition kinetics has not been thoroughly studied. In this study, the ...

  15. Synthesis of Novel Flame Retardant Organophosphorus Compounds for the Application to Cotton Textile

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flame retardancy of textiles is an important property in apparel, bedding, curtains, and other household items. Chemical treatment is one method to increase flame retardancy of textile such as cotton, linenes, and silks. Halogenated compounds (containing chlorine or bromine atoms) have been shown to...

  16. Bioaccumulation of emerging organic compounds (perfluoroalkyl substances and halogenated flame retardants) by earthworm in biosolid amended soils.

    PubMed

    Navarro, Irene; de la Torre, Adrián; Sanz, Paloma; Pro, Javier; Carbonell, Gregoria; Martínez, María de Los Ángeles

    2016-08-01

    In the present work, the bioaccumulation behavior of 49 target emerging organic compounds (20 perfluoroalkyl substances, PFASs, and 29 halogenated flame retardants, HFRs) was studied in soil invertebrates (Eisenia andrei). Multi species soil systems (MS·3) were used to assess the fate and the effects associated with the application of four biosolids in agricultural soil on terrestrial soil organisms. Biosolid amendment increased concentrations 1.5-14-fold for PFASs, 1.1-2.4-fold for polybrominated diphenyl ethers, PBDEs, and 1.1-3.6-fold for chlorinated flame retardants, CFRs. Perfluorooctanesulfonate, PFOS, (25%) and BDE-209 (60%) were the predominant PFAS and HFR compounds, respectively, in biosolids-amended soils. Total concentrations (ng/g dry weight) in earthworms from biosolid-amended soils ranged from 9.9 to 101 for PFASs, from 45 to 76 for PBDEs and 0.3-32 for CFRs. Bioaccumulation factors (BAFs) were calculated to evaluate the degree of exposure of pollutants in earthworms. The mean BAF ranged from 2.2 to 198 for PFASs, 0.6-17 for PBDEs and 0.5-20 for CFRs. The relationship of PFAS and PBDE BAFs in earthworms and their log Kow were compared: PFAS BAFs increased while PBDE BAFs declined with increasing log Kow values. The effect of the aging (21 days) on the bioavailability of the pollutants in amended soils was also assessed: the residence time affected differently to the compounds studied. PMID:27174781

  17. Plant selective uptake of halogenated flame retardants at an e-waste recycling site in southern China.

    PubMed

    Wang, Shaorui; Wang, Yan; Luo, Chunling; Li, Jun; Yin, Hua; Zhang, Gan

    2016-07-01

    The concentrations and homolog patterns of halogenated flame retardants (HFRs) in vegetables grown at an e-waste contaminated site were investigated. Polybrominated diphenyl ethers (PBDEs) were the dominant HFRs in vegetable tissues, with concentrations ranging from 10.3 to 164 ng g(-1) and 1.16-107 ng g(-1) in shoots and roots, respectively, followed by novel brominated flame retardants (NBFRs) and dechlorane plus (DPs). This is an indication that PBDE contamination in vegetables grown around e-waste recycling sites may pose a risk to the local terrestrial ecosystem and residents. In addition, this is the first report on the concentrations and compositions of NBFRs in vegetables around e-waste recycling sites. The HFRs concentrations in vegetables varied greatly with the vegetable species, with the highest concentrations observed in Brassica oleracea var. capitata. Root concentration factors (RCF) decreased with increasing log Kow of HFRs, which indicated that the uptake of HFRs was controlled mainly by log Kow. Dissimilar HFRs profiles in shoots and roots suggested that the uptake and translocation of HFRs by plants were selective, with lower halogenated congeners prone to accumulation in vegetable tissues. Positive relationships between PBDEs and their substitutes were observed in vegetable tissues, suggesting that the replacement of PBDEs by NBFRs has not resulted in an obvious transition in plants within the study area. PMID:27149147

  18. A novel brominated triazine-based flame retardant (TTBP-TAZ) in plastic consumer products and indoor dust.

    PubMed

    Ballesteros-Gómez, Ana; de Boer, Jacob; Leonards, Pim E G

    2014-04-15

    The presence of a novel brominated flame retardant named 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine (TTBP-TAZ) is reported for the first time in plastic parts of consumer products and indoor dust samples. TTBP-TAZ was identified by untargeted screening and can be a replacement of the banned polybrominated diphenyl ethers. Analysis techniques based on ambient mass spectrometry and on liquid chromatography with atmospheric pressure chemical ionization combined with high resolution time-of-flight mass spectrometry were developed for the screening, detection and quantification of this low volatility and high molecular weight compound. TTBP-TAZ was present in 8 of 13 plastic parts of consumer products (from mainly electric and electronic equipment acquired in 2012) at estimated concentrations of 0.01-1.9% by weight of the product (%, w/w). It was not present in any of the older 13 plastic samples that were collected in a recycling park (manufacture date before 2006), this suggests a recent use of TTBP-TAZ. It was also found in 9 of 17 house dust samples in the range of 160-22150 ng g(-1), with the highest levels being found in samples collected on electronic and electrical equipment. These preliminary results highlight the need for further research on TTBP-TAZ and the potential of using alternative analysis methods for the identification of new flame retardants. PMID:24666318

  19. Brominated and organophosphate flame retardants in indoor dust of Jeddah, Kingdom of Saudi Arabia: Implications for human exposure.

    PubMed

    Ali, Nadeem; Eqani, Syed Ali Musstjab Akber Shah; Ismail, Iqbal Mohammad Ibrahim; Malarvannan, Govindan; Kadi, Mohammad W; Albar, Hussain Mohammed Salem; Rehan, Mohammad; Covaci, Adrian

    2016-11-01

    Different flame retardants (FRs) namely polybrominated diphenyl ethers (PBDEs), emerging brominated/chlorinated flame retardants (Br/Cl FRs), and organophosphate FRs (OPFRs) were analyzed in cars, air conditioner (AC) filters and floor dust of different households from Jeddah, Kingdom of Saudi Arabia (KSA). To the best of our knowledge, this is first study in literature reporting emerging Br/Cl FRs and OPFRs in AC filter dust and also first to report on their occurrence in dust from KSA. Chlorinated alkyl phosphate, penta-BDEs, BDE-209, and decabromodiphenylethane (DBDPE) were the major chemicals in dust samples from all microenvironments. ΣOPFRs occurred at median concentrations (ng/g dust) of 15,400, 10,500, and 3750 in AC filter, car and house floor dust, respectively. For all analyzed chemicals, relatively lower levels were observed in floor dust than car and AC filter dust. The profiles of FRs in car dust were different from AC filter and floor dust, which reflected their wider application as FR and plasticizer in variety of household and commercial products. For toddlers, assuming high dust intake and 95th percentile concentrations, the computed exposure estimation for BDE-99 was higher than RfD values. PMID:27343946

  20. Field evaluation of a flow-through sampler for measuring pesticides and brominated flame retardants in the arctic atmosphere.

    PubMed

    Xiao, Hang; Hung, Hayley; Wania, Frank; Lao, Randy; Sabljic, Edwin; Sverko, Ed; Lei, Ying Duan; Fellin, Phil; Barresi, Enzo

    2012-07-17

    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. PMID:22702375

  1. Extent and mechanisms of brominated flame retardant emissions from waste soft furnishings and fabrics: A critical review.

    PubMed

    Stubbings, William A; Harrad, Stuart

    2014-10-01

    Use of brominated flame retardants (BFRs) in soft furnishings has occurred for over thirty years with the phase out of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) only relatively recently begun. As products treated with BFRs reach the end of their lifecycle they enter the waste stream, thereby constituting an important and increasing reservoir of these chemicals. This review highlights the dearth of data on the extent and potential mechanisms of BFR emissions from waste soft furnishings. However, insights into what may occur are provided by scrutiny of the larger (though still incomplete) database related to BFR emissions from electronic waste (e-waste). In many countries, municipal landfills have historically been the primary disposal method of waste consumer products and therefore represent a substantial reservoir of BFRs. Published data for BFR emissions to both air and water from landfill and other waste disposal routes are collated, presented and reviewed. Reported concentrations of PBDEs in landfill leachate range considerably from <1ngL(-1) to 133,000ngΣPBDEL(-1). In addition to direct migration of BFRs from waste materials; there is evidence that some higher brominated flame retardants are able to undergo degradation and debromination during waste treatment, that in some instances may lead to the formation of more toxic and bioavailable compounds. We propose that waste soft furnishings be treated with the same concern as e-waste, given its potential as a reservoir and source of environmental contamination with BFRs. PMID:25042535

  2. Brominated flame retardants in the surrounding soil of two manufacturing plants in China: Occurrence, composition profiles and spatial distribution.

    PubMed

    Li, Wen-Long; Liu, Li-Yan; Zhang, Zi-Feng; Song, Wei-Wei; Huo, Chun-Yan; Qiao, Li-Na; Ma, Wan-Li; Li, Yi-Fan

    2016-06-01

    Surface soil samples were collected surrounding two brominated flame retardants (BFRs) manufacturing plants in China in August 2014 and analyzed for 23 polybrominated diphenyl ethers (PBDEs) and 8 novel brominated flame retardants (NBFRs). BDE209 and decabromodiphenylethane (DBDPE) were the predominant compounds in soil with the median levels of 1600 and 560 ng/g dw, respectively. The PBDEs profiles in soil samples were consistent with that of commercial product (comDecaBDE). The percentage contributions to total PBDEs decreased from higher to lower brominated homologues. Lower concentrations of NBFRs (excluding DBDPE) were detected in soil surrounding the two plants, suggesting they are byproducts or degradation products of the manufacturing activities. The concentrations of most BFRs dropped exponentially within 3-5 km of the manufacturing plants, suggesting recent deposition of these compounds to the soil. Directional distribution indicated that PBDEs and DBDPE concentrations were highest in the north direction of Plants 1. Three-day air parcel forward trajectories confirmed that the air parcel was responsible for the higher concentration of BFRs in the soil of north direction of the plant. PMID:26874313

  3. Thermal decomposition of 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), a novel brominated flame retardant.

    PubMed

    Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z

    2014-12-16

    1,2-Bis(2,4,6-tribromophenoxy)ethane (BTBPE) is currently one of the most commonly applied novel brominated flame retardants. In this contribution, we analyze in detail the mechanisms pertinent to its thermal decomposition in view of analogous experimental findings. We demonstrate that a 1,3-hydrogen shift, leading to 2,4,6-tribromophenol (M9) and 1,3,5-tribromo-2-(vinyloxy)benzene (M10) molecules, dominates direct scission of O-CH2 bonds up to a temperature of ∼ 680 K. H atom abstraction from CH2 sites, followed by a fission of a C-C bond, produce a 2,4,6-tribromophenoxy radical (M2) and a M10 molecule. Bimolecular condensation reactions involving M2, M9, and M10 generate several congeners of brominated diphenyl ethers and their OH/OCHCH2 substituents, which serve as direct precursors for the formation of polybrominated dibenzo-p-dioxins. Reaction of M9 with a model compound of a hydrocarbon chain preferentially yields M2. Strong adsorption energy of the latter on a radical site of a hydrocarbon chain suggests that mechanisms such as Langmuir-Hinshelwood, Eley-Rideal, and Diels-Alder might be operating during the formation of PBDD/Fs from brominated flame retardants (BFRs). Reactions of alkyl primary/secondary radicals and diradical with the BTBPE molecule proceed via H abstraction from a -CH2- moiety. PMID:25340709

  4. Quantitative structure-activity relationship modeling on in vitro endocrine effects and metabolic stability involving 26 selected brominated flame retardants.

    PubMed

    Harju, Mikael; Hamers, Timo; Kamstra, Jorke H; Sonneveld, Edwin; Boon, Jan P; Tysklind, Mats; Andersson, Patrik L

    2007-04-01

    In this work, quantitative structure-activity relationships (QSARs) were developed to aid human and environmental risk assessment processes for brominated flame retardants (BFRs). Brominated flame retardants, such as the high-production-volume chemicals polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A, and hexabromocyclododecane, have been identified as potential endocrine disruptors. Quantitative structure-activity relationship models were built based on the in vitro potencies of 26 selected BFRs. The in vitro assays included interactions with, for example, androgen, progesterone, estrogen, and dioxin (aryl hydrocarbon) receptor, plus competition with thyroxine for its plasma carrier protein (transthyretin), inhibition of estradiol sulfation via sulfotransferase, and finally, rate of metabolization. The QSAR modeling, a number of physicochemical parameters were calculated describing the electronic, lipophilic, and structural characteristics of the molecules. These include frontier molecular orbitals, molecular charges, polarities, log octanol/water partitioning coefficient, and two- and three-dimensional molecularproperties. Experimental properties were included and measured for PBDEs, such as their individual ultraviolet spectra (200-320 nm) and retention times on three different high-performance liquid chromatography columns and one nonpolar gas chromatography column. Quantitative structure-activity relationship models based on androgen antagonism and metabolic degradation rates generally gave similar results, suggesting that lower-brominated PBDEs with bromine substitutions in ortho positions and bromine-free meta- and para positions had the highest potencies and metabolic degradation rates. Predictions made for the constituents of the technical flame retardant Bromkal 70-5DE found BDE 17 to be a potent androgen antagonist and BDE 66, which is a relevant PBDE in environmental samples, to be only a weak antagonist. PMID:17447568

  5. Occurrence of PBDEs and other alternative brominated flame retardants in sludge from wastewater treatment plants in Korea.

    PubMed

    Lee, Sunggyu; Song, Geum-Ju; Kannan, Kurunthachalam; Moon, Hyo-Bang

    2014-02-01

    Studies on the occurrence of polybrominated diphenyl ethers (PBDEs) and other alternative brominated flame retardants in the environment are scarce. In this study, PBDEs and non-PBDE brominated flame retardants (NBFRs), including decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), were measured in sludge collected from three types of wastewater treatment plants (WWTPs) in Korea. Total concentrations of PBDEs (∑PBDE) in sludge ranged from 298 to 48,000 (mean: 3240) ng/g dry weight. Among 10 NBFRs analyzed, DBDPE and BTBPE were the only ones detected in sludge samples. Concentrations of DBDPE and BTBPE ranged from 1) of DBDPE/BDE 209 were found in sludge from I-WWTPs, reflecting a shift in the usage pattern of BFRs by the Korean industry. The nationwide annual emission fluxes of ∑PBDE, DBDPE and BTBPE via WWTPs to the environment were estimated to be 7400, 480, and 3.7 kg/year, respectively. This is the first study on the occurrence of alternative brominated flame retardants in sludge from Korea. PMID:23993837

  6. Versatility of a new bioinorganic catalyst: palladized cells of Desulfovibrio desulfuricans and application to dehalogenation of flame retardant materials.

    PubMed

    Deplanche, K; Snape, T J; Hazrati, S; Harrad, S; Macaskie, L E

    2009-06-01

    The versatility and reaction specificity of a novel bioinorganic catalyst is demonstrated in various reactions. Palladized cells (bioPd) of the sulphate-reducing bacterium Desulfovibrio desulfuricans showed an increased product selectivity and a catalytic activity comparable to a commercial Pd catalyst in several industrially relevant hydrogenations and hydrogenolyses (reductive dehalogenations). The ability of palladized cells to promote the reductive debromination of a polybrominated diphenyl ether (PBDE #47) is demonstrated, although chemically reduced Pd(II) and commercial Pd(0) were more effective debromination agents. Polybrominated diphenyl ethers are being supplanted as flame retardants by other compounds, e.g. tris(chloroisopropyl)phosphate (TCPP), the concentration of which was seen to increase approximately 10-fold in groundwater samples between 2000 and 2004. BioPd dechlorinated TCPP in groundwater samples with >90% recovery of free chloride ion, and was five times more effective than using commercial Pd(0) catalyst. Examination of the spent groundwater using 31P NMR showed a phosphorus species novel to the bioPd-treated solution, which was not evident in a commercial reference sample of TCPP. PMID:19705605

  7. Selected chlorobornanes, polychlorinated naphthalenes and brominated flame retardants in Bjørnøya (Bear Island) freshwater biota.

    PubMed

    Evenset, Anita; Christensen, Guttorm N; Kallenborn, Roland

    2005-08-01

    Levels of selected sparsely investigated persistent organic pollutants (POPs) have been measured in organisms from two Arctic lakes on Bjørnøya (Bear Island). Elevated levels of chlorobornanes (CHBs) (up to 46.7 ng/g wet weight=ww), polybrominated diphenyl ethers (PBDEs) (up to 27.2 ng/g ww), polybrominated biphenyls (PBBs) (up to 1.1 ng/g ww) and polychlorinated naphthalenes (PCNs, only 4 congeners) (up to 62.7 pg/g ww), were measured in biota from Lake Ellasjøen. In Lake Øyangen, located only 5 km north of Ellasjøen, levels of these contaminants were significantly lower. delta(15)N-values were 7-10 per thousand higher in organisms from Ellasjøen as compared to Øyangen. This is attributed to biological inputs related to seabird activities. The present study illustrates that contaminants such as CHBs, brominated flame retardants and PCNs accumulate in the Ellasjøen food web in a manner similar to PCBs and conventional organochlorine pesticides. Transport mechanisms that control PCB and DDT distributions, i.e. atmospheric long-range transport and biotransport by seabirds, are also relevant for the contaminants investigated in the present study. PMID:15862396

  8. Identification of Flame Retardants in Polyurethane Foam Collected from Baby Products

    PubMed Central

    2011-01-01

    With the phase-out of PentaBDE in 2004, alternative flame retardants are being used in polyurethane foam to meet flammability standards. However, insufficient information is available on the identity of the flame retardants currently in use. Baby products containing polyurethane foam must meet California state furniture flammability standards, which likely affects the use of flame retardants in baby products throughout the U.S. However, it is unclear which products contain flame retardants and at what concentrations. In this study we surveyed baby products containing polyurethane foam to investigate how often flame retardants were used in these products. Information on when the products were purchased and whether they contained a label indicating that the product meets requirements for a California flammability standard were recorded. When possible, we identified the flame retardants being used and their concentrations in the foam. Foam samples collected from 101 commonly used baby products were analyzed. Eighty samples contained an identifiable flame retardant additive, and all but one of these was either chlorinated or brominated. The most common flame retardant detected was tris(1,3-dichloroisopropyl) phosphate (TDCPP; detection frequency 36%), followed by components typically found in the Firemaster550 commercial mixture (detection frequency 17%). Five samples contained PBDE congeners commonly associated with PentaBDE, suggesting products with PentaBDE are still in-use. Two chlorinated organophosphate flame retardants (OPFRs) not previously documented in the environment were also identified, one of which is commercially sold as V6 (detection frequency 15%) and contains tris(2-chloroethyl) phosphate (TCEP) as an impurity. As an addition to this study, we used a portable X-ray fluorescence (XRF) analyzer to estimate the bromine and chlorine content of the foam and investigate whether XRF is a useful method for predicting the presence of halogenated flame

  9. Improve the flame retardancy of cellulose fibers by grafting zinc ion.

    PubMed

    Zhang, KeKe; Zong, Lu; Tan, Yeqiang; Ji, Quan; Yun, Weicai; Shi, Ran; Xia, Yanzhi

    2016-01-20

    Zinc ion as the only flame retardant of cellulose fibers was successfully grafted onto cellulose fibers. Grafting maleic anhydride onto cellulose fibers via homogeneous acylation reaction between N,N-dimethyl formamide (DMF) as the first step. Then, graft zinc ion onto the formed cellulose fibers was conducted with zinc carbonate. The resulting copolymers were characterized by FTIR. Flame retardancy and thermal degradation of zinc-ion-modified cellulose fibers (cellulose-Zn fibers) was investigated by limiting oxygen index (LOI), cone calorimeter (CONE), XRD, TG and SEM. Zinc ion could effectively improve flame retardancy and thermal degradation when its content increases up to 4.96 wt%. PMID:26572337

  10. Identification of flame retardants in polyurethane foam collected from baby products.

    PubMed

    Stapleton, Heather M; Klosterhaus, Susan; Keller, Alex; Ferguson, P Lee; van Bergen, Saskia; Cooper, Ellen; Webster, Thomas F; Blum, Arlene

    2011-06-15

    With the phase-out of PentaBDE in 2004, alternative flame retardants are being used in polyurethane foam to meet flammability standards. However, insufficient information is available on the identity of the flame retardants currently in use. Baby products containing polyurethane foam must meet California state furniture flammability standards, which likely affects the use of flame retardants in baby products throughout the U.S. However, it is unclear which products contain flame retardants and at what concentrations. In this study we surveyed baby products containing polyurethane foam to investigate how often flame retardants were used in these products. Information on when the products were purchased and whether they contained a label indicating that the product meets requirements for a California flammability standard were recorded. When possible, we identified the flame retardants being used and their concentrations in the foam. Foam samples collected from 101 commonly used baby products were analyzed. Eighty samples contained an identifiable flame retardant additive, and all but one of these was either chlorinated or brominated. The most common flame retardant detected was tris(1,3-dichloroisopropyl) phosphate (TDCPP; detection frequency 36%), followed by components typically found in the Firemaster550 commercial mixture (detection frequency 17%). Five samples contained PBDE congeners commonly associated with PentaBDE, suggesting products with PentaBDE are still in-use. Two chlorinated organophosphate flame retardants (OPFRs) not previously documented in the environment were also identified, one of which is commercially sold as V6 (detection frequency 15%) and contains tris(2-chloroethyl) phosphate (TCEP) as an impurity. As an addition to this study, we used a portable X-ray fluorescence (XRF) analyzer to estimate the bromine and chlorine content of the foam and investigate whether XRF is a useful method for predicting the presence of halogenated flame

  11. Selective pressurized liquid extraction of replacement and legacy brominated flame retardants from soil.

    PubMed

    McGrath, Thomas J; Morrison, Paul D; Ball, Andrew S; Clarke, Bradley O

    2016-08-01

    Polybrominated diphenyl ethers (PBDEs) are a class of flame retardant registered as UN POPs due to their persistence in the environment, bioaccumulation potential and toxicity. Replacement novel brominated flame retardants (NBFRs) have exhibited similar health hazards and environmental distribution, becoming recognized as significant contaminants. This work describes the development and validation of a sensitive and reliable method for the simultaneous quantitation of PBDEs and NBFRs in environmental soil samples using selective pressurized liquid extraction (S-PLE) and gas chromatography coupled to triple quadrupole mass spectrometry (GC-(EI)-MS/MS). Under optimal conditions, extraction of eight PBDEs (-28, -47, -99, -100, -153, -154, -183 and -209) and five NBFRs; pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) and bis(2,4,6-tribromophenoxy)ethane (BTBPE) was performed at 100°C and 1500psi using a 1:1 mixture of hexane and dichloromethane. The method utilized 33mL capacity PLE cells containing, from bottom to top, a single cellulose filter, 3g activated Florisil, 6g acid silica (10% w/w), 3g Na2SO4, another cellulose filter, 2g activated copper powder and 3g soil sample dispersed in 2g Na2SO4 and 1g of Hydromatrix. The method was evaluated by repeated extraction and analysis of all analytes from 3g soil at three spike concentrations. Good recoveries were observed for most analytes at each of the spiking levels with RSD values generally below 20%. MDLs ranged from 0.01 to 4.8ng/g dw for PBDEs and 0.01-0.55ng/g dw for NBFRs. The described one-step combined extraction and cleanup method reduces sample processing times compared with traditional procedures, while delivering comparable analytical performance. The method was successfully applied to environmental soil samples (n=5), detecting PBDEs in each sample and providing the first account of NBFR contamination in Australian soils

  12. Maternal transfer of emerging brominated and chlorinated flame retardants in European eels.

    PubMed

    Sühring, Roxana; Freese, Marko; Schneider, Mandy; Schubert, Sophia; Pohlmann, Jan-Dag; Alaee, Mehran; Wolschke, Hendrik; Hanel, Reinhold; Ebinghaus, Ralf; Marohn, Lasse

    2015-10-15

    The European eel (Anguilla anguilla) is regarded as a critically endangered species. Scientists are in agreement that the "quality of spawners" is a vital factor for the survival of the species. This quality can be impaired by parasites, disease and pollution. Especially endocrine disrupting organic chemicals pose a potential threat to reproduction and development of offspring. To our knowledge, the findings in this publication for the first time describe maternal transfer of contaminants in eels. We analysed the concentrations of in total 53 polybrominated diphenyl ethers (PBDEs) and their halogenated substitutes in muscle, gonads and eggs of artificially matured European eels and in muscle and gonads of untreated European eels that were used for comparison. We found evidence that persistent organic pollutants such as PBDEs, as well as their brominated and chlorinated substitutes are redistributed from muscle tissue to gonads and eggs. Concentrations ranged from 0.001 ng g(-1)ww for sum Dechlorane metabolites (DPMA, aCL10DP, aCl11DP) to 2.1 ng g(-1)ww for TBA in eggs, 0.001 ng g(-1)ww for Dechlorane metabolites to 9.4 ng g(-1)ww for TBA in gonads and 0.002 ng g(-1)ww for Dechlorane metabolites to 54 ng g(-1)ww for TBA in muscle tissue. Average egg muscle ratios (EMRs) for compounds detectable in artificially matured eels from both Schlei Fjord and Ems River ranged from 0.01 for Dechlorane 602 (DDC-DBF) to 10.4 for PBEB. Strong correlations were found between flame retardant concentrations and lipid content in the analysed tissue types, as well as transfer rates and octanol-water partitioning coefficient, indicating that these parameters were the driving factors for the observed maternal transfer. Furthermore, indications were found, that TBP-DBPE, TBP-AE, BATE and TBA have a significant uptake from the surrounding water, rather than just food and might additionally be formed by metabolism or biotransformation processes. Dechloranes seem to be of increasing

  13. Polybrominated Diphenyl Ethers in Dryer Lint: An Advanced Analysis Laboratory

    ERIC Educational Resources Information Center

    Thompson, Robert Q.

    2008-01-01

    An advanced analytical chemistry laboratory experiment is described that involves environmental analysis and gas chromatography-mass spectrometry. Students analyze lint from clothes dryers for traces of flame retardant chemicals, polybrominated diphenylethers (PBDEs), compounds receiving much attention recently. In a typical experiment, ng/g…

  14. Smoke suppression properties of ferrite yellow on flame retardant thermoplastic polyurethane based on ammonium polyphosphate.

    PubMed

    Chen, Xilei; Jiang, Yufeng; Jiao, Chuanmei

    2014-02-15

    This article mainly studies smoke suppression properties and synergistic flame retardant effect of ferrite yellow (FeOOH) on flame retardant thermoplastic polyurethane (TPU) composites using ammonium polyphosphate (APP) as a flame retardant agent. Smoke suppression properties and synergistic flame retardant effect of FeOOH on flame retardant TPU composites were intensively investigated by smoke density test (SDT), cone calorimeter test (CCT), scanning electron microscopy (SEM), and thermal-gravimetric analysis (TGA). Remarkably, the SDT results show that FeOOH can effectively decrease the amount of smoke production with or without flame. On the other hand, the CCT data reveal that the addition of FeOOH can apparently reduce heat release rate (HRR), total heat release (THR), and total smoke release (TSR), etc. Here, FeOOH is considered to be an effective smoke suppression agent and a good synergism with APP in flame retardant TPU composites, which can greatly improve the structure of char residue realized by TGA and SEM results. PMID:24389005

  15. Neurobehavioral function and low-level exposure to brominated flame retardants in adolescents: a cross-sectional study

    PubMed Central

    2012-01-01

    Background Animal and in vitro studies demonstrated a neurotoxic potential of brominated flame retardants, a group of chemicals used in many household and commercial products to prevent fire. Although the first reports of detrimental neurobehavioral effects in rodents appeared more than ten years ago, human data are sparse. Methods As a part of a biomonitoring program for environmental health surveillance in Flanders, Belgium, we assessed the neurobehavioral function with the Neurobehavioral Evaluation System (NES-3), and collected blood samples in a group of high school students. Cross-sectional data on 515 adolescents (13.6-17 years of age) was available for the analysis. Multiple regression models accounting for potential confounders were used to investigate the associations between biomarkers of internal exposure to brominated flame retardants [serum levels of polybrominated diphenyl ether (PBDE) congeners 47, 99, 100, 153, 209, hexabromocyclododecane (HBCD), and tetrabromobisphenol A (TBBPA)] and cognitive performance. In addition, we investigated the association between brominated flame retardants and serum levels of FT3, FT4, and TSH. Results A two-fold increase of the sum of serum PBDE’s was associated with a decrease of the number of taps with the preferred-hand in the Finger Tapping test by 5.31 (95% CI: 0.56 to 10.05, p = 0.029). The effects of the individual PBDE congeners on the motor speed were consistent. Serum levels above the level of quantification were associated with an average decrease of FT3 level by 0.18 pg/mL (95% CI: 0.03 to 0.34, p = 0.020) for PBDE-99 and by 0.15 pg/mL (95% CI: 0.004 to 0.29, p = 0.045) for PBDE-100, compared with concentrations below the level of quantification. PBDE-47 level above the level of quantification was associated with an average increase of TSH levels by 10.1% (95% CI: 0.8% to 20.2%, p = 0.033), compared with concentrations below the level of quantification. We did not observe effects of

  16. CONCENTRATIONS AND COMPOSITIONS OF POLYBROMINATED BIPHENYLS, -DIBENZO-P-DIOXINS, AND -DIBENZOFURANS IN TECHNICAL POLYBROMINATED DIPHENYL ETHER PREPARATIONS.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) have been used as flame retardants in textiles, electronic equipment and plastics.1 The three major commercial products available in the market are penta-BDE, octa-BDE, and deca-BDE products. Due to their widespread use, persistence, and bio...

  17. Migration of Organophorus Flame Retardants From Closed cell form to Settled Dust

    EPA Science Inventory

    Many industrial and consumer products, such as electrical and electronic products, furniture, plastics, textile, and building materials are manufactured with organophosphorus flame retardants (OPFRs). OPFRs can leach or diffuse out of the products and are released to the surround...

  18. Characterization of organophosphorus flame retardants' sorption on building materials and consumer products

    EPA Science Inventory

    Better understanding the transport mechanisms of organophosphorus flame-retardants (OPFRs) in the residential environment is important to more accurately estimate their indoor exposure and develop risk management strategies that protect human health. This study describes an impro...

  19. Thermal and mechanical behavior of flame retardant epoxy-polyesterurethane blends

    NASA Astrophysics Data System (ADS)

    Patel, R. H.; Hirani, A. V.; Kachhia, P. H.

    2016-05-01

    Polyesterurethanes are used in different applications due to their unique combination of the properties like toughness, flexibility, solvent resistance, etc. Nowadays flame retardant properties of polymers are of commercial interest because of their potential use in high performance applications. In the present study attempts have been taken to improve the flame retardant properties of conventional epoxy resin by incorporating phosphorus based polyesterurethane. Polyesterurethane has been synthesized in the laboratory and characterized by chemical and instrumental analysis techniques. Thermal stability and char value of the blends have been determined using thermogravimetric analysis technique. Limiting Oxygen Index (LOI) and UL-94 test methods have been used to determine the flame retardant properties of neat polymer and their blends in film form. Mechanical properties like tensile strength, elongation and impact resistance of the blends have been found out. Polyblend of epoxy resin with phosphorus based polyesterurethane has improved flame retardant properties compare to neat epoxy resin.

  20. Detection of halogenated flame retardants in polyurethane foam by particle induced X-ray emission

    NASA Astrophysics Data System (ADS)

    Maley, Adam M.; Falk, Kyle A.; Hoover, Luke; Earlywine, Elly B.; Seymour, Michael D.; DeYoung, Paul A.; Blum, Arlene; Stapleton, Heather M.; Peaslee, Graham F.

    2015-09-01

    A novel application of particle-induced X-ray emission (PIXE) has been developed to detect the presence of chlorinated and brominated flame retardant chemicals in polyurethane foams. Traditional Gas Chromatography-Mass Spectrometry (GC-MS) methods for the detection and identification of halogenated flame retardants in foams require extensive sample preparation and data acquisition time. The elemental analysis of the halogens in polyurethane foam performed by PIXE offers the opportunity to identify the presence of halogenated flame retardants in a fraction of the time and sample preparation cost. Through comparative GC-MS and PIXE analysis of 215 foam samples, excellent agreement between the two methods was obtained. These results suggest that PIXE could be an ideal rapid screening method for the presence of chlorinated and brominated flame retardants in polyurethane foams.

  1. Formulation of intumescent flame retardant coatings containing natural-based tea saponin.

    PubMed

    Qian, Wei; Li, Xiang-Zhou; Wu, Zhi-Ping; Liu, Yan-Xin; Fang, Cong-Cong; Meng, Wei

    2015-03-18

    Natural product tea saponin (TS), extracted from the nutshell of camellia (Camellia oleifera Abel, Theaceae), was introduced into intumescent flame retardant formulations as blowing agent and carbon source. The formulations of the flame retardant system were optimized to get the optimum proportion of TS, and intumescent flame retardant coatings containing tea saponin (TS-IFRCs) were then prepared. It was found that TS can significantly affect the combustion behavior and the thermal stability of TS-IFRCs evaluated by cone calorimetry and simultaneous thermal analyzer, respectively. It was shown that TS, degraded to water vapor and carbon at high temperatures, can combine with other components to form a well-developed char layer. The char layer was supposed to inhibit erosion upon exposure to heat and oxygen and enhance the flame retardancy of TS-IFRCs. In addition, the smoke release of TS-IFRCs was also studied, which provided a low amount of smoke production. PMID:25721245

  2. Physical-chemical properties and evaluative fate modelling of 'emerging' and 'novel' brominated and organophosphorus flame retardants in the indoor and outdoor environment.

    PubMed

    Liagkouridis, Ioannis; Cousins, Anna Palm; Cousins, Ian T

    2015-08-15

    Several groups of flame retardants (FRs) have entered the market in recent years as replacements for polybrominated diphenyl ethers (PBDEs), but little is known about their physical-chemical properties or their environmental transport and fate. Here we make best estimates of the physical-chemical properties and undertake evaluative modelling assessments (indoors and outdoors) for 35 so-called 'novel' and 'emerging' brominated flame retardants (BFRs) and 22 organophosphorus flame retardants (OPFRs). A QSPR (Quantitative Structure-Property Relationship) based technique is used to reduce uncertainty in physical-chemical properties and to aid property selection for modelling, but it is evident that more, high quality property data are required for improving future assessments. Evaluative modelling results show that many of the alternative FRs, mainly alternative BFRs and some of the halogenated OPFRs, behave similarly to the PBDEs both indoors and outdoors. These alternative FRs exhibit high overall persistence (Pov), long-range transport potential (LRTP) and POP-like behaviour and on that basis cannot be regarded as suitable replacements to PBDEs. A group of low molecular weight alternative BFRs and non-halogenated OPFRs show a potentially better environmental performance based on Pov and LRTP metrics. Results must be interpreted with caution though since there are significant uncertainties and limited data to allow for thorough model evaluation. Additional environmental parameters such as toxicity and bioaccumulative potential as well as functionality issues should be considered in an industrial substitution strategy. PMID:25933174

  3. Product screening for sources of halogenated flame retardants in Canadian house and office dust.

    PubMed

    Abbasi, Golnoush; Saini, Amandeep; Goosey, Emma; Diamond, Miriam L

    2016-03-01

    Human exposure to halogenated flame retardants (HFRs) such as polybrominated diphenyl ethers (PBDEs) and their replacements, can be related to exposure to indoor dust and direct contact with HFR-containing products. This study aimed to identify electronic products that contributed to HFRs measured in indoor dust and to develop a screening method for identifying HFRs in hard polymer products. Concentrations of 10 PBDEs and 12 halogenated replacements in dust and surface wipe samples of hard polymer casings of electronic products plus Br in the surfaces of those casing measured using X-ray fluorescence (XRF) were analyzed from 35 homes and 10 offices in Toronto (ON, Canada). HFR concentrations in dust and product wipes were positively correlated. Thus, we hypothesize that electronic products with the highest HFR concentrations contribute the most to concentrations in dust, regardless of the volatility of the HFR. Abundant HFRs in dust and product wipes were PBDEs (BDE-47, 99, 100, 153, 154, 183, 209), TDCPP, DBDPE, EH-TBB and BEHTBP. Older CRT TVs had the highest concentration of BDE-209 of all products tested. This was followed by higher concentrations of HFRs in PCs, Audio/Video (A/V) devices, small household appliances (HHAs) and flat screen TVs. The removal of HFRs from polymer surfaces using wipes supports concerns that HFRs could be transferred from these surfaces to hands as a result of direct contact with HFR-containing products. Surface wipe testing shows promise for screening additive HFRs. In comparison, the Br-content obtained using a handheld XRF analyzer did not correspond to concentrations obtained from surface wipe testing. PMID:26747994

  4. In vitro profiling of the endocrine-disrupting potency of brominated flame retardants.

    PubMed

    Hamers, Timo; Kamstra, Jorke H; Sonneveld, Edwin; Murk, Albertinka J; Kester, Monique H A; Andersson, Patrik L; Legler, Juliette; Brouwer, Abraham

    2006-07-01

    Over the last few years, increasing evidence has become available that some brominated flame retardants (BFRs) may have endocrine-disrupting (ED) potencies. The goal of the current study was to perform a systematic in vitro screening of the ED potencies of BFRs (1) to elucidate possible modes of action of BFRs in man and wildlife and (2) to classify BFRs with similar profiles of ED potencies. A test set of 27 individual BFRs were selected, consisting of 19 polybrominated diphenyl ether congeners, tetrabromobisphenol-A, hexabromocyclododecane, 2,4,6-tribromophenol, ortho-hydroxylated brominated diphenyl ether 47, and tetrabromobisphenol-A-bis(2,3)dibromopropyl ether. All BFRs were tested for their potency to interact with the arylhydrocarbon receptor, androgen receptor (AR), progesterone receptor (PR), and estrogen receptor. In addition, all BFRs were tested for their potency to inhibit estradiol (sulfation by estradiol sulfotransferase (E2SULT), to interfere with thyroid hormone 3,3',5-triiodothyronine (T3)-mediated cell proliferation, and to compete with T3-precursor thyroxine for binding to the plasma transport protein transthyretin (TTR). The results of the in vitro screening indicated that BFRs have ED potencies, some of which had not or only marginally been described before (AR antagonism, PR antagonism, E2SULT inhibition, and potentiation of T3-mediated effects). For some BFRs, the potency to induce AR antagonism, E2SULT inhibition, and TTR competition was higher than for natural ligands or clinical drugs used as positive controls. Based on their similarity in ED profiles, BFRs were classified into five different clusters. These findings support further investigation of the potential ED effects of these environmentally relevant BFRs in man and wildlife. PMID:16601080

  5. Probing the debromination of the flame retardant decabromodiphenyl ether in sediments of a boreal lake.

    PubMed

    Orihel, Diane M; Bisbicos, Tommy; Darling, Colin T R; Dupuis, Alain P; Williamson, Mary; Muir, Derek C G

    2016-03-01

    After decades of use of polybrominated diphenyl ethers (PBDEs) as flame retardants, a large reservoir of these toxins has accumulated in ecosystems worldwide. The present study used an innovative approach to examine whether the fully brominated PBDE decabromodiphenyl ether (decaBDE) degrades to more toxic congeners in aquatic environments. The authors incubated intact sediment microcosms with high-purity [(13)C]decaBDE in a remote boreal lake to assess its debromination under ambient conditions. Although the addition of [(13)C]decaBDE increased total PBDE concentrations in sediment more than 10-fold, the relative amount of [(13)C]decaBDE in sediment did not change significantly over a 1-mo incubation. However, observation of small quantities of lower-brominated [(13)C]BDEs lent support to the hypothesis that decaBDE is slowly debrominated. The authors observed a significant increase in octaBDEs and nonaBDEs in profundal, but not littoral, sediment over 30 d. A second experiment in which sediment was incubated under different light and oxygen regimes yielded a surprising result-oxygen significantly stimulated the formation of octaBDEs and nonaBDEs. The authors also conducted a large-scale in situ enclosure experiment in which they followed the fate of experimentally added decaBDE in sediment over 26 mo, but that study yielded little evidence of decaBDE debromination. Overall, the authors suggest that the debromination of decaBDE occurs very slowly, if at all, in natural sediment of boreal lakes, in contrast to the rapid degradation kinetics reported by most laboratory-based studies, which are usually conducted by dissolving decaBDE in organic solvents. The findings reinforce the need for field studies on contaminant fate to inform environmental policy decisions. PMID:26332257

  6. Inhibition of thyroid hormone sulfotransferase activity by brominated flame retardants and halogenated phenolics.

    PubMed

    Butt, Craig M; Stapleton, Heather M

    2013-11-18

    Many halogenated organic contaminants (HOCs) are considered endocrine disruptors and affect the hypothalamic-pituitary-thyroid axis, often by interfering with circulating levels of thyroid hormones (THs). We investigated one potential mechanism for TH disruption, inhibition of sulfotransferase activity. One of the primary roles of TH sulfation is to support the regulation of biologically active T3 through the formation of inactive THs. We investigated TH sulfotransferase inhibition by 14 hydroxylated polybrominated diphenyl ethers (OH BDEs), BDE 47, triclosan, and fluorinated, chlorinated, brominated, and iodinated analogues of 2,4,6-trihalogenated phenol and bisphenol A (BPA). A new mass spectrometry-based method was also developed to measure the formation rates of 3,3'-T2 sulfate (3,3'-T2S). Using pooled human liver cytosol, we investigated the influence of these HOCs on the sulfation of 3,3'-T2, a major substrate for TH sulfation. For the formation of 3,3'-T2S, the Michaelis constant (Km) was 1070 ± 120 nM and the Vmax was 153 ± 6.6 pmol min(-1) (mg of protein)(-1). All chemicals investigated inhibited sulfotransferase activity with the exception of BDE 47. The 2,4,6-trihalogenated phenols were the most potent inhibitors followed by the OH BDEs and then halogenated BPAs. The IC50 values for the OH BDEs were primarily in the low nanomolar range, which may be environmentally relevant. In silico molecular modeling techniques were also used to simulate the binding of OH BDE to SULT1A1. This study suggests that some HOCs, including antimicrobial chemicals and metabolites of flame retardants, may interfere with TH regulation through inhibition of sulfotransferase activity. PMID:24089703

  7. Brominated flame retardants - Exposure and risk assessment for the general population.

    PubMed

    Fromme, H; Becher, G; Hilger, B; Völkel, W

    2016-01-01

    Brominated flame retardants (BFRs) are a large group of different substances used in numerous products to prevent fire hazards. Some of them are persistent in the environment, accumulate in the food chain and are of toxicological concern, while for others current data are limited. Meanwhile, BFRs have been found in many environmental media, foods, and biota including humans. This review presents recent findings obtained from monitoring data in environmental media relevant for human exposure, as well as dietary exposure. In this context, concentrations in indoor and ambient air and in house dust are outlined. Furthermore, we summarize human biomonitoring data on BFR levels in blood and breast milk. Current estimates of the overall exposure of the general population using different relevant subsets are also addressed. All of these data are discussed in relation to currently available toxicological reference values used for risk assessment purposes. Obviously, the exposure of the general population varies considerably in different parts of the world and even within countries. Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) show the highest intake during infancy. While the highest intake for BDE 47 for all groups was observed in the US, the total BDE 209 and HBCD intake was highest in the UK. For HBCD and all PBDEs except BDE 209, diet accounts for a large proportion of the total intake during infancy in all countries. With regard to toddlers and adults, the contribution of diet to total intake is high in Germany and the UK, while in the US, the high concentrations of PBDE in dust resulted in a notably smaller proportion of the intake being attributed to diet. PMID:26412400

  8. Emerging and historical brominated flame retardants in peregrine falcon (Falco peregrinus) eggs from Canada and Spain.

    PubMed

    Guerra, Paula; Alaee, Mehran; Jiménez, Begoña; Pacepavicius, Grazina; Marvin, Chris; MacInnis, Gordia; Eljarrat, Ethel; Barceló, Damià; Champoux, Louise; Fernie, Kim

    2012-04-01

    Comparisons of brominated flame retardants (BFRs) in the eggs of peregrine falcons (Falco peregrinus) recently collected (2003-2007), are made between Canada (N=12) and Spain (N=13). Overall, concentrations of sum (Σ) polybrominated diphenyl ethers (PBDEs; 16 di-deca-BDE congeners) exceeded Σhexabromocyclododecane (HBCD) and were an order of magnitude higher than 2,2'4,4',5,5'-hexabromobiphenyl (BB-153)>hexachlorocyclopentenyl-dibromocyclooctane (HCBDCO)>1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE)>decabromodiphenylethane (DBDPE)>octabromotrimethylphenyllindane (OBIND)>hexabromobenzene (HBB)>bis(2-ethyl-1hexyl)tetrabromophthalate (BEHTBP). This is the first report of detectable HBCDCO and BEHTBP concentrations in biota, and the highest in ovo concentration of ∑HBCD (14,617 ng/glw; Montreal, Canada) to date. There were significantly greater egg concentrations of BB-153, ΣHBCD, and ΣPBDE including BDE-153, -99, -100 and -183, in Canadian than Spanish peregrines with a terrestrial diet. HBB, BTBPE, and OBIND were detected in eggs from both countries, but only Canadian peregrine eggs had detectable levels of HCDBCO (25%) and DBDPE (N=1). The in ovo PBDE congener profile was dominated by BDE-153>BDE-99>BDE-47>BDE-183>BDE-100>BDE-209, with the isomeric HBCD pattern being α-HBCD>γ-HBCD (β-HBCD undetected). The Canadian peregrine eggs had lower enantiomeric HBCD values consistent with their higher fractions of (-) α-HBCD, suggesting selective enantiomeric enrichment or that the (+) α-isomer is more readily metabolized and so deposited in the egg through maternal transfer. Continental differences in egg burdens of peregrines are discussed relative to BFR usage patterns and exposure of peregrines on their breeding grounds. PMID:21862134

  9. Geographical distribution of non-PBDE-brominated flame retardants in mussels from Asian coastal waters.

    PubMed

    Isobe, Tomohiko; Ogawa, Shohei P; Ramu, Karri; Sudaryanto, Agus; Tanabe, Shinsuke

    2012-09-01

    Hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), and decabromodiphenyl ethane (DBDPE) used as alternatives for polybrominated diphenyl ethers (PBDEs) are also persistent in the environment as PBDEs. Limited information on these non-PBDE brominated flame retardants (BFRs) is available; in particular, there are only few publications on environmental pollution by these contaminants in the coastal waters of Asia. In this regard, we investigated the contamination status of HBCDs, BTBPE, and DBDPE in the coastal waters of Asia using mussels as a bioindicator. Concentrations of HBCDs, BTBPE, and DBDPE were determined in green (Perna viridis) and blue mussels (Mytilus edulis) collected from the coastal areas in Cambodia, China (mainland), SAR China (Hong Kong), India, Indonesia, Japan, Malaysia, the Philippines, and Vietnam on 2003-2008. BTBPE and DBDPE were analyzed using GC-MS, whereas HBCDs were determined by LC-MS/MS. HBCDs, BTBPE, and DBDPE were found in mussels at levels ranging from <0.01 to 1,400, <0.1 to 13, and <0.3 to 22 ng/g lipid wt, respectively. Among the three HBCD diastereoisomers, α-HBCD was the dominant isomer followed by γ- and β-HBCDs. Concentrations of HBCDs and DBDPE in mussels from Japan and Korea were higher compared to those from the other Asian countries, indicating extensive usage of these non-PBDE BFRs in Japan and Korea. Higher levels of HBCDs and DBDPE than PBDEs were detected in some mussel samples from Japan. The results suggest that environmental pollution by non-PBDE BFRs, especially HBCDs in Japan, is ubiquitous. This study provides baseline information on the contamination status of these non-PBDE BFRs in the coastal waters of Asia. PMID:22875421

  10. Characterizing the in vitro hepatic biotransformation of the flame retardant BDE 99 by common carp.

    PubMed

    Noyes, Pamela D; Kelly, Shannon M; Mitchelmore, Carys L; Stapleton, Heather M

    2010-04-15

    Polybrominated diphenyl ethers (PBDEs) are a class of flame retardant chemicals known to biomagnify in aquatic foodwebs. However, significant biotransformation of some congeners via reductive dehalogenation has been observed during in vivo and in vitro laboratory exposures, particularly in fish models. Little information is available on the enzyme systems responsible for catalyzing this metabolic pathway in fish. This study was undertaken to characterize the biotransformation of one primary BDE congener, 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), using in vitro techniques. Hepatic sub-cellular fractions were first prepared from individual adult common carp (Cyprinus carpio) to examine metabolism in both microsomal and cytosolic sub-cellular fractions. Debromination rates (i.e. BDE-99 biotransformation to BDE-47) were generally higher in the microsomal fraction than in the cytosolic fraction, and some intra-species variability was observed. Further experiments were conducted to determine the biotransformation kinetics and the influence of specific co-factors, inhibitors and competitive substrates on metabolism using pooled carp liver microsomes. The apparent K(m) and V(max) values were 19.4microM and 1120pmolesh(-1)mgprotein(-1), respectively. Iodoacetate (IaC) and the two thyroid hormones, reverse triodothyronine (rT3) and thyroxine (T4), significantly inhibited the debromination of BDE-99 in microsomal sub-cellular fractions with IC(50) values of 2.2microM, 0.83microM, and >1.0microM, respectively. These results support our hypothesis that deiodinase enzymes may be catalyzing the metabolism of PBDEs in fish liver tissues. Further studies are needed to evaluate metabolic activity in other species and tissues that contain these enzymes. PMID:20080306

  11. Bromine content and brominated flame retardants in food and animal feed from the UK.

    PubMed

    Fernandes, A R; Mortimer, D; Rose, M; Smith, F; Panton, S; Garcia-Lopez, M

    2016-05-01

    Current occurrence data for polybrominated diphenyl ethers (PBDE) and hexa-bromocyclododecane (HBCD) measured in most commonly consumed foods (n = 156) and animal feeds (n = 51) sampled in the UK, demonstrates an ongoing ubiquity of these contaminants in human and animal diets. PBDE concentrations for the sum of 17 measured congeners ranged from 0.02 ng/g to 8.91 ng/g whole weight for food, and 0.11 ng/g to 9.63 ng/g whole weight for animal feeds. The highest concentration ranges, and mean values were detected in fish, processed foods and fish feeds. HBCD diastereomers (alpha-HBCD was the most commonly detected) generally occurred at lower concentrations (from <0.01 ng/g to 10.1 ng/g for food and <0.01 ng/g to 0.66 ng/g for animal feed) and less frequently than PBDEs, but tetrabromobisphenol A which was also measured, was rarely detected. The total bromine content of the samples was also determined in an attempt to use a mass balance approach to investigate some of these samples for the occurrence of novel and emerging BFRs. Although the approach was further refined by measuring organic bromine content, the concentrations of bromine were too high (in most cases by orders of magnitude) to allow use of the approach. A selected sub-set of samples was screened by GC-MS, for the presence of novel/emerging brominated flame retardants (PBT, TBX, PBEB, DBHCTD, HCTBPH and OBTMPI) but these were not detected at the higher limits of detection that result from full scan (GC-MS) screening. This data will contribute to the EU wide risk assessment on these contaminants. PMID:26733012

  12. Associations between brominated flame retardants in human milk and Thyroid-Stimulating Hormone (TSH) in neonates

    PubMed Central

    Eggesbø, Merete; Thomsen, Cathrine; Jørgensen, Jens V.; Becher, Georg; Odland, Jon Øyvind; Longnecker, Matthew P.

    2011-01-01

    Background Brominated flame retardants (BFRs) have been in widespread use in a vast array of consumer products since the 1970s. The metabolites of some BFRs show a structural similarity to thyroid hormones and experimental animal studies have confirmed that they may interfere with thyroid hormone homeostasis. A major concern has been whether intrauterine exposure to BFRs may disturb thyroid homeostasis since the fetal brain is particularly susceptible to alterations in thyroid hormones. However, few reports on newborns have been published to date. Objectives To evaluate the association between BFRs and neonatal thyroid-stimulating hormone (TSH). Methods We studied six polybrominated diphenyl ethers (PBDEs) measured in milk samples from 239 women who were part of the “Norwegian Human Milk Study” (HUMIS), 2003–2006. Hexabromocyclododecane (HBCD) and BDE-209 were measured in a subset of the women (193 and 46 milk samples, respectively). The milk was sampled at a median of 33 days after delivery. TSH was measured in babies three days after delivery as part of the routine national screening program for early detection of congenital hypothyroidism. Additional information was obtained through the Medical Birth Registry and questionnaires to the mothers. Results The PBDE concentrations in human milk in Norway were comparable to concentrations reported from other European countries and Asia, but not the US and Canada where levels are approximately one order of magnitude higher. We observed no statistically significant associations between BDE-47, 99, 153, 154, 209 and HBCD in human milk and TSH in models adjusted for possible confounders and other environmental toxicants including polychlorinated biphenyls (PCBs). Conclusions We did not observe an association between TSH and exposure to HBCD and PBDEs within the exposure levels observed. PMID:21601188

  13. [Brominated flame retardants: environmental contamination, exposure sources and potential negative health effects].

    PubMed

    Fiore, Maria; Floridia, Adriana; Oliveri Conti, Gea; Ledda, Caterina; Mauceri, Cristina; Ferrante, Margherita

    2015-01-01

    This article summarizes recent evidence regarding brominated flame retardants. These represent the most common type of flame retardants used and recent studies have highlighted their presence in various concentrations in different environmental matrices, including areas distant from production areas, and in human biological samples. Many doubts persist regarding exposure sources, toxicity, metabolism and transformation processes once these products are released into the environment. PMID:26722829

  14. Intumescent flame-retardant and self-healing superhydrophobic coatings on cotton fabric.

    PubMed

    Chen, Shanshan; Li, Xiang; Li, Yang; Sun, Junqi

    2015-04-28

    Flame-retardant and self-healing superhydrophobic coatings are fabricated on cotton fabric by a convenient solution-dipping method, which involves the sequential deposition of a trilayer of branched poly(ethylenimine) (bPEI), ammonium polyphosphate (APP), and fluorinated-decyl polyhedral oligomeric silsesquioxane (F-POSS). When directly exposed to flame, such a trilayer coating generates a porous char layer because of its intumescent effect, successfully giving the coated fabric a self-extinguishing property. Furthermore, the F-POSS embedded in cotton fabric and APP/bPEI coating produces a superhydrophobic surface with a self-healing function. The coating can repetitively and autonomically restore the superhydrophobicity when the superhydrophobicity is damaged. The resulting cotton fabric, which is flame-resistant, waterproof, and self-cleaning, can be easily cleaned by simple water rinsing. Thus, the integration of self-healing superhydrophobicity with flame retardancy provides a practical way to resolve the problem of washing durability of the flame-retardant coatings. The flame-retardant and superhydrophobic fabric can endure more than 1000 cycles of abrasion under a pressure of 44.8 kPa without losing its flame retardancy and self-healing superhydrophobicity, showing potential applications as multifunctional advanced textiles. PMID:25777158

  15. Organophosphorous flame retardants in biota from Svalbard, Norway.

    PubMed

    Hallanger, Ingeborg G; Sagerup, Kjetil; Evenset, Anita; Kovacs, Kit M; Leonards, Pim; Fuglei, Eva; Routti, Heli; Aars, Jon; Strøm, Hallvard; Lydersen, Christian; Gabrielsen, Geir Wing

    2015-12-15

    Eight arctic species, including fish, birds and mammals, from diverse habitats (marine and terrestrial) within the Svalbard Archipelago, Norway, were screened for 14 organophosphorus flame retardant (PFR) compounds. Ten PFRs were detected: tris(2-chloroethyl)phosphate (TCEP), tris(2-chloroisopropyl)phosphate (TCIPP), tris(1,3-dichloro-2-propyl)phosphate (TDCIPP), triphenyl phosphate (TPHP); 2-ethylhexyl diphenyl phosphate (EHDPP); tris(2-butoxyethyl)phosphate (TBOEP); tritolyl phosphate (TCrP); triisobutyl phosphate (TIBP); tris(2-ethylhexyl)phosphate (TEHP); and butyl diphenyl phosphate (DPhBP). The greatest number of different PFR compounds, and the highest detection frequency were measured in capelin (Mallotus villotus), and the lowest in Brünnich's guillemot (Uria lomvia). The highest concentrations of ΣPFR, as well as the highest concentration of a single PFR compound, TBOEP, were measured in arctic fox (Vulpes lagopus). The presence of PFR compounds in arctic biota indicates that these compounds can undergo long-range transport and are, to some degree, persistent and bioaccumulated. The potential for biomagnification from fish to higher trophic levels seems to be limited. PMID:26453403

  16. Flame Retardant Effect of Aerogel and Nanosilica on Engineered Polymers

    NASA Technical Reports Server (NTRS)

    Williams, Martha K.; Smith, Trent M.; Roberson, Luke B.; Yang, Feng; Nelson, Gordon L.

    2010-01-01

    Aerogels are typically manufactured vIa high temperature and pressure-critical-point drying of a colloidal metal oxide gel filled with solvents. Aerogel materials derived from silica materials represent a structural morphology (amorphous, open-celled nanofoams) rather than a particular chemical constituency. Aerogel is not like conventional foams in that it is a porous material with extreme microporosity and composed of individual features only a few nanometers in length with a highly porous dendriticlike structure. This unique substance has unusual properties such as low thermal conductivity, refractive index and sound suppression; in addition to its exceptional ability to capture fast moving dust. The highly porous nature of the aerogel's structure provides large amounts of surface area per unit weight. For instance, a silica aerogel material with a density of 100 kilograms per cubic meters can have surface areas of around 800 to 1500 square meters per gram depending on the precursors and process utilized to produce it. To take advantage of the unique properties of silica aerogels, especially the ultra light weight and low thermal conductivity, their composites with various engineering polymers were prepared and their flammability was investigated by Cone Calorimetry. The flammability of various polystyrene/silica aerogel nanocomposites were measured. The combination of these nanocomposites with a NASA patented flame retardant SINK were also studied. The results were compared with the base polymer to show the differences between composites with different forms of silica.

  17. Catalytic degradation of brominated flame retardants by copper oxide nanoparticles.

    PubMed

    Yecheskel, Yinon; Dror, Ishai; Berkowitz, Brian

    2013-09-01

    The catalytic degradation of two brominated flame retardants (BFRs), tribromoneopentyl alcohol (TBNPA) and 2,4 dibromophenol (2,4-DBP) by copper oxide nanoparticles (nCuO) was investigated. The degradation kinetics, the debromination, and the formation of intermediates by nCuO catalysis were also compared to Fenton oxidation and nano zero-valent iron (nZVI) reduction methods. BFRs have been added to various products like plastic, textile, electronics and synthetic polymers at growing rates. In spite of the clear advantages of reducing fire damages, many of these BFRs may be released to the environment after their beneficial use and become contaminants. The two studied BFRs were fully degraded with sufficient time (hours to days) and oxidation agent (H2O2). Shorter reaction times showed differences in reaction pathway and kinetics. The 2,4-DBP showed faster degradation than TBNPA, by nCuO catalysis. Relatively high resistance to degradation was recorded for 2,4-DBP with nZVI, yielding 20% degradation after 24h, while the TBNPA was degraded by 85% within 12h. Electron Spin Resonance (ESR) measurements show generation of both hydroxyl and superoxide radicals. In addition, inhibition of 2,4-DBP degradation in the presence of spin traps implies a radical degradation mechanism. A catalytic mechanism for radical generation and BFR degradation by nCuO is proposed. It is further suggested that H2O2 plays an essential role in the activation of the catalyst. PMID:23786809

  18. Brominated flame retardants and seafood safety: a review.

    PubMed

    Cruz, Rebeca; Cunha, Sara C; Casal, Susana

    2015-04-01

    Brominated flame retardants (BFRs), frequently applied to industrial and household products to make them less flammable, are highly persistent in the environment and cause multi-organ toxicity in human and wildlife. Based on the review of BFRs presence in seafood published from 2004 to 2014, it is clear that such pollutants are not ideally controlled as the surveys are too restricted, legislation inexistent for some classes, the analytical methodologies diversified, and several factors as food processing and eating habits are generally overlooked. Indeed, while a seafood rich diet presents plenty of nutritional benefits, it can also represent a potential source of these environmental contaminants. Since recent studies have shown that dietary intake constitutes a main route of human exposure to BFRs, it is of major importance to review and enhance these features, since seafood constitutes a chief pathway for human exposure and biomagnification of priority environmental contaminants. In particular, more objective studies focused on the variability factors behind contamination levels, and subsequent human exposure, are necessary to support the necessity for more restricted legislation worldwide. PMID:25700249

  19. Synthesis, structural and flammability studies of novel phosphonates triazine derivative as economic flame retardant for cotton

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Organophosphorous flame retardants have been known to be more effective when used in conjunction with nitrogen-containing systems. Their mixture produces incombustible non-toxic gases which can dilute the concentration of the oxygen near the flame, and the charred layers become protective barriers t...

  20. Development of the phosphorus and nitrogen containing flame retardant for value added cotton product

    Technology Transfer Automated Retrieval System (TEKTRAN)

    It is our desire to develop new crosslinking agents for cotton textiles that afford useful flame protection regardless of fabric construction. Herein we present the synthesis and the application of the triazine and piperazine derivatives as flame retardant on cotton. Novel phosphorus-nitrogen contai...

  1. Piperazine-phosphonate derivatives: their flame retardant and thermal degradation properties on cotton fibers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    It has been known that phosphorus-nitrogen system shows greater flame resistance in cotton textiles at a lower level than phosphorus used alone. This research aims to compare the effectiveness of Tetraethyl piperazine-1,4-diyldiphosphonate (TEPP) as a flame retardant (FR) for cotton fabric to a prev...

  2. Method for producing flame retardant porous products and products produced thereby

    DOEpatents

    Salyer, Ival O.

    1998-08-04

    A method for fire retarding porous products used for thermal energy storage and products produced thereby is provided. The method includes treating the surface of the phase change material-containing porous products with a urea fire-retarding agent. Upon exposure to a flame, the urea forms an adduct with the phase change material which will not sustain combustion (is self-extinguishing) in air. No halogens or metal oxides are contained in the fire retardant, so no potentially noxious halide smoke or fumes are emitted if the product is continuously exposed to a flame.

  3. Method for Producing Flame Retardant Porous Products and Products Produced Thereby

    DOEpatents

    Salyer, Ival O.

    1998-08-04

    A method for fire retarding porous products used for thermal energy storage and products produced thereby is provided. The method includes treating the surface of the phase change material-containing porous products with a urea fire-retarding agent. Upon exposure to a flame, the urea forms an adduct with the phase change material which will not sustain combustion (is self-extinguishing) in air. No halogens or metal oxides are contained in the fire retardant, so no potentially noxious halide smoke or fumes are emitted if the product is continuously exposed to a flame.

  4. Method for producing flame retardant porous products and products produced thereby

    DOEpatents

    Salyer, I.O.

    1998-08-04

    A method for fire retarding porous products used for thermal energy storage and products produced thereby is provided. The method includes treating the surface of the phase change material-containing porous products with a urea fire-retarding agent. Upon exposure to a flame, the urea forms an adduct with the phase change material which will not sustain combustion (is self-extinguishing) in air. No halogens or metal oxides are contained in the fire retardant, so no potentially noxious halide smoke or fumes are emitted if the product is continuously exposed to a flame. 1 fig.

  5. Flame retardation of cellulose-rich fabrics via a simplified layer-by-layer assembly.

    PubMed

    Yang, Jun-Chi; Liao, Wang; Deng, Shi-Bi; Cao, Zhi-Jie; Wang, Yu-Zhong

    2016-10-20

    Due to the high cellulose content of cotton (88.0-96.5%), the flame retardation of cotton fabrics can be achieved via an approach for the flame retardation of cellulose. In this work, a facile water-based flame retardant coating was deposited on cotton fabrics by a 'simplified' layer-by-layer (LbL) assembly. The novel coating solution was based on a mild reaction between ammonium polyphosphate (APP) and branched polyethyleneimine (BPEI), and the reaction mechanism was studied. TGA results showed that the char residues of coated fabrics were remarkably increased. The fabric with only 5wt% coating showed self-extinguishing in the horizontal flame test, and the peak heat release rate (pHRR) in cone calorimeter test decreased by 51%. Furthermore, this coating overcame a general drawback of flame-retardant LbL assembly which was easily washed away. Therefore, the simplified LbL method provides a fast, low-cost, eco-friendly and wash-durable flame-retardant finishing for the cellulose-rich cotton fabrics. PMID:27474586

  6. Human health risk associated with brominated flame-retardants (BFRs).

    PubMed

    Lyche, Jan L; Rosseland, Carola; Berge, Gunnar; Polder, Anuschka

    2015-01-01

    The purposes of this review are to assess the human exposure and human and experimental evidence for adverse effects of brominated flame-retardants (BFRs) with specific focus on intake from seafood. The leakage of BFRs from consumer products leads to exposure of humans from fetal life to adulthood. Fish and fish products contain the highest levels of BFRs and dominate the dietary intake of frequent fish eaters in Europe, while meat, followed by seafood and dairy products accounted for the highest US dietary intake. House dust is also reported as an important source of exposure for children as well as adults. The levels of BFRs in the general North American populations are higher than those in Europe and Japan and the highest levels are detected in infants and toddlers. The daily intake via breast milk exceeds the RfD in 10% of US infants. BFRs including PBDEs, HBCDs and TBBP-A have induced endocrine-, reproductive- and behavior effects in laboratory animals. Furthermore, recent human epidemiological data demonstrated association between exposure to BFRs and similar adverse effects as observed in animal studies. Fish including farmed fish and crude fish oil for human consumption may contain substantial levels of BFRs and infants and toddlers consuming these products on a daily basis may exceed the tolerable daily intake suggesting that fish and fish oil alone represent a risk to human health. This intake comes in addition to exposure from other sources (breast milk, other food, house dust). Because potential harmful concentrations of BFRs and other toxicants occur in fish and fish products, research on a wider range of products is warranted, to assess health hazard related to the contamination of fish and fish products for human consumption. PMID:25454234

  7. Brominated flame retardants and dechloranes in eels from German Rivers.

    PubMed

    Sühring, Roxana; Möller, Axel; Freese, Marko; Pohlmann, Jan-Dag; Wolschke, Hendrik; Sturm, Renate; Xie, Zhiyong; Hanel, Reinhold; Ebinghaus, Ralf

    2013-01-01

    The levels of PBDEs, alternate BFRs and dechloranes in European Eel (Anguilla anguilla) samples (elvers, yellow and silver eels) were investigated to compare the contamination of eels from the rivers Elbe and Rhine and to estimate the BFR contamination throughout the eel's life cycle. PBDEs were the dominating flame retardants (FRs) in muscle tissues of yellow and silver eels, while the alternate BFR 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and the Dechlorane 602 were the dominating FRs in elvers (juvenile eels). Concentrations of FRs in silver eels from river Rhine were generally higher than concentrations in other eels analysed with up to 46 ng g(-1) wet weight (ww) ∑PBDEs. The concentrations in yellow and silver eels from river Elbe were similar with an average of 9.0±5.1 ng g(-1)ww and 8.1±3.7 ng g(-1)ww respectively. PBDE concentrations in elvers were comparably low (0.02 (BDE-100) to 0.1 (BDE-183) ng g(-1)ww), which lead to the conclusion that these contaminants were mostly ingested within the rivers. Among the alternate BFRs and dechloranes, DPTE as well as the Dechlorane 602 and Dechlorane Plus (DP) were found in all life cycle stages and rivers with concentrations between 0.01 ng g(-1)ww and 0.7 ng g(-1)ww. Dechlorane 603 could only be detected in silver eels from river Rhine. Pentabromoethylbenzene (PBEB) was only found in yellow and silver eels and bis(2-ethylhexyl)tetrabromophthalate (BEHTBP) could only be detected in elvers. These are the first reports of Dec-602 and 603 in aquatic organisms from Europe. The results of this study show the lasting relevance of PBDEs as contaminants in rivers and river-dwelling species but also the growing relevance of emerging contaminants such as alternate BFRs and dechloranes. PMID:22985592

  8. Brominated flame retardants in offices in Michigan, USA.

    PubMed

    Batterman, Stuart; Godwin, Christopher; Chernyak, Sergei; Jia, Chunrong; Charles, Simone

    2010-08-01

    Brominated flame retardants (BFRs) are now ubiquitous contaminants with large reservoirs and high concentrations in buildings. Most of the information documenting BFR levels has been obtained in residences, and other environments that can lead to exposure have received relatively little attention, including offices that contain numerous BFR sources and where individuals spend considerable time. The aim of this study is to characterize BFR concentrations, potential emission sources, and migration pathways in office environments. We measure BFR levels in floor dust, indoor air, ventilation filter dust, and carpets in ten commercial and institutional buildings in Michigan, U.S.A. The median concentration of total BDEs in settled dust was 8754 ng g(-1), at the upper range of levels previously reported. Especially elevated levels were found in offices in buildings that contained known or likely BFR sources, e.g., computer servers. A trends analysis in a newly constructed building showed remarkable increases in concentrations of BFRs in settled dust and indoor air, and apparent steady-state levels were reached 5 to 8 months after building completion, a particularly striking finding given that the building was constructed and furnished several years after the voluntary phase-out of the penta- and octa-mixtures. Airborne particulate matter collected in a building's HVAC system filters contained PBDEs, including BDE-209, at levels exceeding the concentration of floor dust. In conjunction with estimates of building air flow rates, filter efficiency and other parameters, mass balance calculations for this building were used to estimate the emission rates and reservoirs of PBDEs. The widespread distribution of BFRs found in offices in both new and old buildings suggests the significance of workplace exposures, the need for controls to minimize human exposure, intra-building migration, and environmental releases of these chemicals, and the need for monitoring in new buildings

  9. Trends in the levels of halogenated flame retardants in the Great Lakes atmosphere over the period 2005-2013.

    PubMed

    Liu, Liang-Ying; Salamova, Amina; Venier, Marta; Hites, Ronald A

    2016-01-01

    Air (vapor and particle phase) samples were collected every 12days at five sites near the North American Great Lakes from 1 January 2005 to 31 December 2013 as a part of the Integrated Atmospheric Deposition Network (IADN). The concentrations of 35 polybrominated diphenyl ethers (PBDEs) and eight other halogenated flame retardants were measured in each of the ~1,300 samples. The levels of almost all of these flame retardants, except for pentabromoethylbenzene (PBEB), hexabromobenzene (HBB), and Dechlorane Plus (DP), were significantly higher in Chicago, Cleveland, and Sturgeon Point. The concentrations of PBEB and HBB were relatively high at Eagle Harbor and Sturgeon Point, respectively, and the concentrations of DP were relatively high at Cleveland and Sturgeon Point, the two sites closest to this compound's production site. The data were analyzed using a multiple linear regression model to determine significant temporal trends in these atmospheric concentrations. The concentrations of PBDEs were decreasing at the urban sites, Chicago and Cleveland, but were generally unchanging at the remote sites, Sleeping Bear Dunes and Eagle Harbor. The concentrations of PBEB were decreasing at almost all sites except for Eagle Harbor, where the highest PBEB levels were observed. HBB concentrations were decreasing at all sites except for Sturgeon Point, where HBB levels were the highest. DP concentrations were increasing with doubling times of 3-9years at all sites except those closest to its source (Cleveland and Sturgeon Point). The levels of 1,2-bis(2,4,6-tribromophenoxy)ethane (TBE) were unchanging at the urban sites, Chicago and Cleveland, but decreasing at the suburban and remote sites, Sturgeon Point and Eagle Harbor. The atmospheric concentrations of 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB) and bis(2-ethylhexyl)-tetrabromophthalate (BEHTBP) were increasing at almost every site with doubling times of 3-6years. PMID:27160856

  10. Quantification of tetrabromo benzoic acid and tetrabromo phthalic acid in rats exposed to the flame retardant Uniplex FPR-45.

    PubMed

    Silva, Manori J; Hilton, Donald; Furr, Johnathan; Gray, L Earl; Preau, James L; Calafat, Antonia M; Ye, Xiaoyun

    2016-03-01

    The first withdrawal of certain polybrominated diphenyl ethers flame retardants from the US market occurred in 2004. Since then, use of brominated non-PBDE compounds such as bis(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (BEH-TEBP) and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB) in commercial formulations has increased. Assessing human exposure to these chemicals requires identifying metabolites that can potentially serve as their biomarkers of exposure. We administered by gavage a dose of 500 mg/Kg bw of Uniplex FRP-45 (>95 % BEH-TEBP) to nine adult female Sprague-Dawley rats. Using authentic standards and mass spectrometry, we positively identified and quantified 2,3,4,5-tetrabromo benzoic acid (TBBA) and 2,3,4,5-tetrabromo phthalic acid (TBPA) in 24-h urine samples collected 1 day after dosing the rats and in serum at necropsy, 2 days post-exposure. Interestingly, TBBA and TBPA concentrations correlated well (R (2) = 0.92). The levels of TBBA, a known metabolite of EH-TBB, were much higher than the levels of TBPA both in urine and serum. Because Uniplex FRP-45 was technical grade and EH-TBB was present in the formulation, TBBA likely resulted from the metabolism of EH-TBB. Taken together, our data suggest that TBBA and TBPA may serve as biomarkers of exposure to non-PBDE brominated flame retardant mixtures. Additional research can provide useful information to better understand the composition and in vivo toxicokinetics of these commercial mixtures. PMID:25804200

  11. Piloted Ignition to Flaming in Smoldering Fire-Retarded Polyurethane Foam

    NASA Technical Reports Server (NTRS)

    Putzeys, O.; Fernandez-Pello, A. C.; Urban, D. L.

    2007-01-01

    Experimental results are presented on the piloted transition from smoldering to flaming in the fire-retarded polyurethane foam Pyrell . The samples are small rectangular blocks with a square cross section, vertically placed in the wall of a vertical wind tunnel. Three of the vertical sample sides are insulated and the fourth side is exposed to an upward oxidizer flow of variable oxygen concentration and to a variable radiant heat flux. The gases emitted from the smoldering reaction pass upwards through a pilot, which consists of a coiled resistance heating wire. In order to compensate for the solid-phase and gas-phase effects of the fire retardants on the piloted transition from smoldering to flaming in Pyrell, it was necessary to assist the process by increasing the power supplied to the smolder igniter and the pilot (compared to that used for non-fire retarded foam). The experiments indicate that the piloted transition from smoldering to flaming occurs when the gaseous mixture at the pilot passes the lean flammability limit. It was found that increasing the oxygen concentration or the external heat flux increases the likelihood of a piloted transition from smoldering to flaming, and generally decreases the time delay to transition. The piloted transition to flaming is observed in oxygen concentrations of 23% and above in both low-density and high-density Pyrell. Comparisons with previous experiments show that the piloted transition from smoldering to flaming is possible under a wider range of external conditions (i.e. lower oxygen concentration) than the spontaneous transition from smoldering to flaming. The results show that the fire retardants in Pyrell are very effective in preventing the piloted transition to flaming in normal air, but Pyrell is susceptible to smoldering and the piloted transition to flaming in oxygen-enriched environments. Therefore, precautions should be taken in the design of applications of Pyrell in oxygen-enriched environments to reduce

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

    PubMed

    McKinney, Melissa A; Cesh, Lillian S; Elliott, John E; Williams, Tony D; Garcelon, David K; Letcher, Robert J

    2006-10-15

    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. PMID:17120553

  13. Urinary biomarkers of flame retardant exposure among collegiate U.S. gymnasts.

    PubMed

    Carignan, Courtney C; Fang, Mingliang; Stapleton, Heather M; Heiger-Bernays, Wendy; McClean, Michael D; Webster, Thomas F

    2016-09-01

    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. PMID:27395335

  14. An efficient mono-component polymeric intumescent flame retardant for polypropylene: preparation and application.

    PubMed

    Shao, Zhu-Bao; Deng, Cong; Tan, Yi; Chen, Ming-Jun; Chen, Li; Wang, Yu-Zhong

    2014-05-28

    We found in our previous study that ethylenediamine- or ethanolamine-modified ammonium polyphosphates could be used alone as an intumescent flame retardant for polypropylene (PP), but their flame-retardant efficiency was not very high. In this present work, a novel highly-efficient mono-component polymeric intumescent flame retardant, piperazine-modified ammonium polyphosphate (PA-APP) was prepared. The oxygen index value of PP containing 22 wt % of PA-APP reached 31.2%, which increased by 58.4% compared with that of PP with equal amount of APP, and the vertical burning test (UL-94) could pass V-0 rating. Cone calorimeter (CC) results indicated that PP/PA-APP composite exhibited superior performance compared with PP/APP composite. For PP containing 25 wt % of PA-APP, fire growth rate (FGR) and smoke production rate (SPR) peak were reduced by 86.4% and 78.2%, respectively, compared with PP blended with 25 wt % APP. The relevant flame-retardant mechanism of PA-APP was investigated by Fourier transform infrared spectroscopy etc. The P-N-C structure with the alicyclic amine was formed during the thermal decomposition of piperazine salt (-NH2(+)-O-P-), and the rich P-N-C structure facilitated the formation of stable char layer at the later stage, consequently improving the flame-retardant efficiency of APP. PMID:24742305

  15. Flame retardant finishing of cotton fabric based on synergistic compounds containing boron and nitrogen.

    PubMed

    Xie, Kongliang; Gao, Aiqin; Zhang, Yongsheng

    2013-10-15

    Boric acid and compound containing nitrogen, 2,4,6-tri[(2-hydroxy-3-trimethyl-ammonium)propyl]-1,3,5-triazine chloride (Tri-HTAC) were used to finish cotton fabric. The flame retardant properties of the finished cotton fabrics and the synergetic effects of boron and nitrogen elements were investigated and evaluated by limited oxygen index (LOI) method. The mechanism of cross-linking reaction among cotton fiber, Tri-HTAC, and boric acid was discussed by FTIR and element analysis. The thermal stability and surface morphology of the finished cotton fabrics were investigated by thermogravimetric analysis (TGA) and scanning electron microscope (SEM), respectively. The finishing system of the mixture containing boron and nitrogen showed excellent synergistic flame retardancy for cotton fabric. The cotton fabric finished with mixture system had excellent flame retardancy. The LOI value of the treated cotton fabric increased over 27.5. Tri-HTAC could form covalent bonds with cellulose fiber and boric acid. The flame retardant cotton fabric showed a slight decrease in tensile strength and whiteness. The surface morphology of flame retardant cotton fiber was smooth. PMID:23987402

  16. Synthesis of brominated acenaphthylenes and their flame-retardant effects on ethylene-propylene-diene terpolymer

    SciTech Connect

    Morita, Y.; Hagiwara, M.

    1982-09-01

    Bromoacenaphthylenes and their condensates as flame-retardant reagents were synthesized by bromination of acenaphthylene using ZnCl/sub 2/ - CF/sub 3/COOH or FeCl/sub 3/ as catalysts and subsequent dehydrobromination. The chief components were identified as bromoacenaphthylene monomers when ZnCl/sub 2/ - CF/sub 3/COOH were used, and as their condensates (mostly trimers) in the case of FeCl/sub 3/. Their performance as flame-retardant reagents for ethylene-propylene-diene terpolymer (EPDM) was evaluated by measuring the oxygen index of finished compounds, and flammability by a vertical flammability test based on UL-94-VO. Both the monomers and the condensates demonstrated high flame-retardant effectiveness. The high efficiency was attributed to their excellent dispersity in the base polymer and their characteristic thermal decomposition behavior. In thermal gravimetric analysis (TGA), they decomposed in a very wide range of temperature (ca.200-560/sup 0/C), which covers the decomposition range of EPDM. This was attributed to the existence of bromines of different thermal stabilities in one molecule. This paper is a part of a series of studies to develop new flame retardants which can give high flame retardancy as well as stabilty against ionizing radiation to EPDM.

  17. Aluminum hypophosphite microencapsulated to improve its safety and application to flame retardant polyamide 6.

    PubMed

    Ge, Hua; Tang, Gang; Hu, Wei-Zhao; Wang, Bi-Bo; Pan, Ying; Song, Lei; Hu, Yuan

    2015-08-30

    Aluminum hypophosphite (AHP) is an effective phosphorus-containing flame retardant. But AHP also has fire risk that it will decompose and release phosphine which is spontaneously flammable in air and even can form explosive mixtures with air in extreme cases. In this paper, AHP has been microencapsulated by melamine cyanurate (MCA) to prepare microencapsulated aluminum hypophosphite (MCAHP) with the aim of enhancing the fire safety in the procedure of production, storage and use. Meanwhile, MCA was a nitrogen-containing flame retardant that can work with AHP via the nitrogen-phosphorus synergistic effect to show improved flame-retardant property than other capsule materials. After microencapsulation, MCA presented as a protection layer inhibit the degradation of AHP and postpone the generation of phosphine. Furthermore, the phosphine concentration could be effectively diluted by inert decomposition products of MCA. These nonflammable decomposition products of MCA could separate phosphine from air delay the oxidizing reaction with oxygen and decrease the heat release rate, which imply that the fire safety of AHP has been improved. Furthermore, MCAHP was added into polyamide 6 to prepare flame retardant polyamide 6 composites (FR-PA6) which show good flame retardancy. PMID:25867591

  18. Investigating a novel flame retardant known as V6: measurements in baby products, house dust, and car dust.

    PubMed

    Fang, Mingliang; Webster, Thomas F; Gooden, David; Cooper, Ellen M; McClean, Michael D; Carignan, Courtney; Makey, Colleen; Stapleton, Heather M

    2013-05-01

    With the phase-out of polybrominated diphenyl ether (PBDE) flame retardants, the use of new and alternate flame retardants has been increasing. 2,2-bis(chloromethyl)propane-1,3-diyltetrakis(2-chloroethyl) bisphosphate, known as V6, is a flame retardant applied to polyurethane foam commonly found in furniture and automobile foam. However, to the authors' knowledge, no research has been conducted on V6 levels in the environment. The intention of this study was to measure the concentration of V6 in foam collected from baby products where it was recently detected and measure levels in dust samples collected from homes and automobiles in the Boston, MA area. To accomplish this, a pure V6 commercial standard was purchased from a Chinese manufacturer and purified (>98%). An analytical method to measure V6 in dust samples using liquid chromatography tandem mass spectrometry (LC/MS-MS) was developed. Extraction was conducted using accelerated solvent extraction (ASE) and extracts were purified using an ENVI-Florisil SPE column (500 mg, 3 mL). V6 was measured in foam samples collected from baby products with a concentration ranging from 24,500,000 to 59,500,000 ng/g of foam (n = 12, average ± sd: 46,500,000 ± 12,000,000 ng/g; i.e., on average, 4.6% of the foam mass was V6). V6 was also detected in 19 of 20 car dust samples and 14 of 20 house dust samples analyzed. The concentration of V6 in the house dust ranged from <5 ng/g to 1110 ng/g with a median of 12.5 ng/g, and <5 ng/g to 6160 ng/g in the car dust with a median of 103.0 ng/g. Concentrations in car dust were significantly higher than in the house dust potentially indicating higher use of V6 in automobiles compared to products found in the home. Furthermore, tris (2-chloroethyl) phosphate (TCEP), a known carcinogen, was found in the V6 commercial mixture (14% by weight) as an impurity and was consistently detected with V6 in the foam samples analyzed. A significant correlation was also observed between V6 and TCEP in

  19. Investigating A Novel Flame Retardant Known as V6: Measurements in Baby Products, House Dust and Car Dust

    PubMed Central

    Fang, Mingliang; Webster, Thomas F.; Gooden, David; Cooper, Ellen M.; McClean, Michael D.; Carignan, Courtney; Makey, Colleen; Stapleton, Heather M.

    2013-01-01

    With the phase-out of polybrominated diphenyl ether (PBDE) flame retardants, the use of new and alternate flame retardants has been increasing. 2,2-bis(chloromethyl)propane-1,3-diyltetrakis(2-chloroethyl) bisphosphate, known as V6, is a flame retardant applied to polyurethane foam commonly found in furniture and automobile foam. However, to the authors’ knowledge, no research has been conducted on V6 levels in the environment. The intention of this study was to measure the concentration of V6 in foam collected from baby products where it was recently detected, and measure levels in dust samples collected from homes and automobiles in the Boston, MA area. To accomplish this a pure V6 commercial standard was purchased from a Chinese manufacturer and purified (> 98%). An analytical method to measure V6 in dust samples using liquid chromatography tandem mass spectrometry (LC/MS-MS) was developed. Extraction was conducted using Accelerated Solvent Extraction (ASE) and extracts were purified using an ENVI-Florisil SPE column (500 mg, 3mL). V6 was measured in foam samples collected from baby products with a concentration ranging from 24,500,000 to 59,500,000 ng/g of foam (n = 12, average ± sd: 46,500,000 ± 12,000,000 ng/g; i.e., on average, 4.6 % of the foam mass was V6). V6 was also detected in 19 of 20 car dust samples and 14 of 20 house dust samples analyzed. The concentration of V6 in the house dust ranged from < 5 ng/g to 1,110 ng/g with a median of 12.5 ng/g, and < 5 ng/g to 6,160 ng/g in the car dust with a median of 103.0 ng/g. Concentrations in car dust were significantly higher than the house dust, potentially indicating higher use of V6 in automobiles compared to products found in the home. Furthermore, tris (2-chloroethyl) phosphate (TCEP), a known carcinogen, was found in the V6 commercial mixture (14% by weight) as an impurity and was consistently detected with V6 in the foam samples analyzed. A significant correlation was also observed between V6 and

  20. Atmospheric deposition of chlorinated organophosphate flame retardants (OFR) onto soils

    NASA Astrophysics Data System (ADS)

    Mihajlović, Ivana; Fries, Elke

    2012-09-01

    This study highlights the influence of dry and wet deposition on concentrations of chlorinated organophosphate flame retardants (OFR) in soil. Soil samples were collected in 2010/11 during a period of snow falling to snow melting, a period of rainfall and a dry period. Snow and rainwater samples were also collected from the soil sampling site. Tris(2-chloroethyl)phosphate (TCEP), tris(2-chloroisopropyl)phosphate (TCPP) and tris(1,3-dichloro-2-propyl)phosphate (TDCP) were analysed in soil samples using a combination of Twisselmann extraction and solid-phase microextraction (SPME), followed by gas chromatography-mass spectrometry (GC-MS). SPME/GC-MS was applied to analyse TCEP, TCPP and TDCP in aqueous samples. Concentrations of TCEP were between 236 and 353 ng L-1 in snow and 78 and 234 ng L-1 in rain. TCPP concentrations were between 226 and 284 ng L-1 in snow and 371 and 385 ng L-1 in rain. In soil samples, concentrations ranged from 5.07 to 23.48 ng g-1 dry weight (dwt) for TCEP and 5.66 to 19.82 ng g-1 dwt for TCPP. Concentrations of TDCP in rainwater and snow samples were rather low (46 and 100 ng L-1, respectively); concentrations of TDCP were below the limit of detection in soil samples. Snow melting caused enhanced soil concentrations of TCEP and TCPP, but greater effect of snow melting was observed for TCEP than for TCPP soil concentrations. No significant correlation between precipitation amounts and soil concentrations was observed. The influence of wet deposition on soil contents of TCEP and TCPP may be covered by volatilisation or by the mobility of both compounds in soil and their transport to deeper soil zones with seepage water. Snow was found to be a more efficient scavenger and transporter of chlorinated OFR into soil than rainwater. During dry weather, the soil concentrations of both compounds seemed to be driven mainly by air concentrations, which are determined by source emission strengths and photochemical degradation in the atmosphere. Values

  1. Lithium-Ion Electrolytes Containing Flame Retardant Additives for Increased Safety Characteristics

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C. (Inventor); Smith, Kiah A. (Inventor); Bugga, Ratnakumar V. (Inventor); Prakash, Surya G. (Inventor); Krause, Frederick Charles (Inventor)

    2014-01-01

    The invention discloses various embodiments of Li-ion electrolytes containing flame retardant additives that have delivered good performance over a wide temperature range, good cycle life characteristics, and improved safety characteristics, namely, reduced flammability. In one embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a fluorinated co-solvent, a flame retardant additive, and a lithium salt. In another embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a flame retardant additive, a solid electrolyte interface (SEI) film forming agent, and a lithium salt.

  2. Irradiation crosslinking and halogen-free flame retardation of EVA using hydrotalcite and red phosphorus

    NASA Astrophysics Data System (ADS)

    Jiao, Chuanmei; Wang, Zhengzhou; Chen, Xilei; Yu, Benyi; Hu, Yuan

    2006-05-01

    Halogen-free flame retarded ethylene vinyl acetate copolymer (EVA) composites using Mg-Al-CO 3 hydrotalcite (MALDH) and microcapsulated red phosphorus (MRP) have been prepared in a melt process. The flame retardation of the composites has been studied by the limited oxygen index (LOI) and UL-94 methods, and the thermal decomposition by the thermogravimetric analysis (TGA). The changes of their properties of the composites before and after the Gamma irradiation are compared. The synergistic effect in the flame retardation between MALDH and MRP in EVA has been found. The EVA/MALDH/MRP composites after the irradiation crosslinking result in a great increase in the Vicat softening point. The LOI value, the mechanical properties and thermal stability are also improved for the composites irradiated by a suitable irradiation dose.

  3. Accumulation and DNA damage in fathead minnows (Pimephales promelas) exposed to 2 brominated flame-retardant mixtures, Firemaster 550 and Firemaster BZ-54.

    PubMed

    Bearr, Jonathan S; Stapleton, Heather M; Mitchelmore, Carys L

    2010-03-01

    Firemaster 550 and Firemaster BZ-54 are two brominated formulations that are in use as replacements for polybrominated diphenyl ether (PBDE) flame retardants. Two major components of these mixtures are 2,3,4,5-tetrabromo-ethylhexylbenzoate (TBB) and 2,3,4,5-tetrabromo-bis(2-ethylhexyl) phthalate (TBPH). Both have been measured in environmental matrices; however, scant toxicological information exists. The present study aimed to determine if these brominated flame-retardant formulations are bioavailable and adversely affect DNA integrity in fish. Fathead minnows (Pimephales promelas) were orally exposed to either FM 550, FM BZ54, or the nonbrominated form of TBPH, di-(2-ethylhexyl) phthalate (DEHP) for 56 d and depurated (e.g., fed clean food) for 22 d. At several time points, liver and blood cells were collected and assessed for DNA damage. Homogenized fish tissues were extracted and analyzed on day 0 and day 56 to determine the residue of TBB and TBPH and the appearance of any metabolites using gas chromatography-electron-capture negative ion mass spectrometry (GC/ECNI-MS). Significant increases (p < 0.05) in DNA strand breaks from liver cells (but not blood cells) were observed during the exposure period compared with controls, although during depuration these levels returned to control. Both parent compounds, TBB and TBPH, were detected in tissues at approximately 1% of daily dosage along with brominated metabolites. The present study provides evidence for accumulation, metabolism, and genotoxicity of these new formulation flame retardants in fish and highlights the potential adverse effects of TBB- and TBPH-formulated fire retardants to aquatic species. PMID:20821500

  4. Organophosphate flame retardants in household dust before and after introduction of new furniture.

    PubMed

    Keimowitz, A R; Strunsky, N; Wovkulich, K

    2016-04-01

    Flame retardant compounds originating from household items collect in household dust, a reasonable proxy for human exposure. Contributions of specific items or behaviors to dust are difficult to separate. This study examined standardized college housing before and after the introduction of new, flame retardant couches in order to explore any effect that changing upholstered furniture may have on flame retardant concentrations in dust. Two contradictory hypotheses were posited: (1) that new furniture might increase flame retardant releases immediately after introduction due to initial off-gassing of new materials or (2) that older furniture would release more flame retardants due to mechanical breakdown of polyurethane foam. This study was designed to determine which of these processes dominated. Prior to the introduction of new furniture, TDCIPP was detected in 12/20 samples at a median concentration of 22 μg/g and TCEP was detected in 1/20 samples at a concentration of 16 μg/g. TDCIPP and TCEP were not detected in any samples (N = 29) after the introduction of new couches. TPHP was detected both before (in 11/20 samples) and after (in 5/29 samples) introduction of new couches; the median concentrations before and after were 63 ± 49 and 16 ± 11 μg/g (standard deviation shown). Introduced couches contained TDCIPP (and not TPHP) at ∼1.25% (w/w). These data support the second hypothesis and indicate that removal of older furniture decreases TDCIPP and TCEP concentrations in dust and may potentially reduce total flame retardant concentrations in dust, at least immediately after introduction of the new furniture. PMID:26841288

  5. Formation of polybrominated dibenzofurans from polybrominated biphenyls.

    PubMed

    Altarawneh, Mohammednoor; Dlugogorski, Bogdan Z

    2015-01-01

    Decades after phasing out their production and use, especially in the formulations of brominated flame retardants (BFRs), polybrominated biphenyls (PBBs) still pose serious environmental and health problems. The oxidation of PBB has been hypothesised as a pathway for the formation of the notorious polybrominated dibenzofurans (PBDFs) and their dispersion in the environment. However, the exact reaction corridor remains misunderstood, with the existing mechanisms predicting the reaction to proceed via a high energy process that involves the breakage of C-C linkage (∼118.0 kcal mol(-1)) and the subsequent formation of bromophenols molecules, where the latter are supposed to act as precursors for the formation of PBDFs (∼40.0-60.0 kcal mol(-1)). Herein, we show that PBBs produce PBDFs in a facile mechanism through a series of highly exothermic reactions (i.e., overall barriers reside 8.2-10.0 kcal mol(-1) below the entrance channel). Whilst the fate of the ROO-type intermediates in oxidation of all aromatics is to emit CO or CO2, PBDFs constitute the dominant products from the oxidation of PBBs. Initially formed R-OO adduct evolves in a very exoergic mechanism to yield PBDFs. In view of the facile oxidative transformation of PBBs into PBDFs, we conclude that, it is unsafe to dispose BFRs in oxidation processes, as this practice generates high yields of toxic PBDFs. PMID:25303667

  6. Legacy and current-use brominated flame retardants in the Barn Owl.

    PubMed

    Eulaers, Igor; Jaspers, Veerle L B; Pinxten, Rianne; Covaci, Adrian; Eens, Marcel

    2014-02-15

    The present study investigated the current-use brominated flame retardants (BFRs) tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD), simultaneously with legacy polybrominated diphenyl ethers (PBDEs), in Barn Owls (Tyto alba) collected from two regions with a contrasting degree of urbanisation and vicinity to point sources (Flanders in Belgium versus Normandy in France). Both tissues (muscle, liver, adipose and preen gland) and feathers (primary, tail and body feathers) showed elevated HBCD concentrations in Flanders, close to Europe's sole HBCD production plant in the Netherlands, and identified Normandy as a historical source region for PBDEs. In sharp contrast, the reactive BFR TBBPA bioaccumulated poorly (2.3%) in tissue samples, but was present in 96% of all body feather samples (0.36-7.07ngg(-1)dw), equally in both regions. PBDE concentrations in tissues (7.46-903 ng g(-1)lw) were considerably lower in the investigated Flemish Barn Owls, collected in 2008/2009, compared to specimens collected in 2003/2004 (46-11,000 ng g(-1)lw), possibly suggesting the effectiveness of the 2004 European ban of Penta- and Octa-BDE mixtures. Feathers showed a similar trend and additionally exhibited HBCD concentrations (0.02-333 ng g(-1)dw) surpassing those of PBDEs (0.50-10.4 ng g(-1)dw). While body feathers were a reliable matrix to predict both internal PBDE (0.21 ≤ R(2)≤ 0.67) and HBCD body burdens (0.20 ≤ R(2) ≤ 0.37), the suitability of primary and tail feathers appeared to be confounded by external contamination and moult. In conclusion, the present study clearly showed that the reactive versus additive use of BFRs results in contrasting exposure scenarios in a species higher up the food chain, and therefore may have profound implications for environmental health. In addition, the presented results extend the promising use of feathers as a non-destructive sampling strategy for current-use BFRs, and show that birds of prey are valid early

  7. Low level exposure to the flame retardant BDE-209 reduces thyroid hormone levels and disrupts thyroid signaling in fathead minnows

    PubMed Central

    Noyes, Pamela D.; Lema, Sean C.; Macaulay, Laura J.; Douglas, Nora K.; Stapleton, Heather M.

    2013-01-01

    Polybrominated diphenyl ether (PBDE) flame retardants have been shown to disrupt thyroid hormone regulation, neurodevelopment, and reproduction in some animals. However, effects of the most heavily used PBDE, decabromodiphenyl ether (BDE-209), on thyroid functioning remain unclear. This study examined low-dose effects of BDE-209 on thyroid hormone levels and signaling in fathead minnows. Adult males received dietary exposures of BDE-209 at a low dose (~3 ng/g bw-day) and high dose (~300 ng/g bw-day) for 28 days followed by a 14-day depuration to evaluate recovery. Compared to controls, fish exposed to the low dose for 28 days experienced a 53% and 46% decline in circulating total thyroxine (TT4) and 3,5,3'-triiodothyronine (TT3), respectively, while TT4 and TT3 deficits at the high dose were 59% and 62%. Brain deiodinase activity (T4-ORD) was reduced by ~65% at both doses. BDE-209 elevated the relative mRNA expression of genes encoding deiodinases, nuclear thyroid receptors, and membrane transporters in the brain and liver in patterns that varied with time and dose, likely in compensation to hypothyroidism. Declines in the gonadal-somatic index (GSI) and increased mortality were also measured. Effects at the low dose were consistent with the high dose, suggesting non-linear relationships between BDE-209 exposures and thyroid dysfunction. PMID:23899252

  8. Spatial and temporal trends in brominated flame retardants in seabirds from the Pacific coast of Canada.

    PubMed

    Miller, Aroha; Elliott, John E; Elliott, Kyle H; Guigueno, Mélanie F; Wilson, Laurie K; Lee, Sandi; Idrissi, Abde

    2014-12-01

    Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDD) are bioaccumulative flame retardants. PBDEs increased in many ecosystems during the late 20th century, but recently have declined in some environments. To examine trends in the northern Pacific, we analysed PBDEs, HBCDD and carbon and nitrogen stable isotopes (δ13C and δ15N) to account for dietary effects in archived eggs of three seabird species from British Columbia, Canada, 1990-2011 (rhinoceros auklets, Cerorhinca monocerata; Leach's storm-petrels, Oceanodroma leucorhoa; ancient murrelets, Synthliboramphus antiquus, 2009 only). PBDEs increased until approximately 2000 and then decreased, while HBCDD increased exponentially throughout the examined period. No significant changes in dietary tracers were observed. HBCDD and ΣPBDE levels varied among species; ΣPBDE also varied among sites. Temporal changes in contaminant concentrations are unlikely to have been caused by dietary changes, and likely reflect the build-up followed by decreases associated with voluntary phase-outs and regulations implemented in North America to control PBDEs. PMID:25194271

  9. Three decades (1983-2010) of contaminant trends in East Greenland polar bears (Ursus maritimus). Part 2: brominated flame retardants.

    PubMed

    Dietz, Rune; Rigét, Frank F; Sonne, Christian; Born, Erik W; Bechshøft, Thea; McKinney, Melissa A; Drimmie, Robert J; Muir, Derek C G; Letcher, Robert J

    2013-09-01

    Brominated flame retardants were determined in adipose tissues from 294 polar bears (Ursus maritimus) sampled in East Greenland in 23 of the 28years between 1983 and 2010. Significant linear increases were found for sum polybrominated diphenyl ether (ΣPBDE), BDE100, BDE153, and hexabromocyclododecane (HBCD). Average increases of 5.0% per year (range: 2.9-7.6%/year) were found for the subadult polar bears. BDE47 and BDE99 concentrations did not show a significant linear trend over time, but rather a significant non-linear trend peaking between 2000 and 2004. The average ΣPBDE concentrations increased 2.3 fold from 25.0ng/g lw (95% C.I.: 15.3-34.7ng/g lw) in 1983-1986 to 58.5ng/g lw (95% C.I.: 43.6-73.4ng/g lw) in 2006-2010. Similar but fewer statistically significant trends were found for adult females and adult males likely due to smaller sample size and years. Analyses of δ(15)N and δ(13)C stable isotopes in hair revealed no clear linear temporal trends in trophic level or carbon source, respectively, and non-linear trends differed among sex and age groups. These increasing concentrations of organobromine contaminants contribute to complex organohalogen mixture, already causing health effects to the East Greenland polar bears. PMID:23137556

  10. Occurrences and inventories of heavy metals and brominated flame retardants in wastes from printed circuit board production.

    PubMed

    Zhou, Xiaoyu; Guo, Jie; Zhang, Wei; Zhou, Peng; Deng, Jingjing; Lin, Kuangfei

    2014-09-01

    Pollutants including heavy metals and brominated flame retardant were detected in 10 types of production wastes from a typical printed circuit board manufacturing plant, and their inventories were estimated. Rinsing water from etching process had the highest concentrations of copper (665.51 mg/L), lead (1.02 mg/L), nickel (3.60 mg/L), chromium (0.97 mg/L), and tin (1.79 mg/L). Powdered solid waste (SW) from the cut lamination process contained the highest tetrabromobisphenol-A (TBBPA) levels (49.86 mg/kg). Polybrominated diphenyl ethers (PBDEs) were absent in this plant, in agreement with the international regulations of PBDE phase out. The pollutant inventories in the wastes exhibited in the order of copper > > zinc > tin ≈ nickel > lead > chromium > > TBBPA. The potential environmental impact of pollutants in SW during production and disposal were further investigated. A high partitioning of pollutant concentration between the total suspended particle and SW (-0.10 < log K TS < 2.12) was observed for most pollutants, indicating the emission pathway from SW to the airborne atmosphere in the workshop. Although SW met the toxicity characteristic leaching procedure, drilling powder with the smallest particle diameter still showed high leachabilities of lead and tin which may lead to a negative environmental impact during disposal. PMID:24777328

  11. Comparing human exposure to emerging and legacy flame retardants from the indoor environment and diet with concentrations measured in serum.

    PubMed

    Cequier, Enrique; Marcé, Rosa Maria; Becher, Georg; Thomsen, Cathrine

    2015-01-01

    This study investigates associations between serum concentrations of emerging and legacy halogenated flame retardants (HFRs) in 46 Norwegian women and measured indoor air and dust concentrations of the HFRs as well as detailed information on diet and household factors. Hexabromobenzene (median 0.03ng/g lipid) and Dechlorane 602 (median 0.18ng/g lipid) were detected in about 50% of the samples and Dechlorane Plus syn (median 0.45ng/g lipid) and anti (median 0.85ng/g lipid) in more than 78%. The most abundant polybrominated diphenyl ethers were 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153; median 0.82ng/g lipid) and 2,2',4,4'-tetrabromodiphenyl ether (BDE-47; median 0.49ng/g lipid) detected in more than 70% of the samples. In the bivariate analysis, no consistent associations were observed between the biomonitoring data and measured concentrations in indoor air and dust. On the other hand, consumption of specific food items (mainly lamb/mutton and margarine) correlated significantly with more than two HFR serum concentrations, while this was not the case for household factors (electronic appliances). Only the significant bivariate associations with diet were confirmed by multivariate linear regression analyses, which might indicate a higher contribution from food compared to the indoor environment to the variation of the body burden of these HFRs. PMID:25454220

  12. Brominated flame retardants in mangrove sediments of the Pearl River Estuary, South China: spatial distribution, temporal trend and mass inventory.

    PubMed

    Zhang, Zai-Wang; Sun, Yu-Xin; Sun, Kai-Feng; Xu, Xiang-Rong; Yu, Shen; Zheng, Tian-Ling; Luo, Xiao-Jun; Tian, Yun; Hu, Yong-Xia; Diao, Zeng-Hui; Mai, Bi-Xian

    2015-03-01

    Sediments were collected from three mangrove wetlands in the Pearl River Estuary (PRE) of South China to investigate spatial and temporal distributions of polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE). Concentrations of ΣPBDEs, DBDPE and BTBPE in mangrove sediments of the PRE ranged from 1.25-206, 0.364-34.9, and not detected-0.794 ng g(-1) dry weight, respectively. The highest concentrations of ΣPBDEs, DBDPE and BTBPE were found at the mangrove wetland from Shenzhen, followed by Zhuhai and Guangzhou, showing the dependence on the proximity to urban areas. PBDEs were the predominant brominated flame retardants (BFRs) in mangrove sediments. The concentrations of ΣPBDEs, DBDPE and BTBPE in sediment cores showed an increasing trend from the bottom to top layers, reflecting the increasing usage of these BFRs. The inventories of ΣPBDEs, DBDPE and BTBPE in mangrove sediments were 1962, 245, and 4.10 ng cm(-2), respectively. This is the first study to report the occurrence of DBDPE and BTBPE in mangrove ecosystems. PMID:25482977

  13. Brominated flame retardants (BFRs) in breast milk and associated health risks to nursing infants in Northern Tanzania.

    PubMed

    Müller, M H B; Polder, A; Brynildsrud, O B; Lie, E; Løken, K B; Manyilizu, W B; Mdegela, R H; Mokiti, F; Murtadha, M; Nonga, H E; Skaare, J U; Lyche, J L

    2016-01-01

    The main aim of this study was to assess brominated flame retardants (BFRs) in breast milk in the Northern parts of Tanzania. Ninety-five colostrum samples from healthy, primiparous mothers at Mount Meru Regional Referral Hospital (MMRRH), Arusha Tanzania, were analyzed for polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), hexabromobenzene (HBB), (2,3-dibromopropyl) (2,4,6-tribromophenyl) ether (DPTE), pentabromoethylbenzene (PBEB) and 2,3,4,5,6-pentabromotoluene (PBT). The Ʃ7PBDE (BDE 28, 47, 99, 100, 153, 154, 183) ranged from below level of detection (

  14. Historical contaminants, flame retardants, and halogenated phenolic compounds in peregrine Falcon (Falco peregrinus) nestlings in the Canadian Great Lakes Basin.

    PubMed

    Fernie, Kim J; Letcher, Robert J

    2010-05-01

    Concentrations and spatial patterns of persistent organic (chlorinated) pollutants (POPs), polybrominated diphenyl ether (PBDE), hexabromocyclododecane (HBCD), other flame retardants, and hydroxylated (OH) PBDE and PCB compounds were determined in nestling peregrine falcons across the Canadian Great Lakes Basin. The highest geometric mean plasma POP concentrations (ng/g ww) were sum (Sigma)PCBs (35.16), SigmaPBDEs (15.38), and SigmaOH-PCB (8.77) with the lowest mean levels in nestlings from urban versus remote nests. PBDE congeners derived from PentaBDE and OctaBDE technical mixtures had the highest concentrations, sometimes exceeding 100 ng/g wet weight (ww); BDE-99, -153, -47, -100, and -183 comprised 92.7% of the Sigma(14)PBDE levels. BDE-209 proportions were minimal (<1%). North Shore (Lake Superior) nestlings had the highest Sigma(14)PBDE concentrations, with BDE-99, -153, and -47 dominant. Urban nestlings had higher BDE-99:BDE-153 ratios, higher BDE-183 proportions, and the only detectable HBCD concentrations, suggesting greater and more localized exposure to HBCD and PBDEs derived from OctaBDEs. Spatial patterns reflected differences in diet, local contaminant sources, and/or atmospheric deposition. Metabolism of PCBs and PBDEs likely occurred in these nestlings: OH-PCB metabolites were detected, and 4-OH-CB187 was the most abundant of these metabolites. Low ppb levels of putative OH-PBDE metabolites, dominated by 6'-OH-BDE47, were also detected in the peregrine nestlings. PMID:20384324

  15. Concentrations of "legacy" and novel brominated flame retardants in matched samples of UK kitchen and living room/bedroom dust.

    PubMed

    Kuang, Jiangmeng; Ma, Yuning; Harrad, Stuart

    2016-04-01

    Concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and 5 novel brominated flame retardants (NBFRs) were measured in paired samples of kitchen and living room/bedroom dust sampled in 2015 from 30 UK homes. BDE-209 was most abundant (22-170,000 ng/g), followed by γ-HBCDD (1.7-21,000 ng/g), α-HBCDD (5.2-4,900 ng/g), β-HBCDD (2.3-1,600 ng/g), BDE-99 (2.6-1,440 ng/g), BDE-47 (0.4-940 ng/g), decabromodiphenyl ethane (DBDPE) (nd-680 ng/g) and bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEH-TEBP) (2.7-630 ng/g). The concentrations in kitchens and living rooms/bedrooms are moderate compared with previous studies. Concentrations of BDE-209 in living room/bedroom dust were significantly lower and those of DBDPE significantly higher (p < 0.05) compared to concentrations recorded in UK house dust in 2006 and 2007. This may reflect changes in UK usage of these BFRs. All target BFRs were present at higher concentrations in living rooms/bedrooms than kitchens. With the exception of BDE-28, pentabromoethylbenzene (PBEB) and DBDPE, these differences were significant (p < 0.05). No specific source was found that could account for the higher concentrations in living rooms/bedrooms. PMID:26859606

  16. Tissue distribution of polybrominated diphenyl ethers in male ratsand implications for biomonitoring

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are a class of widely-used flame retardants which have been found to persist, bioaccumulate, and potentially affect development in animals. Exposure to PBDEs can be through both diet and the environment and is generally estimated by measuri...

  17. DEVELOPMENTAL EXPOSURE TO POLYBROMINATED DIPHENYL ETHERS DOES IMPAIRS SYNAPTIC TRANSMISSION AND LTP IN HIPPOCAMPUS.

    EPA Science Inventory

    Polybrominated diphenyl ether (PBDE) flame retardants bioaccumulate in wildlife and in humans and reduce circulating levels of thyroxine (T4). The present work examined hippocampal function in adult offspring of LE rats treated daily by oral gavage with 0, 30 or 100 mg/kg of a ...

  18. CHANGES IN MITOGEN-ACTIVATED PROTEIN KINASE IN CEREBELLAR GRANULE NEURONAL CULTURES BY POLYBROMINATED DIPHENYL ETHERS.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are used as additive flame-retardants and have been detected in human blood, adipose tissue, and breast milk; clarifying the nature of the risks posed is important for clean-up and remediation. Both in vitro and in vivo studies have shown t...

  19. Neurobehavioral Development following Exposure of Male Mice to Polybrominated Diphenyl Ether 47 on Postnatal Day 10

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are commonly used as commercial flame retardants in a variety of products including plastics and textiles. Previous studies in our laboratory and in the literature have shown that exposure to a specific PBDE congener, PBDE 47, during a crit...

  20. Neurochemical Changes Following a Single Dose Polybrominated Diphenyl Ether 47 in Mice

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are commonly used as commercial flame retardants in a variety of products including plastics and textiles. Previous studies in our laboratory, and in the literature, have shown that exposure to a specific PBDE congener (PBDE 47) during a cri...

  1. Tissue distribution of polybrominated diphenyl ethers in male rats and implications for biomonitoring

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Polybrominated diphenyl ethers (PBDEs) are a class of widely-used flame retardants which have been found to persist, bioaccumulate, and potentially affect development in animals. Exposure to PBDEs can be through both diet and the environment and is generally estimated by measuring PBDEs in blood, a...

  2. Distribution of brominated flame retardants and dechloranes between sediments and benthic fish--A comparison of a freshwater and marine habitat.

    PubMed

    Sühring, Roxana; Busch, Friederike; Fricke, Nicolai; Kötke, Danijela; Wolschke, Hendrik; Ebinghaus, Ralf

    2016-01-15

    A total of 53 halogenated flame retardants (HFRs) were analysed in sediments, European eels and dabs from both freshwater and marine sampling stations in the German Bight and the river Elbe. Classic HFRs, such as polybrominated diphenylethers (PBDEs), were the highest concentrated HFRs in eels as well as in most dabs (apart from 1,2,5,6-tetrabromocyclooctane (TBCO)). In sediments, on the other hand, alternate BFRs and especially dechloranes dominated the contamination pattern. Dabs were still found to be statistically representative for the contamination patterns and relative magnitude in sediments from their respective habitats. Contamination patterns in eels seemed to be more driven by the contamination situation in the food chain or historical contamination of their habitat. Unsuspectedly the alternate flame retardant TBCO was found in comparably high concentrations (up to 12 ng g(-1) ww) in dabs from two sampling stations as well as in sediments from these stations (up to 1.2 ng g(-1) dw). It could not be detected in any other analysed fish or sediment samples, indicating a localised contamination source in the area. This study provides information on HFR contamination patterns and behaviour in both marine and freshwater sediments and their potential role as contamination source for benthic fish. PMID:26544886

  3. Distributions and compositions of old and emerging flame retardants in the rhizosphere and non-rhizosphere soil in an e-waste contaminated area of South China.

    PubMed

    Wang, Shaorui; Wang, Yan; Song, Mengke; Luo, Chunling; Li, Jun; Zhang, Gan

    2016-01-01

    We investigated rhizosphere effects on the distributions and compositions of polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), and dechlorane plus (DPs) in rhizosphere soils (RS) and non-rhizosphere soils (NRS) in an e-waste recycling area in South China. The concentrations of PBDEs, NBFRs, and DPs ranged from 13.9 to 351, 11.6 to 70.8, and 0.64 to 8.74 ng g(-1) in RS and 7.56 to 127, 8.98 to 144, and 0.38 to 8.45 ng g(-1) in NRS, respectively. BDE-209 and DBDPE were the dominant congeners of PBDEs and NBFRs, respectively. PBDEs, NBFRs, and DPs were more enriched in RS than NRS in most vegetables species. Further analysis suggested that the differentiation of the rhizosphere effect on halogenated flame retardants (HFRs) was not solely controlled by the octanol-water coefficients. This difference was also reflected by the correlations between total organic carbon (TOC) and PBDEs, NBFRs, or DPs, which indicated that organic carbon was a more pivotal controlling factor for PBDEs and DPs than for NBFRs in soil. We also found significant positive correlations between PBDEs and their replacement products, which indicated a similar emission pattern and environmental behaviour. PMID:26552538

  4. Study of Phosphorous and Nitrogen Containing Economic Flame Retardant Materials and Their Textile Application

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Recently, we have discovered that cyanuric chloride is excellent starting materials for preparing with phosphonates that interact well with cotton to improve flame retardant (FR) performance properties. The mono- or bis-(dimethoxy-hydroxymethyl phosphonyl) cyanurate derivatives have been prepared by...

  5. The influences of piperazine-phosphonates derivatives on flame retardancy and thermal behaviors of cotton cellulose

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In an effort to create the environmentally-friendly flame retardants (FRs) for cotton cellulose, two phosphoramidates derivatives, tetraethyl piperazine-1,4-diyldiphosphonate (PDP) and diethyl 4-methylpiperazin-1-ylphosphoramidate (PAP), have been developed. Both were synthesized in high yield and ...

  6. Surface coating for flame retardant behavior of cotton fabric by layer-by-layer processing

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flame retardant behavior has been prepared by the layer-by layer assemblies of branched polyethylenimine (BPEI), kaolin, urea, diammonium phosphate (dibasic) on cotton fabrics. Three different kinds of cotton fabrics (print cloth, mercerized print cloth, and mercerized twill fabric) were prepared wi...

  7. Development for phosphorus-nitrogen containing flame retardant compound and its textile application

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A novel flame retardant Diethyl 4-methylpiperazin-1-ylphosphoramidate, CN-3 containing phosphorous and nitrogen has been prepared. Its chemical structure was confirmed by nuclear magnetic resonance (1H, 13C, 31P NMR), Fourier transform infrared spectrometry (FTIR), and elemental analysis. Print ...

  8. Toxicokinetics of the Flame Retardant Hexabromocyclododecane Gamma: Effect of Dose, Timing, Route, Repeated Exposure and Metabolism

    Technology Transfer Automated Retrieval System (TEKTRAN)

    1,2,5,6,9,10-Hexabromocyclododecane-gamma ('-HBCD) is the predominate diastereoisomer in the commercial HBCD mixture used as a flame retardant in a wide variety of consumer products. Three main diastereoisomers, alpha (a), beta (ß) and gamma (') comprise the commercial mixture. Despite the '-diaster...

  9. Effects of Organophosphorus Flame Retardants on Spontaneous Activity in Neuronal Networks Grown on Microelectrode Arrays

    EPA Science Inventory

    EFFECTS OF ORGANOPHOSPHORUS FLAME RETARDANTS ON SPONTANEOUS ACTIVITY IN NEURONAL NETWORKS GROWN ON MICROELECTRODE ARRAYS TJ Shafer1, K Wallace1, WR Mundy1, M Behl2,. 1Integrated Systems Toxicology Division, NHEERL, USEPA, RTP, NC, USA, 2National Toxicology Program, NIEHS, RTP, NC...

  10. Influence of N-P base fiber reactive organophosphorus flame retardant on cotton thermal behavior

    Technology Transfer Automated Retrieval System (TEKTRAN)

    An efficient synergistic effect between a nitrogen-containing organophosphorus compound in the presence of a catalytic amount of chlorine is proposed based on the cyanuric chloride-linked organophosphorus flame retardant, tetraethyl-2,2'-(6-chloro-1,3,5-triazine-2,4-diyl)bis(azanediyl)bis(ethane-2,1...

  11. Enhanced flame retardant property of fiber reactive halogen-free organophosphonate

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In this paper, we studied the synthesis, characterization, and flammability of the water-soluble, non-halogenated organophosphorus flame retardant (FR), dimethyl-[1,3,5-(3,5-triacryloylhexahydro)triazinyl]-3-oxopropylphosphonate, for application to cotton farbics. The FR was synthesized in a one-st...

  12. Green application of flame retardant cotton fabric using supercritical carbon dioxide

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Due to its environmentally benign character, supercritical carbon dioxide (scCO2) is considered in green chemistry as a substitute for organic solvents in chemical reactions. In this poster, an innovative approach for preparation of flame retardant woven and nonwoven fabrics were obtained by utiliz...

  13. Thermal decomposition reactions of cotton fabric treated with piperazine-phosphonates derivatives as a flame retardant

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There has been a great scientific interest in exploring the great potential of the piperazine-phosphonates in flame retardant (FR) application on cotton fabric by investigating the thermal decomposition of cotton fabric treated with them. This research tries to understand the mode of action of the t...

  14. Approach for achieving flame retardancy while retaining physical properties in a compatible polymer matrix

    NASA Technical Reports Server (NTRS)

    Williams, Martha K. (Inventor); Smith, Trent M. (Inventor)

    2007-01-01

    The invention provides polymer blends containing polyhydroxyamide and one or more flammable polymers. The polymer blends are flame retardant and have improved durability and heat stability compared to the flammable polymer portion of the blends. Articles containing the polymer blends are also provided.

  15. Innovative layer-by-layer processing for flame retardant behavior of cotton fabric

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Flame retardant behavior has been prepared by the layer-by layer assemblies of kaolin/casein with inorganic chemicals on cotton fabrics. Three different kinds of cotton fabrics (print cloth, mercerized print cloth, and mercerized twill fabric) were prepared with solutions of mixture of BPEI, urea, ...

  16. Toxicokinetics of the Flame Retardant Hexabromocylodecane alpha: Effect of dose, timing, route, repeated exposure and metabolism

    EPA Science Inventory

    Alpha-hexabromocyclododecane (a-HBCD) is an emerging persistent organic pollutant present in the hexabromocyclododecane (HBCD) commercial mixture. HBCD is used as an additive flame retardant in a wide variety of household consumer products. Three main stereoisomers, alpha (a), be...

  17. TOXICOKINETICS OF THE FLAME RETARDANT HEXABROMOCYCLODODECANE GAMMA: EFFECT OF DOSE, TIMING, ROUTE, REPEATED EXPOSURE AND METABOLISM

    EPA Science Inventory

    1,2,5,6,9,10-Hexabromocyc1ododecane-gamma (y-HBCD) is the predominate diastereoisomer in the commercial HBCD mixture used as a flame retardant in a wide variety of consumer products. Three main diastereoisomers, alpha (a), beta (B) and gamma (y) comprise the commercial mixture. D...

  18. Approach for achieving flame retardancy while retaining physical properties in a compatible polymer matrix

    NASA Technical Reports Server (NTRS)

    Williams, Martha K. (Inventor); Smith, Trent M. (Inventor)

    2011-01-01

    The invention provides polymer blends containing polyhydroxyamide and one or more flammable polymers. The polymer blends are flame retardant and have improved durability and heat stability compared to the flammable polymer portion of the blends. Articles containing the polymer blends are also provided.

  19. A CASE STUDY ON THE RISKS AND BENEFITS OF DECABDE, A MAJOR BROMINATED FLAME RETARDANT

    EPA Science Inventory

    This is a proposal for a roundtable presentation at the 2008 Society of Toxicology Annual Meeting. ABSTRACT BODY: Decabromodiphenyl ether (DecaBDE) is a high production volume chemical used as a flame retardant in a variety of consumer applications; examples of uses in h...

  20. Citric acid based durable and sustainable flame retardant treatment for lyocell fabric.

    PubMed

    Mengal, Naveed; Syed, Uzma; Malik, Samander Ali; Ali Sahito, Iftikhar; Jeong, Sung Hoon

    2016-11-20

    Pyrovatex CP New, is a commonly used organophosphorus based flame retardant (FR) reagent for cellulosic materials. However, it has a drawback of high formaldehyde release when used with methylated melamine (MM) based cross-linker, a known carcinogenous compound. In the present approach, a durable and sustainable flame retarding recipe formulation for lyocell fabrics is developed using citric acid (CA) as a cross-linker. The FR finish was applied by pad-dry-cure process. The treated fabrics were characterized for surface morphology, elemental analysis, TG analysis, char study and FT-IR spectroscopy. Furthermore, flame retardancy, washing durability, formaldehyde release and breaking strength were also assessed, and compared with the conventional MM based FR recipe. The fabric samples treated with 400gL(-1) of FR with either 40 or 80gL(-1) of CA demonstrate flame retardancy even after 10 washing cycles. Furthermore, a 75% reduction in formaldehyde release is achieved. Higher char yield and lower decomposition temperature are found compared to untreated and FR+ MM treated lyocell. Such an improved sustainable recipe formulation can be used for lyocell fabric without any health risk in apparel wear. PMID:27561474

  1. Flame Retardant Behavior of Polyelectrolyte-Clay Thin Film Assemblies on Cotton Fabric

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cotton fabric was treated with flame-retardant coatings composed of branched polyethylenimine (BPEI) and sodium montmorillonite (MMT) clay, prepared via layer-by-layer (LbL) assembly. Four coating recipes were created by exposing fabric to aqueous solutions of BPEI (pH 7 or 10) and MMT(0.2 or 1 wt. ...

  2. Toxicokinetics of the flame retardant hexabromocyclododecane alpha: effect of dose, timing, route, repeated exposure and metabolism

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Hexabromocyclododecane (HBCD) is an additive flame retardant in many household products. Three stereoisomers, alpha (a), beta (b), and gamma (g), comprise roughly 10%, 10%, and 80% of the mixture, respectively. a-HBCD is the major stereoisomer found in biota, including breast milk and blood in Nor...

  3. First insight into the levels and distribution of flame retardants in potable water in Pakistan: An underestimated problem with an associated health risk diagnosis.

    PubMed

    Khan, Muhammad Usman; Li, Jun; Zhang, Gan; Malik, Riffat Naseem

    2016-09-15

    To date, very little is known about the occurrence of flame retardants (FRs) in potable water and its associated health risk to the exposed human population. The current study was designed to investigate the differences in the contamination levels of selected FRs in the potable water of industrial, rural and background zones of Pakistan. In addition, the health risk assessment for the exposed human population was estimated. For this purpose, the concentrations of the selected FRs: polybrominated diphenylethers (PBDEs), dechlorane plus (DP), novel brominated flame retardants (NBFRs) and organophosphate flame retardants (OPFRs), were analyzed in a total of 39 samples of potable water from the above mentioned three zones. We found elevated concentrations of ∑OPFRs (BDL-71.05ng/L), ∑PBDEs (BDL-0.82pg/L), ∑NBFRs (BDL-1.39pg/L) and ∑DP (BDL-0.29pg/L) in the potable water samples from industrial zones, smaller concentrations in the samples from rural zones, and negligible concentrations in the samples from background zones. Among all the FRs analyzed, Tris-(2-chloroisopropyl)-phosphate (∑TCPP), anti-DP, BDE-47 and 1.2-bis(pentabromodiphenyl)ethane (DBDPE) were the dominant compounds in all three selected zones. Principal component analysis (PCA) revealed that most of the FRs are associated with the industrial zones. The estimated daily intake (EDI) for all selected FRs was found to be higher in children than adults. However, both children and adults were found to be at low risk (i.e., Hazard quotient (HQ)<1) of FRs exposure through potable water consumption. We predict that FRs might be leached out from wastewater bodies and subsequently mixed with nearby potable water facilities. FRs may also spill out from the aluminum or plastic pipes and tanks most commonly used for potable water storage in Pakistan. The present study suggests initiating measures to minimize human exposure to FRs in the future. PMID:27177141

  4. A novel reutilization method for waste printed circuit boards as flame retardant and smoke suppressant for poly (vinyl chloride).

    PubMed

    Xiu, Fu-Rong; Weng, Huiwei; Qi, Yingying; Yu, Gending; Zhang, Zhigang; Zhang, Fu-Shen

    2016-09-01

    In this study, a novel reutilization method for waste printed circuit boards (PCBs) as flame retardant and smoke suppressant for poly (vinyl chloride) (PVC) was successfully testified. A supercritical water oxidation (SCWO) process was applied to treat waste PCBs before they could be used as flame retardants of PVC. The results indicated that SCWO conditions had a significant effect on the flame retarding and smoke suppressing properties of waste PCBs for PVC. Cu2O, CuO, and SnO2 were the main active ingredients in waste PCBs-derived flame retardants. A conversion of Cu elements (Cu(0)→Cu(+)→Cu(2+)) during SCWO process with the increase of reaction temperature was found to be the key influence factor for the flame retarding properties of SCWO-treated PCBs. The experiment results also showed that there was a synergistic effect of flame retardancy between Cu(+) and Cu(2+). After the optimized SCWO treatment, SCWO-treated PCBs significantly improved the flame retardancy and smoke suppression of PVC. Limiting oxygen index (LOI) and char yield (CY) increased with increasing SCWO-treated PCBs content in PVC, while smoke density rating (SDR) and maximum smoke density (MSD) decreased markedly. The mechanical properties of PVC samples were influenced in different degree by adding different content SCWO-treated PCBs. PMID:27179704

  5. Evaluation of Flame Retardancy, Mechanical Properties, and Bicompatibility of HIPS/PBrS Blends

    NASA Astrophysics Data System (ADS)

    Zhang, Liudi; Pack, Seongchan; Beaulieu, Coralie; Rafailovich, Miriam

    2012-02-01

    Our research focused on thermal and mechanical properties of High Impact Polystyrene (HIPS) system. Brominated Polystyrene (PBrS) was incorporated to replace halogenated Flame Retardant (DB) in HIPS blends. We have previously shown that ditallow functionalized clays could become nearly universal class of compatiblizers [si-2006]. Here we show that a new type of surface with Resorcinol bis (biphenyl phosphate) (RDP) could achieve the same goals. We demonstrate the strong compatibilization on the highly immiscible systems of HIPS/PBrS. Furthermore, we show that this system also works well, when a third component, Antimony Trioxide (AO) is added to provide flame retardant properties. Tensile test, dynamic mechanical analysis, and UL-94 flame test were applied to investigate this system. We found that the amount of AO used in flame retardant formulations could be minimized by addition of RDP clay, which could also increase some mechanical properties that Cloisite 20A clay couldn't. Besides, we evaluated the toxicity of Cloiste 20A and RDP clay. Langmuir-Blodgett trough and atomic force microscopy were used to make and check monolayer clay. Confocal Microscopy was used to assess cell morphology. The results showed RDP clay has potential for biomaterial applications.

  6. Development of a broad spectrum method for measuring flame retardants - overcoming the challenges of non-invasive human biomonitoring studies.

    PubMed

    Kucharska, Agnieszka; Covaci, Adrian; Vanermen, Guido; Voorspoels, Stefan

    2014-10-01

    Flame retardants (FRs), such as polybrominated diphenyl ethers (PBDEs) and phosphate flame retardants (PFRs), are a diverse group of compounds that are used to improve fire safety in many consumer products, such as furniture, textiles, electronics, etc. As these compounds are potentially harmful for human health, there is a need to better understand human exposure. Exposure to environmental contaminants can be monitored by the measurement of external sources of exposures and also by the determination of contaminant levels in human samples. For ethical and practical reasons, noninvasive matrices, such as hair, are preferred but, unfortunately, not widely used due to methodological limitations. A major challenge is sample availability: only small amounts can be sampled per individual. Multi-residue methods are therefore essential in order to determine multiple compounds in low sample amounts. In the framework of the FP7 project (INFLAME), an analytical method for the simultaneous determination of PBDEs and PFRs in human hair has been optimized and validated. Before extraction, hair samples (200 mg) were denaturated in nitric acid (HNO3) for 25 min at 25 °C. Consecutively, the samples were extracted using a mixture of hexane:dichloromethane, and extracts were further fractionated on Florisil. Fraction A which contained PBDEs was additionally cleaned on acidified silica gel and measured by gas chromatography coupled with electron capture negative ionization mass spectrometry (GC-ECNI-MS), while fraction B containing PFRs was directly analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS). This approach resulted in recoveries between 81-120% for PBDEs and 75-113% for PFRs (relative standard deviation (RSD) < 16%, n = 9). The optimized multi-residue method has been applied to 20 human hair samples. The obtained results indicated that the levels of PBDEs in hair samples were very low (0.2-12 ng/g) in relation to PBDE levels in human hair samples

  7. In vitro effects of brominated flame retardants and metabolites on CYP17 catalytic activity: A novel mechanism of action?

    SciTech Connect

    Canton, Rocio F. . E-mail: r.Fernandezcanton@iras.uu.nl; Sanderson, J. Thomas; Nijmeijer, Sandra; Bergman, Ake; Letcher, Robert J.; Berg, Martin van den

    2006-10-15

    Fire incidents have decreased significantly over the last 20 years due, in part, to regulations requiring addition of flame retardants (FRs) to consumer products. Five major classes of brominated flame retardants (BFRs) are hexabromocyclododecane isomers (HBCDs), tetrabromobisphenol-A (TBBPA) and three commercial mixtures of penta-, octa- and deca-polybrominated diphenyl ether (PBDE) congeners, which are used extensively as commercial FR additives. Furthermore, concentrations of PBDEs have been rapidly increasing during the 1999s in human breast milk and a number of endocrine effects have been reported. We used the H295R human adrenocortical carcinoma cell line to assess possible effects of some of these BFRs (PBDEs and several of their hydroxylated (OH) and methoxylated (CH{sub 3}O) metabolites or analogues), TBBPA and brominated phenols (BPs) on the combined 17{alpha}-hydroxylase and 17,20-lyase activities of CYP17. CYP17 enzyme catalyzes an important step in sex steroidogenesis and is responsible for the biosynthesis of dehydroepiandrosterone (DHEA) and androstenedione in the adrenals. In order to study possible interactions with BFRs, a novel enzymatic method was developed. The precursor substrate of CYP17, pregnenolone, was added to control and exposed H295R cells, and enzymatic production of DHEA was measured using a radioimmunoassay. In order to avoid pregnenolone metabolism via different pathways, specific chemical inhibitor compounds were used. None of the parent/precursor BFRs had a significant effect (P < 0.05) on CYP17 activity except for BDE-183, which showed significant inhibition of CYP17 activity at the highest concentration tested (10 {mu}M), with no signs of cytotoxicity as measured by mitochondrial toxicity tests (MTT). A strong inhibition of CYP17 activity was found for 6-OH-2,2',4,4'-tetrabromoDE (6-OH-BDE47) with a concentration-dependent decrease of almost 90% at 10 {mu}M, but with a concurrent decrease in cell viability at the higher

  8. Characterizing the Peroxisome Proliferator-Activated Receptor (PPARγ) Ligand Binding Potential of Several Major Flame Retardants, Their Metabolites, and Chemical Mixtures in House Dust

    PubMed Central

    Fang, Mingliang; Webster, Thomas F.; Ferguson, P. Lee

    2014-01-01

    Background: Accumulating evidence has shown that some environmental contaminants can alter adipogenesis and act as obesogens. Many of these contaminants act via the activation of the peroxisome proliferator-activated receptor γ (PPARγ) nuclear receptor. Objectives: Our goal was to determine the PPARγ ligand binding potency of several major flame retardants, including polybrominated diphenyl ethers (PBDEs), halogenated phenols and bisphenols, and their metabolites. Ligand binding activity of indoor dust and its bioactivated extracts were also investigated. Methods: We used a commercially available fluorescence polarization ligand binding assay to investigate the binding potency of flame retardants and dust extracts to human PPARγ ligand-binding domain. Rosiglitazone was used as a positive control. Results: Most of the tested compounds exhibited dose-dependent binding to PPARγ. Mono(2-ethylhexyl) tetrabromophthalate, halogenated bisphenols and phenols, and hydroxylated PBDEs were found to be potent PPARγ ligands. The most potent compound was 3-OH-BDE-47, with an IC50 (concentration required to reduce effect by 50%) of 0.24 μM. The extent of halogenation and the position of the hydroxyl group strongly affected binding. In the dust samples, 21 of the 24 samples tested showed significant binding potency at a concentration of 3 mg dust equivalent (DEQ)/mL. A 3–16% increase in PPARγ binding potency was observed following bioactivation of the dust using rat hepatic S9 fractions. Conclusion: Our results suggest that several flame retardants are potential PPARγ ligands and that metabolism may lead to increased binding affinity. The PPARγ binding activity of house dust extracts at levels comparable to human exposure warrants further studies into agonistic or antagonistic activities and their potential health effects. Citation: Fang M, Webster TF, Ferguson PL, Stapleton HM. 2015. Characterizing the peroxisome proliferator-activated receptor (PPARγ) ligand binding

  9. Effect of gravity on halogenated hydrocarbon flame retardant effectiveness

    NASA Technical Reports Server (NTRS)

    Ronney, P. D.

    1984-01-01

    Flammability limits, burning velocities, and minimum ignition energies under initially quiescent conditions were measured for stoichiometric and fuel-lean methane-, ethane-, and propane-air mixtures containing varying concentrations of Halon 1301. The characteristics of near-limit flames were strongly affected by fuel type but not Halon concentration. The conclusions were that the mechanism of the flammability limits was affected by fuel type but not Halon concentration, that the zero-g flammability limit is probably related to a stability criterion which is affected mostly by the molecular diffusion characteristics of the reactant gases and is mostly independent of chemical kinetics, and that the one-g upward flammability and ignition limits provide adequate criteria for safety at one-g and zero-g for both uninhibited and inhibited mixtures.

  10. Phosphoryl-rich flame-retardant ions (FRIONs): towards safer lithium-ion batteries.

    PubMed

    Rectenwald, Michael F; Gaffen, Joshua R; Rheingold, Arnold L; Morgan, Alexander B; Protasiewicz, John D

    2014-04-14

    The functionalized catecholate, tetraethyl (2,3-dihydroxy-1,4-phenylene)bis(phosphonate) (H2 -DPC), has been used to prepare a series of lithium salts Li[B(DPC)(oxalato)], Li[B(DPC)2], Li[B(DPC)F2], and Li[P(DPC)3]. The phosphoryl-rich character of these anions was designed to impart flame-retardant properties for their use as potential flame-retardant ions (FRIONs), additives, or replacements for other lithium salts for safer lithium-ion batteries. The new materials were fully characterized, and the single-crystal structures of Li[B(DPC)(oxalato)] and Li[P(DPC)3] have been determined. Thermogravimetric analysis of the four lithium salts show that they are thermally stable up to around 200 °C. Pyrolysis combustion flow calorimetry reveals that these salts produce high char yields upon combustion. PMID:24615890

  11. Influence of intumescent flame retardant and sepiolite on the mechanical and rheological behavior of polypropylene

    NASA Astrophysics Data System (ADS)

    Pappalardo, Salvatore; Acierno, Domenico; Russo, Pietro

    2016-05-01

    The mechanical and dynamic-mechanical properties and the capillary rheological behavior of polypropylene (PP) containing an intumescent flame retardant and sepiolite nanoparticles are investigated. Previous studies demonstrated that the combination of 0.5 wt% of organically modified sepiolite (OSEP) with 12 wt% of flame retardant (ET) allows to obtain interesting fire properties. In this study it is shown that such combination also ensure an improvement of the mechanical properties with respect to both the neat resin and the corresponding binary formulations. This result may be related to the higher degree of crystallinity observed for this ternary formulation by DSC characterization. This advantages are obtained without worsening the processability of the hosting matrix.

  12. Advanced treatment process for pharmaceuticals, endocrine disruptors, and flame retardants removal.

    PubMed

    Sundaram, Vijay; Emerick, Robert W; Shumaker, Stanley E

    2014-02-01

    The objective of this project was to demonstrate the effectiveness of an advanced treatment process that did not utilize reverse osmosis for the removal of pharmaceuticals, endocrine disruptors and flame retardants (collectively referred as contaminants of emerging concern [CECs]) from municipal effluent. The advanced treatment process consisted of (in the order of use): membrane filtration, ozonation (O3), and biologically active carbon (BAC) filtration. Ozone dosage of 5 mg/L or more was needed for desired CEC removal. Biologically active carbon removed flame retardants, and ozonation byproducts including NDMA and aldehydes. The project successfully demonstrated 1) the removal of a wide range of CECs, 2) reduction of estrogen activity to background levels, and 3) removal of ozonation byproducts. Treatment was achieved at lower costs and power utilization than reverse osmosis and without generating a concentrate stream. Results from this project could make CEC removal feasible, especially in situations where reverse osmosis treatment is infeasible. PMID:24645541

  13. Retrospective analysis of "new" flame retardants in the global atmosphere under the GAPS Network.

    PubMed

    Lee, Sum Chi; Sverko, Ed; Harner, Tom; Pozo, Karla; Barresi, Enzo; Schachtschneider, JoAnne; Zaruk, Donna; DeJong, Maryl; Narayan, Julie

    2016-10-01

    A retrospective analysis was conducted on air samples that were collected in 2005 under the Global Atmospheric Passive Sampling (GAPS) Network around the time period when the Stockholm Convention on Persistent Organic Pollutants came into force. Results are presented for several new flame retardants, including hexabromocyclododecane (HBCD), which was recently listed under the Convention (2013). These results represent the first global-scale distributions in air for these compounds. The targeted compounds are shown to have unique global distributions in air, which highlights the challenges in understanding the sources and environmental fate of each chemical, and ultimately in their assessments as persistent organic pollutants. The study also demonstrates the feasibility of using the PUF disk passive air sampler to study these new flame retardants in air, many of which exist entirely in the particle-phase as demonstrated in this study using a KOA-based partitioning model. PMID:26857525

  14. Aerobic biodegradation of the brominated flame retardants, dibromoneopentyl glycol and tribromoneopentyl alcohol.

    PubMed

    Segev, Osnat; Meusel, Wolfram; Friedenberger, Melanie; Brenner, Asher; Kushmaro, Ariel

    2009-09-01

    Halogenated organic compounds constitute one of the largest and most diverse groups of chemicals in the environment. Many of these compounds are toxic, persistent and, as a result of their often limited biodegradability, tend to bioaccumulate in the environment. Dibromoneopentyl glycol (DBNPG) and tribromoneopentyl alcohol (TBNPA) are brominated flame retardants commonly used as additives during the manufacture of plastic polymers and as chemical intermediates in the synthesis of other flame retardants. Both are classified as not readily biodegradable. In this paper, we demonstrate the biodegradation of both DBNPG and TBNPA by a common bacterial consortium under aerobic conditions in enrichment cultures containing yeast extract. DBNPG and TBNPA biodegradation is accompanied by a release of bromide into the medium, due to a biological debromination reaction. Molecular analysis of the clone library PCR amplified 16S rRNA gene was used to characterize the bacterial consortium involved in the biodegradation. PMID:19205903

  15. Flame retardancy and thermal stability of polyurethane foam composites containing carbon additives

    NASA Astrophysics Data System (ADS)

    Lee, Pyoung-Chan; Kim, Bo-Ram; Jeoung, Sun Kyoung; Lee, Geesoo; Han, San Wook; Kim, Hyunchul; Lee, Ki-Dong; Han, Joo-Kwon

    2016-03-01

    Polyurethane (PU) is an important class of polymers that have wide application in a number of different industrial sectors. The goal of this work was the synthesis of flame-retarded PU foam with expandable graphite (EG) or commercial graphene. The flame retardancy and thermal stability of the foams has been studied through cone calorimeter analysis, the limited oxygen index and thermal conductivity. The presence of expandable graphite brings an improvement in fire behavior. In particular, the limited oxygen index increases in a linear way and the highest limited oxygen index values are obtained for EG-PU foams. The results from the cone calorimeter are in agreement with those of oxygen index; EG filled foams show a considerable decrease of maximum-heat release rate (M-HRR) with respect to unfilled foams. The results of thermal conductivity show that an increase in expandable graphite amount in PU foams lead to an increased conductivity.

  16. Brominated flame retardant emissions from the open burning of five plastic wastes and implications for environmental exposure in China.

    PubMed

    Ni, Hong-Gang; Lu, Shao-You; Mo, Ting; Zeng, Hui

    2016-07-01

    Based on the most widely used plastics in China, five plastic wastes were selected for investigation of brominated flame retardant (BFR) emission behaviors during open burning. Considerable variations were observed in the emission factors (EF) of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) from the combustion of different plastic wastes. Distribution of BFR output mass showed that ΣPBDE was emitted mainly by the airborne particle (51%), followed by residual ash (44%) and the gas phase (5.1%); these values for ΣHBCD were 62%, 24%, and 14%, respectively. A lack of mass balance after the burning of the plastic wastes for some congeners (output/input mass ratios>1) suggested that formation and survival exceeded PBDE decomposition during the burns. However, that was not the case for HBCD. A comparison with literature data showed that the open burning of plastic waste is major source of PBDE compared to regulated combustion activities. Even for state-of-the-art waste incinerators equipped with sophisticated complex air pollution control technologies, BFRs are released on a small scale to the environment. According to our estimate, ΣPBDE release to the air and land from municipal solid waste (MSW) incineration plants in China in 2015 were 105 kg/year and 7124 kg/year. These data for ΣHBCD were 25.5 and 71.7 kg/year, respectively. Considering the fact that a growing number of cities in China are switching to incineration as the preferred method for MSW treatment, our estimate is especially important. This study provides the first data on the environmental exposure of BFRs emitted from MSW incineration in China. PMID:27064612

  17. Characterization of anthropogenic impacts in a large urban center by examining the spatial distribution of halogenated flame retardants.

    PubMed

    Wei, Yan-Li; Bao, Lian-Jun; Wu, Chen-Chou; Zeng, Eddy Y

    2016-08-01

    Anthropogenic impacts have continuously intensified in mega urban centers with increasing urbanization and growing population. The spatial distribution pattern of such impacts can be assessed with soil halogenated flame retardants (HFRs) as HFRs are mostly derived from the production and use of various consumer products. In the present study, soil samples were collected from the Pearl River Delta (PRD), a large urbanized region in southern China, and its surrounding areas and analyzed for a group of HFRs, i.e., polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane, bis(hexachlorocyclopentadieno)cyclooctane (DP) and hexabromobenzene. The sum concentrations of HFRs and PBDEs were in the ranges of 0.66-6500 and 0.37-5700 (mean: 290 and 250) ng g(-1) dry weight, respectively, around the middle level of the global range. BDE-209 was the predominant compound likely due to the huge amounts of usage and its persistence. The concentrations of HFRs were greater in the land-use types of residency, industry and landfill than in agriculture, forestry and drinking water source, and were also greater in the central PRD than in its surrounding areas. The concentrations of HFRs were moderately significantly (r(2) = 0.32-0.57; p < 0.05) correlated with urbanization levels, population densities and gross domestic productions in fifteen administrative districts. The spatial distribution of DP isomers appeared to be stereoselective as indicated by the similarity in the spatial patterns for the ratio of anti-DP versus the sum of DP isomers (fanti-DP) and DP concentrations. Finally, the concentrations of HFRs sharply decreased with increasing distance from an e-waste recycling site, indicating that e-waste derived HFRs largely remained in local soil. PMID:27203466

  18. Leaching of brominated flame retardants from mixed wastes in lysimeters under conditions simulating landfills in developing countries.

    PubMed

    Kajiwara, Natsuko; Hirata, Osamu; Takigami, Hidetaka; Noma, Yukio; Tachifuji, Ayako; Matsufuji, Yasushi

    2014-12-01

    In developing countries, wastes are usually not separated before being disposed of in solid-waste landfills, most of which are open dumps without adequate measures to prevent environmental pollution. To understand the leaching behavior of brominated flame retardants (BFRs) from waste consumer products in landfills, we have been conducting a long-term landfill lysimeter experiment since 2006 under conditions designed to mimic three types of landfill conditions in developing countries: aerobic, semi-aerobic, and anaerobic. Pilot-scale lysimeters (60-cm i.d.) were filled with a 400-cm layer of mixed wastes consisting of 35 wt% food, 20 wt% paper, 20 wt% paper pulp, 13 wt% plastic, 10 wt% wood chips, 1 wt% glass, and 1 wt% metals, proportions that are typical of unsorted municipal solid waste in Asian developing countries. In the present study, we determined the concentrations of polybrominated diphenyl ethers, tetrabromobisphenol A, tribromophenols, and hexabromocyclododecanes in leachate samples collected from the lysimeters during the first 3.5 years of the experiment, to evaluate BFR elution behavior in early-stage landfills. Under all three conditions, BFR elution started at the beginning of the experiment. The BFR concentrations in the leachates from the aerobic lysimeter tended to be lower than those from the anaerobic lysimeter, suggesting that the presence of air inside landfills considerably reduces BFR elution to the surrounding environment. During the 3.5-year experiment, BFR outflow from the lysimeters was only 0.001-0.58% of the total BFRs in the loaded waste; that is, most of the BFRs in the waste remained in the lysimeters. PMID:24560282

  19. Trophodynamics of hexabromocyclododecanes and several other non-PBDE brominated flame retardants in a freshwater food web.

    PubMed

    Wu, Jiang-Ping; Guan, Yun-Tao; Zhang, Ying; Luo, Xiao-Jun; Zhi, Hui; Chen, She-Jun; Mai, Bi-Xian

    2010-07-15

    Several currently used non-polybrominated diphenyl ether (PBDE) brominated flame retardants (BFRs), including hexabromocyclododecanes (HBCDs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), pentabromoethylbenzene (PBEB), and pentabromotoluene (PBT), are examined in the components of a freshwater food web from an electronic waste recycling site, South China. All these BFRs are detectable in the food web, with average concentrations of 13.9-868, 1.71-518, < 3.8-338, 197-3099, 3.98-25.6, and 1.20-3.60 ng/g lipid wt for HBCDs, BTBPE, DBDPE, HBB, PBEB, and PBT, respectively. Food web magnification is observed for (+)-alpha-, (-)-alpha-, (+/-)-alpha-, and total HBCDs, and HBB, with trophic magnification factors (TMFs) of 2.22, 2.18, 2.19, 1.82, and 1.46, respectively; whereas there is trophic dilution of BTBPE and PBT through the food web. The TMFs for (+)-alpha-, (-)-alpha-, and (+/-)-alpha-HBCDs are comparable to those of PBDEs detected previously in the same food web. Biota samples show a shift from gamma- toward alpha-HBCD compared with the suspended particles, sediment, and HBCD technical mixtures, with a significant increase of alpha-HBCD on ascending trophic levels. Except for alpha-HBCD in suspended particles and sediment, all the HBCD enantiomers detected are nonracemic in the environmental matrix. In biota, nonracemic residues of alpha-HBCD were observed in mud carp and crucian carp; beta-HBCD in prawn, mud carp, and crucian carp; and gamma-HBCD in water snake, with preferences for (+)-alpha-, (-)-beta-, and (+)-gamma-HBCDs. PMID:20575536

  20. Gestational and Early Postnatal Exposure to an Environmentally Relevant Mixture of Brominated Flame Retardants: General Toxicity and Skeletal Variations.

    PubMed

    Tung, Emily W Y; Yan, Han; Lefèvre, Pavine L C; Berger, Robert G; Rawn, Dorothea F K; Gaertner, Dean W; Kawata, Alice; Rigden, Marc; Robaire, Bernard; Hales, Barbara F; Wade, Michael G

    2016-06-01

    Brominated flame retardants (BFRs) are stable environmental contaminants known to exert endocrine-disrupting effects. Developmental exposure to polybrominated diphenyl ethers (PBDEs) is correlated with impaired thyroid hormone signaling, as well as estrogenic and anti-androgenic effects. As previous studies have focused on a single congener or technical mixture, the purpose of the current study was to examine the effects of gestational and early postnatal exposure to an environmentally relevant mixture of BFRs designed to reflect house dust levels of PBDEs and hexabromocyclododecane on postnatal developmental outcomes. Pregnant Sprague-Dawley rats were exposed to the PBDE mixture from preconception to weaning (PND 21) through the diet containing 0, 0.75, 250, and 750 mg mixture/kg diet. BFR exposure induced transient reductions in body weight at PND 35 in male and from PND 30-45 in female offspring (250 and 750 mg/kg). Liver weights (PND 21) and xenobiotic metabolizing enzyme activities (PND 21 and 46) were increased in both male and female offspring exposed to 250 and 750 mg/kg diets. Furthermore, serum T4 levels were reduced at PND 21 in both,male and female offspring (250 and 750 mg/kg). At PND 21, Serum alkaline phosphatase (ALP) was decreased in males exposed to 750 mg/kg dietat, and females exposed to 250 and 750 mg/kg diets. At PND 46 ALP was significantly elevated in males (250 and 750 mg/kg). Variations in the cervical vertebrae and phalanges were observed in pups at PND 4 (250 and 750 mg/kg). Therefore, BFR exposure during gestation through to weaning alters developmental programming in the offspring. The persistence of BFRs in the environment remains a cause for concern with regards to developmental toxicity. PMID:27286044

  1. Existence state of bromine as an indicator of the source of brominated flame retardants in indoor dust.

    PubMed

    Suzuki, Go; Kida, Akiko; Sakai, Shin-ichi; Takigami, Hidetaka

    2009-03-01

    Indoor dust is an important medium for human exposure to brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs). In this study, we used micro X-ray fluorescence spectrometry (XRFS), digital optical microscopy, and gas chromatography-high resolution mass spectrometry to investigate the existence state of bromine as an indicator of the source of BFRs in indoor dusts and in dusts from the interior of televisions collected in Japan. By means of micro XRFS bromine mapping conducted at a 0.5-s dwell time, we were able to detect bromine levels as low as about 0.1% at each point of about a beam diameter of 50 microm across. The presence of fragments containing 1.0% or more bromine was confirmed in 27 of the 48 dust samples tested. Using magnified images of the fragments, we classified them roughly into particulates and fibrous substances. We analyzed PBDEs in the fragments containing high concentrations of bromine (> or = 0.1%) and confirmed that the fragments contained PBDEs, mainly BDE 209. Furthermore, to detect bromine concentrations < or = 0.1% in the dust samples, we analyzed the samples at a dwell time of 100 s to enhance the detection sensitivity of mapping; atthis dwell time, we confirmed the presence of bromine in the dust coating. Our results suggest that bromine is transferred from products to dust matrixes not only through miniaturization and subsequent direct migration into dust as plastic and textile fragments but also through other pathways such as vaporization and airborne transfer of microparticulates. PMID:19350916

  2. Epigenetic effects of low perinatal doses of flame retardant BDE-47 on mitochondrial and nuclear genes in rat offspring

    PubMed Central

    Byun, Hyang-Min; Benachour, Nora; Zalko, Daniel; Frisardi, Maria Chiara; Colicino, Elena; Takser, Larissa; Baccarelli, Andrea A.

    2015-01-01

    Polybrominated diphenyl ethers (PBDEs) are known endocrine disrupting chemicals used commonly as flame retardants in everything from electronics to furniture. Exposure to PBDEs during early development has been linked to neurodevelopmental delays. Despite mounting evidence of neurological harm from PBDE exposure, the molecular mechanisms underlying these effects on brain function remain unknown. We examined the effects of perinatal exposure to BDE-47, the most biologically active and prevalent BDE congener in North America, on epigenetic patterns in the frontal lobe of Wistar rats. Dams were gavaged with BDE-47 (0.002 and 0.2 mg/kg body weight) at gestation days 9 and 16, and postnatal days 1, 8, and 15. Frontal lobes from offspring at postnatal day 41 were collected to measure 5-methylcytosine (5mC) in mitochondrial cytochrome c oxidase genes (Mt-co1, Mt-co2, and Mt-co3), global nuclear 5-hydroxymethylcytosine (5hmC) content, 5mC in repetitive elements L1Rn, and 5mC in nuclear genes (Bdnf, Crhr1, Mc2r, Nr3c1, and Snca) related to behavioral and brain functions in the nuclear genome. We observed a significant decrease in %5mC in Mt-co2 (difference from control= −0.68%, p=0.01 at the 0.2 mg/kg BDE-47). 5mC in repetitive elements L1Rn decreased at 0.002 mg/kg BDE-47 (difference= −1.23%, p=0.02). Decreased nuclear 5mC was observed in Bdnf and Nr3c1 in BDE-47 exposed rats. However, we did not observe significant effects of PBDE toxicity on DNA methylation patterns for the majority of genes in the brain. PMID:25533936

  3. The brominated flame retardant BDE-47 causes oxidative stress and apoptotic cell death in vitro and in vivo in mice

    PubMed Central

    Costa, Lucio G.; Pellacani, Claudia; Dao, Khoi; Kavanagh, Terrance J.; Roque, Pamela J.

    2015-01-01

    Polybrominated diphenyl ethers (PBDEs), used for decades as flame retardants, have become widespread environmental contaminants. Exposure is believed to occur primarily through diet and dust, and infants and toddlers have the highest body burden, raising concern for potential developmental neurotoxicity. The exact mechanisms of PBDE neurotoxicity have not been elucidated, but two relevant modes of action relate to impairment of thyroid hormone homeostasis and to direct effects on brain cells causing alterations in signal transduction, oxidative stress and apoptotic cell death. The present study shows that BDE-47 (2,2′,4,4′-tetrabromodiphenyl ether) induces oxidative stress and ensuing apoptotic cell death in mouse cerebellar granule neurons in vitro. Similarly, in vivo administration of BDE-47, according to an exposure protocol shown to induce behavioral and biochemical alterations (10 mg/kg, per os on post-natal day 10), induces oxidative stress and apoptosis, without altering serum levels of thyroid hormones. The effects of BDE-47 both in vitro and in vivo were more pronounced in a mouse model lacking the modifier subunit of glutamate cysteine ligase (GCLM) which results in reduced anti-oxidant capability due to low levels of GSH. Concentrations of BDE-47 in brain were in the mid-nanomolar range. These findings indicate that effects observed with BDE-47 in vitro are also present after in vivo administration, suggesting that in addition to potential endocrine effects, which were not seen here, direct interactions with brain cells should be considered as a potential mechanism of BDE-47 neurotoxicity. PMID:25797475

  4. Novel flame retardants in urban-feeding ring-billed gulls from the St. Lawrence River, Canada.

    PubMed

    Gentes, Marie-Line; Letcher, Robert J; Caron-Beaudoin, Elyse; Verreault, Jonathan

    2012-09-01

    This study investigated the occurrence of a comprehensive suite of polybrominated diphenyl ethers (PBDEs) and current-use flame retardants (FRs) in ring-billed gulls breeding in a highly industrialized section of the St. Lawrence River, downstream from Montreal (QC, Canada). Despite major point-sources and diffuse contamination by FRs, nearly no FR data have been reported in birds from this area. Bis(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (BEHTBP) was detected in 89% of ring-billed gull livers (mean: 2.16 ng/g ww; max: 17.6 ng/g ww). To our knowledge, this is the highest detection frequency and highest concentrations reported thus far in any avian species or populations. Dechlorane Plus (DP) isomers were also particularly abundant (anti-DP detected in 100% and syn-DP in 93% of livers). Other detected FR compounds (3-14% detection) included 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB), hexachlorocyclopentenyl-dibromocyclooctane (HCDBCO) and β-1,2-dibromo-4-(1.2-dibromoethyl)-cyclohexane (β-TBECH). Mean BDE-209 (57.2 ± 12.2 ng/g ww) in ring-billed gull livers was unexpectedly high for this midtrophic gull species, exceeding levels reported in several apex raptors such as peregrine falcons. BDE-209's relative contribution to ∑PBDEs was on average 25% (exceeding BDE-47 and BDE-99) and contrasted with profiles typically reported for fish-eating gull species. The present study highlighted preoccupying gaps in upcoming FR regulations and stressed the need for further investigation of the sources of FR exposure in highly urbanized areas. PMID:22845168

  5. Brominated flame retardants in aquatic organisms from the North Sea in comparison with biota from the high Arctic marine environment.

    PubMed

    Sørmo, Eugen G; Jenssen, Bjørn M; Lie, Elisabeth; Skaare, Janneche U

    2009-10-01

    The extent of trophic transfer of brominated flame retardants (BFRs), including hexabromocyclododecane (HBCD) and seven polybrominated diphenyl ethers (PBDEs), were examined in pelagic and benthic aquatic animals (invertebrates and fish) in a near-shore estuary environment of the southeastern North Sea (Norway; 59 degrees N). Whole-body burdens of HBCD and several of the most abundant PBDEs biomagnified with increasing trophic position in the food web. Biomagnification of HBCD was particularly strong, resulting in whole-body burdens of this compound comparable to those of total PBDEs in the higher-trophic-level species. Body burdens of PBDEs were higher in pelagic than in benthic aquatic organisms. This was particularly evident for the lesser-brominated and volatile PBDE congeners. Atmospheric gas-water-phytoplankton exchange of these volatile compounds over the water surface may account for this observation. The PBDE burdens in pelagic zooplankton from the North Sea were more than 60-fold greater than those in corresponding pelagic zooplankton from the colder high Arctic latitudes (>78 degrees N) of Norway (Svalbard). This great difference may relate to reduced chemical gas-water exchange over open waters at the colder Arctic latitudes. However, previously measured whole-body burdens of BFRs in other aquatic marine organisms from the high Arctic were comparable or even exceeded those in the North Sea samples of the present study. These include sympagic (sea ice-associated) invertebrates and fish accumulating high burdens of particle-associated BFRs. The present study provides new insight regarding the distribution of BFRs in ecologically different compartments of marine ecosystems, essential information for understanding the food-web transfer and geographical dispersal of these compounds. PMID:19459721

  6. European starlings ( Sturnus vulgaris ) suggest that landfills are an important source of bioaccumulative flame retardants to Canadian terrestrial ecosystems.

    PubMed

    Chen, Da; Martin, Pamela; Burgess, Neil M; Champoux, Louise; Elliott, John E; Forsyth, Douglas J; Idrissi, Abde; Letcher, Robert J

    2013-01-01

    Landfills are used as the primary means for the disposal of municipal solid waste in Canada. In the present study, polybrominated diphenyl ethers (PBDEs) and other flame retardants (FRs) were determined in fresh European starling ( Sturnus vulgaris ) eggs collected in 2009, 2010, and 2011 from nest boxes established within, adjacent to, and 10 and 40 km distant to five major urban centers across Canada, i.e., Vancouver, British Columbia (BC); Calgary, Alberta (AB); Hamilton, Ontario (ON); Montréal, Québec (QC); and Halifax, Nova Scotia (NS). Nest boxes were located in several land use types: urban industrial areas (districts of industrial activity within city limits), landfill sites (adjacent to cities), and rural (agricultural) sites located 10 and 40 km distant from the major urban centers, as well as a national reference site. Of the 14 PBDE congeners and 16 non-PBDE FR substances determined in the starling eggs, BDE-17, -28, -47, -49, -66, -85, -99, -100, -138, -153, -154, -183, and -209, Dechlorane Plus isomers (anti and syn), and bis(2-ethylhexyl)-3,4,5,6-tetrabromophthalate (BEHTBP) were most frequently quantifiable. The data revealed orders of magnitude greater PBDE concentrations in eggs from starlings nesting in landfill sites (median: 28-280 ng/g wet weight) relative to those from urban industrial and rural environments. However, the percent fractional composition of the PBDE congener patterns did not vary significantly between the types of land uses or between years. Additionally, the median ∑PBDE concentration in eggs from landfill sites and the human population density of the metropolitan region that the landfill serves were highly correlated (r(2) = 0.998, p < 0.001). As the first transcontinental effort in assessing FR contamination in Canadian terrestrial ecosystems, the present study strongly suggest that landfills are an important FR source to starlings nesting nearby and that other terrestrial organisms could also be similarly exposed. PMID

  7. Occurrence of halogenated flame retardants in sediment off an urbanized coastal zone: association with urbanization and industrialization.

    PubMed

    Liu, Hui-Hui; Hu, Yuan-Jie; Luo, Pei; Bao, Lian-Jun; Qiu, Jian-Wen; Leung, Kenneth M Y; Zeng, Eddy Y

    2014-01-01

    To examine the impacts of urbanization and industrialization on the coastal environment, sediment samples were collected from an urbanized coastal zone (i.e., Daya Bay and Hong Kong waters of South China) and analyzed for 20 polybrominated diphenyl ethers (PBDEs) and 10 alternative halogenated flame retardants (AHFRs). The sum concentration of PBDEs was in the range of 1.7-55 (mean: 17) ng g(-1), suggesting a moderate pollution level compared to the global range. The higher fractions of AHFRs (i.e., TBB+TBPH, BTBPE and DBDPE) than those of legacy PBDEs (i.e., penta-BDE, octa-BDE and deca-BDE) corresponded with the phasing out of PBDEs and increasing demand for AHFRs. Heavy contamination occurred at the estuary of Dan'ao River flowing through the Daya Bay Economic Zone, home to a variety of petrochemicals and electronics manufacturing facilities. The concentrations of HFRs in surface sediments of Hong Kong were the highest in Victoria Harbor, which receives around 1.4 million tons of primarily treated sewage daily, and a good relationship (r(2) = 0.80; p < 0.0001) between the HFR concentration and population density in each council district was observed, highlighting the effect of urbanization. Moreover, the AHFR concentrations were significantly correlated (r(2) > 0.73; p < 0.05) with the production volume of electronic devices, production value of electronic industries and population size, demonstrating the importance of industrializing and urbanizing processes in dictating the historical input patterns of AHFRs. PMID:24988362

  8. Variations of Flame Retardant, Polycyclic Aromatic Hydrocarbon, and Pesticide Concentrations in Chicago's Atmosphere Measured using Passive Sampling.

    PubMed

    Peverly, Angela A; Ma, Yuning; Venier, Marta; Rodenburg, Zachary; Spak, Scott N; Hornbuckle, Keri C; Hites, Ronald A

    2015-05-01

    Atmospheric concentrations of flame retardants, polycyclic aromatic hydrocarbons, and pesticides were measured using passive air samplers equipped with polyurethane foam disks to find spatial information in and around Chicago, Illinois. Samplers were deployed around the greater Chicago area for intervals of 6 weeks from 2012 to 2013 (inclusive). Volumes were calculated using passive sampling theory and were based on meteorology and the compounds' octanol-air partition coefficients. Geometric mean concentrations of total polybrominated diphenyl ethers ranged from 11 to 150 pg/m3, and tributyl phosphate, tris(2-chloroethyl)phosphate, tris(1-chloro-2-propyl)phosphate, and triphenyl phosphate concentrations were in the ranges of 54-290, 32-340, 130-580, and 170-580 pg/m3, respectively. The summed concentrations of 16 PAHs ranged from 8700 to 52,000 pg/m3 over the sampling area, and DDT, chlordane, and endosulfan concentrations were in the ranges of 2.7-9.9, 8.2-66, and 16-85 pg/m3, respectively. Sampling sites were split into two groups depending on their distances from the Illinois Institute of Technology campus in Chicago. With a few exceptions, the concentrations of most compound groups in the city's center were the same or slightly higher than those measured >45 km away. The data also showed that the concentrations measured with a passive atmospheric sampling system are in good agreement with those measured with an active, high-volume, sampling system. Given that the sampling times are different (passive, 43 days; active, 1 day), and that both of these measured concentrations cover about 5 orders of magnitude, the agreement between these passive and active sampling methods is excellent. PMID:25874663

  9. Tissue distribution of polybrominated diphenyl ethers in rats following oral exposure and the relationship to body burdens

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are a class of widely-used flame retardants which have been found to persist, bioaccumulate, and potentially affect development in animals. Humans are exposed to PBDEs through both their diet and indoor environment. In human exposure studies...

  10. IN VITRO EFFECTS OF ENVIRONMENTALLY RELEVANT POLYBROMINATED DIPHENYL ETHER (PBDE) CONGENERS ON CALCIUM BUFFERING MECHANISMS IN RAT BRAIN

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame-retardants and have been detected in human blood, adipose tissue, and breast milk. Developmental and long-term exposures to these chemicals may pose a human health risk, especially to children. We have previ...

  11. Polybrominated Diphenyl Ethers Alter Hepatic Phosphoenolpyruvate Carboxykinase Enzyme Kinetics in Male Wistar Rats: Implications for Lipid and Glucose Metabolism

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDE) are a family of lipophilic brominated flame-retardants consisting of 209 possible congeners. Three PBDE commercially-produced mixtures are decabrominated diphenyl ether (e.g. deca-BDE or DE-83R); octabrominated diphenyl ether (e.g. octa-BDE o...

  12. THE CONCENTRATION AND DISTRIBUTION OF POLYBROMINATED DIPHENYL ESTERS (PBDES) IN FISH FROM STREAMS OF THE MID-ATLANTIC REGION

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are used in the United States as flame-retardants in a wide range of products including paints, plastics, textiles, and electronics. In contrast to other persistent organic pollutants such as such as polychlorinated biphenyls (PCBs), organo...

  13. Changes in mitogen-activated protein kinase in cerebeller granule neurons by polybrominated diphenyl ethers and polychlorinated biphenyls

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are used as additive flame retardants and have been detected in human blood, adipose tissue, and breast milk. Both in vitro and in vivo studies have shown that the effects of PBDEs are similar to the known human developmental neurotoxicants ...

  14. CONGENER PROFILES OF POLYBROMINATED BIPHENYLS, -DIBENZO-P-DIOXINS AND -DIBENZOFURANS AS IMPURITIES IN TECHNICAL PREPARATION OF POLYBROMIANTED DIPHENYL ETHERS.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are flame retardants used in textiles, and electronic equipment to prevent these products from burning. PBDEs have been marketed as penta- (DE-71), octa- (DE-79), and deca-brominated (DE-83) preparations. Commercial PBDE preparations were an...

  15. Acute developmental exposure to polybrominated diphenyl ether 47 (PBDE 47) alters dopamine concentration within the brains of male mice.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are commonly used as commercial flame retardants in a variety of products including plastics and textiles. Previous studies in our laboratory and in the literature have shown that exposure to a specific PBDE congener, PBDE 47, during a criti...

  16. Tissue distribution of polybrominated diphenyl ethers in rats following oral exposure and the relationship to body burdens

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Polybrominated diphenyl ethers (PBDEs) are a class of widely-used flame retardants which have been found to persist, bioaccumulate, and potentially affect development in animals. Humans are exposed to PBDEs through both their diet and indoor environment. In human exposure studies, blood, adipose t...

  17. House Dust Concentrations of Organophosphate Flame Retardants in Relation to Hormone Levels and Semen Quality Parameters

    PubMed Central

    Meeker, John D.; Stapleton, Heather M.

    2010-01-01

    Background Organophosphate (OP) compounds, such as tris(1,3-dichloro-2-propyl) phosphate (TDCPP) and triphenyl phosphate (TPP), are commonly used as additive flame retardants and plasticizers in a wide range of materials. Although widespread human exposure to OP flame retardants is likely, there is a lack of human and animal data on potential health effects. Objective We explored relationships of TDCPP and TPP concentrations in house dust with hormone levels and semen quality parameters. Methods We analyzed house dust from 50 men recruited through a U.S. infertility clinic for TDCPP and TPP. Relationships with reproductive and thyroid hormone levels, as well as semen quality parameters, were assessed using crude and multivariable linear regression. Results TDCPP and TPP were detected in 96% and 98% of samples, respectively, with widely varying concentrations up to 1.8 mg/g. In models adjusted for age and body mass index, an interquartile range (IQR) increase in TDCPP was associated with a 3% [95% confidence interval (CI), −5% to −1%) decline in free thyroxine and a 17% (95% CI, 4–32%) increase in prolactin. There was a suggestive inverse association between TDCPP and free androgen index that became less evident in adjusted models. In the adjusted models, an IQR increase in TPP was associated with a 10% (95% CI, 2–19%) increase in prolactin and a 19% (95% CI, −30% to −5%) decrease in sperm concentration. Conclusion OP flame retardants may be associated with altered hormone levels and decreased semen quality in men. More research on sources and levels of human exposure to OP flame retardants and associated health outcomes are needed. PMID:20194068

  18. Study of a novel phosphorus-containing flame retardant for cotton fabric

    NASA Astrophysics Data System (ADS)

    Gao, W. W.; Lu, Y. H.; Xu, F.; Zhang, G. X.; Zhang, F. X.

    2015-07-01

    In this paper, a high efficiency FR named HPA was applied to treat cotton fabric. The results of LOI values and vertical flammability test showed that HPA treated cotton fabric had the best flame retardancy (LOI value was 36.0%), when the FR concentration is 50 g/L, and cured at 180°C for 7 min. During the process of holding back the combustion, HPA behaves the excellent properties of FR for cotton fabric.

  19. Prenatal Exposure to Polybrominated Flame Retardants and Fetal Growth in the INMA Cohort (Spain)

    PubMed Central

    2015-01-01

    Our aim was to investigate the relation between PBDEs and fetal growth or newborn anthropometry in a Spanish cohort (2003–2008). PBDE congeners (BDE-47, -99, -153, -154, and -209) were determined in serum of 670 mothers at gestational week 12 and in 534 umbilical cord samples. Abdominal circumference (AC), estimated fetal weight (EFW), femur length (FL), and biparietal diameter (BPD) during gestation were measured by ultrasounds. At birth, weight (BW), head circumference (HC), and length (BL) were also measured. We assessed growth in the intervals between 12–20 and 20–34 weeks of gestation and size at birth by standard deviation (SD)-scores adjusted for constitutional characteristics. We conducted multivariate linear regression analyses between PBDE congeners and their sum (ΣPBDEs) and outcomes. We found statistically significant inverse associations between ΣPBDEs and AC, EFW, and BPD at weeks 20–34 and HC at birth. Regarding congeners, the association was clearer with BDE-99, with inverse associations being found with AC, EFW, and BPD at weeks 20–34, and with BW and HC at delivery. These outcomes decreased between 1.3% and 3.5% for each 2-fold PBDE increase. Concerning matrices, we found statistically significant inverse associations with BPD, HC, and BW when using maternal serum, and for AC and EFW with cord serum. In conclusion, PBDEs may impair fetal growth in late pregnancy and reduce birth size. PMID:26181825

  20. Selective and Sensitive Sensing of Flame Retardant Chemicals Through Phage Display Discovered Recognition Peptide.

    PubMed

    Jin, Hyo-Eon; Zueger, Chris; Chung, Woo-Jae; Wong, Winnie; Lee, Byung Yang; Lee, Seung-Wuk

    2015-11-11

    We report a highly selective and sensitive biosensor for the detection of an environmentally toxic molecule, decabrominated diphenyl ether (DBDE), one of the most common congeners of the polybrominated frame retardants (polybrominated diphenyl ether (PBDE)), using newly discovered DBDE peptide receptors integrated with carbon nanotube field-effect transistors (CNT-FET). The specific DBDE peptide receptor was identified using a high-throughput screening process of phage library display. The resulting binding peptide carries an interesting consensus binding pocket with two Trp-His/Asn-Trp repeats, which binds to the DBDE in a multivalent manner. We integrated the novel DBDE binding peptide onto the CNT-FET using polydiacetylene coating materials linked through cysteine-maleimide click chemistry. The resulting biosensor could detect the desired DBDE selectively with a 1 fM detection limit. Our combined approaches of selective receptor discovery, material nanocoating through click chemistry, and integration onto a sensitive CNT-FET electronic sensor for desired target chemicals will pave the way toward the rapid development of portable and easy-to-use biosensors for desired chemicals to protect our health and environment. PMID:26455834

  1. Effects of Hoods and Flame-Retardant Fabrics on WBGT Clothing Adjustment Factors.

    PubMed

    Ashley, Candi D; Bernard, Thomas E

    2008-01-01

    Personal protective clothing (PPC) may include hoods and flame-retardant (FR) fabrics that may affect heat transfer and, thus, the critical wet bulb globe temperature (WBGT crit) to maintain thermal equilibrium. The purpose of this study was to compare the differences in WBGT crit for hooded vs. nonhooded versions of particle barrier and vapor barrier coveralls as well as for coveralls made of two flame-retardant fabrics (INDURA cotton and Nomex). Acclimated men (n = 11) and women (n = 4) walked on a treadmill in a climatic chamber at 180 W/m2 wearing four different ensembles: limited-use, particle barrier coveralls with and without a hood (Tyvek 1427), and limited-use vapor barrier coveralls with and without a hood (Tychem QC, polyethylene-coated Tyvek). Twelve of the participants wore one of two flame-retardant coveralls. All participants wore standard cotton clothing. Progressive exposure testing at 50% relative humidity (rh) was designed so that each subject established a physiological steady-state followed by a clear loss of thermal equilibrium. WBGT crit was the WBGT 5 min prior to a loss of thermal equilibrium. Hooded ensembles had a lower WBGT crit than the nonhooded ensembles. The difference suggested a clothing adjustment of 1 degrees C for hoods. There were no significant differences among the FR ensembles and cotton work cloths, and the proposed clothing adjustment for FR coveralls clothing is 0 degrees C. PMID:18041645

  2. Discrimination of hexabromocyclododecane from new polymeric brominated flame retardant in polystyrene foam by nuclear magnetic resonance.

    PubMed

    Jeannerat, Damien; Pupier, Marion; Schweizer, Sébastien; Mitrev, Yavor Nikolaev; Favreau, Philippe; Kohler, Marcel

    2016-02-01

    Hexabromocyclododecane (HBCDD) is a brominated flame retardant (BFR) and major additive to polystyrene foam thermal insulation that has recently been listed as a persistent organic pollutant by the Stockholm Convention. During a 2013/2014 field analytical survey, we measured HBCDD content ranging from 0.2 to 2.4% by weight in 98 polystyrene samples. Liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) analyses indicated that expandable (EPS) and extruded (XPS) polystyrene foams significantly differed in the α/γ HBCDD isomer ratio, with a majority of α and γ isomers in XPS and EPS, respectively. Interestingly, this technique indicated that some recent materials did not contain HBCDD, but demonstrated bromine content when analysed with X-ray fluorescence (XRF). Further investigation by Nuclear Magnetic Resonance (NMR) was able to discriminate between the BFRs present. In addition to confirming the absence or presence of HBCDD in polystyrene samples, high-field NMR spectroscopy provided evidence of the use of brominated butadiene styrene (BBS) as copolymer in the production of polystyrene. Use of this alternative flame retardant is expected to cause fewer health and environmental concerns. Our results highlight a trend towards the use of copolymerized BFRs as an alternative to HBCDD in polystyrene foam boards. In addition to providing a rapid NMR method to identify polymeric BFR, our analytical approach is a simple method to discriminate between flame-retardants in polystyrene foam insulating materials. PMID:26492426

  3. Influence of radiation-crosslinking on flame retarded polymer materials-How crosslinking disrupts the barrier effect

    NASA Astrophysics Data System (ADS)

    Sonnier, Rodolphe; Caro-Bretelle, Anne-Sophie; Dumazert, Loïc; Longerey, Marc; Otazaghine, Belkacem

    2015-01-01

    Fire behavior of flame retardant-free and flame retarded PP/PA6 blends was studied using pyrolysis-combustion flow calorimeter, cone calorimeter and epiradiator equipped with infrared camera and pyrometer. Blends were previously γ-irradiated in presence of crosslinking agents at various doses (up to 100 kGy) in order to assess the influence of irradiation crosslinking on flame retardancy. Crosslinked specimens exhibit a solid-like behavior under high temperature gradient in cone calorimeter and then distort considerably. The influence of such a behavior depends on the material properties. When the flame retardancy is provided by heat shielding effect, heat distortion disrupts the top protective layer leading to a substantial increase of peak of heat release rate (pHRR). The barrier layer is no longer able to prevent the heat transfer to the underlying condensed phase. In other cases (flame retardant-free blends or flame retardancy provided by other effects than heat shielding), heat distortion has negligible influence on heat release rate curves in cone calorimeter tests.

  4. Flame-Retardant Paper from Wood Fibers Functionalized via Layer-by-Layer Assembly.

    PubMed

    Köklükaya, Oruç; Carosio, Federico; Grunlan, Jaime C; Wågberg, Lars

    2015-10-28

    The highly flammable character of cellulose-rich fibers from wood limits their use in some advanced materials. To suppress the flammability and introduce flame-retardant properties to individual pulp fibers, we deposited nanometer thin films consisting of cationic chitosan (CH) and anionic poly(vinylphosphonic acid) (PVPA) on fibers using the layer-by-layer (LbL) technique. The buildup of the multilayer film was investigated in the presence and absence of salt (NaCl) using model cellulose surfaces and a quartz crystal microbalance technique. Fibers were then treated with the same strategy, and the treated fibers were used to prepare paper sheets. A horizontal flame test (HFT) and cone calorimetry were conducted to evaluate the combustion behavior of paper sheets as a function of the number of bilayers deposited on fibers. In HFT, paper made of fibers coated with 20 CH/PVPA bilayers (BL), self-extinguished the flame, while uncoated fibers were completely consumed. Scanning electron microscopy of charred paper after HFT revealed that a thin shell of the charred polymeric multilayer remained after the cellulose fibers had been completely oxidized. Cone calorimetry demonstrated that the phosphorus-containing thin films (20 BL is ∼25 nm) reduced the peak heat release rate by 49%. This study identifies a unique and highly effective way to impart flame-retardant characteristic to pulp fibers and the papers made from these fibers. PMID:26457504

  5. Organo-modified bentonites as new flame retardant fillers in epoxy resin nanocomposites

    NASA Astrophysics Data System (ADS)

    Benelli, Tiziana; D'Angelo, Emanuele; Mazzocchetti, Laura; Saraga, Federico; Sambri, Letizia; Franchini, Mauro Comes; Giorgini, Loris

    2016-05-01

    The present work deals with two organophilic bentonites, based on nitrogen-containing compounds: these organoclays were synthesized via an ion exchange process starting from pristine bentonite with 6-(4-butylphenyl)-1,3,5-triazine-2,4-diamine (BFTDA) and 11-amino-N-(pyridine-2yl)undecanamide (APUA) and then used for the production of epoxy-based flame retardant nanocomposites. The amount of organic modifier in the organoclays Bento-BFTDA and Bento-APUA was determined with a TGA analysis and is around 0.4mmol/g for both samples. The effect of the organoclays on a commercial epoxy resin nanocomposite's thermo-mechanical and flammability properties was investigated. Composites containing 3wt% and 5wt% of the nanofillers were prepared by solventless addition of each organoclay to the epoxy resin, followed by further addition of the hardener component. For the sake of comparison a similar nanocomposite with the plain unmodified bentonite was produced in similar condition. The nanocomposites's thermo-mechanical properties of all the produced samples were measured and they resulted slightly improved or practically unaffected. On the contrary, when the flame behaviour was assessed in the cone-calorimeter, an encouraging decrease of 17% in the peak heat released rate (pHRR) was obtained at 3wt% loading level with Bento-APUA. This is a promising result, assessing that the APUA modified organoclay might act as flame retardant.

  6. Emissions of brominated flame retardants in Asia: consideration of its potential risk form the view point of the Norwegian regulation

    NASA Astrophysics Data System (ADS)

    Kikuchi, Ryunosuke; Gerardo, Romeu; Gorbacheva, Tamara

    2010-05-01

    Flame retardants can be divided into two broad categories: additive or reactive, which can be further more divided into brominated or non-brominated sub-categories. These retardants are found in many commercial products such as computers, television sets, furniture, carpets, etc. They are of environmental concern due to their persistence, potential for bioaccumulation and widespread distribution via atmospheric transport, and possible adverse effects in wildlife and humans. Tetrabromobisphenol-A (TBBPA) is mainly used in electrical and electronic appliances (circuit board in particular), and the application of TBBPA accounts for about two thirds of the global production of brominated flame retardant (BFR). The European Union Risk Assessment does not support the restriction of TBBPA: i.e. no risk is identified for the reactive use of TBBPA such as in epoxy resin used in circuit boards. By contrast, in 2007 Norway notified the World Trade Organization of its intention to prohibit 18 substances from consumer goods (Notification No. 2007/9016/N), called the Prohibition on Certain Hazardous Substances in Consumer Products (PoHS). TBBPA is listed in this prohibition list. Marine conservation is recognized as a key issue in Norwegian fishery management e.g. wastewater management in the framework of the North Sea Declarations. TBBPA is very water-soluble, and dimethyl-TBBPA is lipophilic and may accumulate in fat. TBBPA is not readily biodegradable and can have long-term effects in the aquatic environment. Norwegian examples are summarized: TBBPA was found in marine sediment samples from Tromsø harbor (northern Norway) and in Atlantic cod from Lofoten and Varanger; TBBPA has been detected in Norwegian peregrine falcon and golden eagle eggs; and TBBPA has been detected in the blood in the general population of Norway. From these viewpoints, it can be considered that Norway needs to strictly control TBBPA emissions. In recent times, Asia has emerged as one of the leading

  7. In Vitro Metabolism of Photolytic Breakdown Products of Tetradecabromo-1,4-diphenoxybenzene Flame Retardant in Herring Gull and Rat Liver Microsomal Assays.

    PubMed

    Su, Guanyong; Greaves, Alana K; Teclechiel, Daniel; Letcher, Robert J

    2016-08-01

    Tetradecabromo-1,4-diphenoxybenzene (TeDB-DiPhOBz) is used as a flame retardant chemical and has been hypothesized to be the precursor of methoxylated polybrominated diphenoxybenzene (MeO-PB-DiPhOBz) contaminants reported in herring gulls from sites across the Laurentian Great Lakes. Here, by irradiating the parent TeDB-DiPhOBz (solution 1) with natural sunlight or UV, we prepared three solutions where solution 2 was dominated by the Br8-11-PB-DiPhOBzs, along with Br5-8-PB-DiPhOBzs (solution 3) and Br4-6-PB-DiPhOBzs (solution 4). The in vitro metabolism of TeDB-DiPhOBz and PB-DiPhOBzs was investigated using harvested wild herring gull (Larus argentatus) and adult male Wister-Han rat liver microsomal assays. After a 90 min incubation period of solution 1 in gull or rat microsomal assays, there was no significant (p > 0.05) depletion of TeDB-DiPhOBz. OH-PB-DiPhOBz metabolites were detectable after gull and rat microsomal assay incubation with solutions 3 or 4, and showed clear species-specific differences. Also detected were two polybrominated hydroxylated metabolites having polybenzofuran structures. Overall, this study suggested that TeDB-DiPhOBz is slowly metabolized in vitro, and also indicated that if wild herring gulls are exposed (e.g., via the diet) to photolytic products of TeDB-DiPhOBz, OH-PB-DiPhOBz and other metabolites could be formed. OH-PH-DiPhOBz are likely precursors to MeO-PB-DiPhOBz contaminants that we reported previously in eggs of wild Great Lakes herring gulls. PMID:27351066

  8. Durable flame retardant finish for silk fabric using boron hybrid silica sol

    NASA Astrophysics Data System (ADS)

    Zhang, Qiang-hua; Gu, Jiali; Chen, Guo-qiang; Xing, Tie-ling

    2016-11-01

    A hybrid silica sol was prepared via sol gel method using tetraethoxysilane (TEOS) as a precursor and boric acid (H3BO3) as flame retardant additive and then applied to silk fabric. In order to endow silk fabric with durable flame retardancy, 1,2,3,4-butanetetracarboxylic acid (BTCA) was used as cross-linking agent for the sake of strong linkage formation between the hybrid silica sol and silk fabric. The FT-IR and XPS analysis demonstrated the Si-O-B formation in the sol system, as well as the linkage between the sol and silk after the treatment. The limiting oxygen index (LOI) and smoke density test indicated good flame retardancy and smoke suppression of the treated silk fabrics. The micro calorimeter combustion (MCC) test and thermo gravimetric (TG) analysis showed that the treated samples had less weight loss in the high temperature and lower heat release rate when burning. The washing durability evaluation results indicated that there was a distinct improvement for the silk samples treated with BTCA even after 30 times washing. In addition, the influence of the processing order of BTCA and silica sol treatment on the limiting oxygen index (LOI) of the finished silk fabric was also investigated. And the results demonstrated that the sample treated with BTCA first and then with the silica sol exhibited better LOI value (32.3%) than that of the sample by the conversed treatment order. Moreover the tensile property of treated samples was nearly unchanged, but the handle of sol treated samples obviously decreased.

  9. Rapid methodology to screen flame retardants in upholstered furniture for compliance with new California labeling law (SB 1019).

    PubMed

    Petreas, Myrto; Gill, Ranjit; Takaku-Pugh, Sayaka; Lytle, Eric; Parry, Emily; Wang, Miaomiao; Quinn, John; Park, June-Soo

    2016-06-01

    In response to concerns regarding the widespread use of flame retardants, the California Legislature passed a law (SB1019) requiring labels on furniture products to indicate whether they do or do not contain flame retardants. To support the enforcement of the new law, our laboratory developed a step-wise, screening approach to test for brominated (BFR) and phosphorus-based flame retardants (OPFRs) in several types of furniture components (foam, fabric, batting, plumage, etc.). We used X-Ray Fluorescence (XRF) to screen for the presence of Br (and other elements) and Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES) to identify and measure the concentration of P (and other elements). The same samples were also extracted by dichloromethane using sonication and analyzed by a single injection into a Gas Chromatograph - Tandem Mass Spectrometer to obtain concentrations of specific BFRs and OPFRs. Our approach showed excellent screening potential for Br and Sb by XRF and for P by ICP-OES, with both tests having predictive values of a negative equal to 1. To explore and screen for flame retardants in products not included in our current list of target chemicals, we used Liquid Chromatography/Time-of-Flight Mass Spectrometry operated with electrospray ionization, to identify additional flame retardants to be incorporated in quantitative methods. We are making all our methodologies public to facilitate simple and low cost methods that can help manufacturers and suppliers have their products tested and correctly labeled, ultimately benefitting the consumer. PMID:26991383

  10. Low-smoke, halogenfree ship-offshore/onshore cables with improved flame retardance and fire resistance

    NASA Astrophysics Data System (ADS)

    Pedersen, J. R.; Holte, T. A.; Johansen, E.

    Cables with improved fire resistance and flame retardance have been developed. They will continue to function at least 3 hours even at temperatures up to 1000 C and do not propagate fire when tested according to IEC 332 part 3 1982, category A. Made with halogenfree materials they give off no corrosive gases and very little visible smoke in cases of fire. Cables are made for power, signal and instrument installations in hospitals, high rise buildings, railroad cars, subways, on board ship, oil rigs and oil production platforms. The offshore cables are specially constructed to withstand the rugged climatic conditions in the North Sea area.

  11. Eco-friendly functionalized superhydrophobic recycled paper with enhanced flame-retardancy.

    PubMed

    Si, Yifan; Guo, Zhiguang

    2016-09-01

    Recycled paper with superhydrophobicity and flame-retardancy has been demonstrated here due to the synergistic action of dopamine-silica trimethylsilyl modified gel powder and stearic acid modified Mg(OH)2. This multifunctional recycled paper displays great self-cleaning and anti-fouling ability and can be used for oil-water separation. Surprisingly, the absorbed organic can be reused as fuel via simple combustion method for multiple cycles. This work will not only expand the usable range of paper but also ease the energy and environment crisis. PMID:27244592

  12. LACK OF ALTERATIONS IN THYROID HORMONES FOLLOWING EXPOSURE TO POLYBROMINATED DIPHENYL ETHER 47 DURING A PERIOD OF RAPID BRAIN DEVELOPMENT IN MICE

    EPA Science Inventory

    Polybrominated diphenyl ether 47 (PBDE-47) is one of a class of commonly used flame retardants that are accumulating in the environment, including human tissues. There are reports of thyroid alterations following exposure to PBDE mixtures, and it is possible that disruptions in t...

  13. POLYBROMINATED DIPHENYL ETHER (PBDE) EFFECTS IN RAT NEURONAL CULTURES: 14C-PBDE ACCUMULATION, BIOLOGICAL EFFECTS AND STRUCTURE-ACTIVITY RELATIONSHIPS.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are widely used as flame-retardants, are now recognized as a globally distributed pollutants, and are detected in most environmental and biological samples, including human blood, adipose tissue, and breast milk. Due to their wide use in com...

  14. DIFFERENTIAL EFFECTS OF POLYBROMINATED DIPHENYL ETHERS AND POLYCHLORINATED BIPHENYLS ON [3H]ARACHIDONIC ACID RELEASE IN RAT CEREBELLAR GRANULE NEURONS.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs), which are widely used as flame-retardants, have been increasing in the past 20-30 years while the presence of other structurally related persistent organic pollutants, such as polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-d...

  15. Construction of flame retardant nanocoating on ramie fabric via layer-by-layer assembly of carbon nanotube and ammonium polyphosphate

    NASA Astrophysics Data System (ADS)

    Zhang, Tao; Yan, Hongqiang; Peng, Mao; Wang, Lili; Ding, Hongliang; Fang, Zhengping

    2013-03-01

    A new flame retardant nanocoating has been constructed by the alternate adsorption of polyelectrolyte amino-functionalized multiwall carbon nanotube (MWNT-NH2) and ammonium polyphosphate (APP) onto flexible and porous ramie fabric. Scanning electron microscopy indicates that the adsorbed carbon nanotube coating is a randomly oriented and overlapped network structure, which is a promising candidate for flame retardancy applications. Attenuated total reflection Fourier transform infrared spectroscopy and energy-dispersive X-ray analysis confirm that the APP is successfully incorporated into the multilayers sequentially. Assessment of the thermal and flammability properties for the pristine and nanocoated ramie fabrics shows that the thermal stability, flame retardancy and residual char are enhanced as the concentration of MWNT-NH2 suspension and number of deposition cycles increases. The enhancements are mostly attributed to the barrier effect of intumescent network structure, which is composed of MWNT-NH2 and the absorbed APP.

  16. Construction of flame retardant nanocoating on ramie fabric via layer-by-layer assembly of carbon nanotube and ammonium polyphosphate.

    PubMed

    Zhang, Tao; Yan, Hongqiang; Peng, Mao; Wang, Lili; Ding, Hongliang; Fang, Zhengping

    2013-04-01

    A new flame retardant nanocoating has been constructed by the alternate adsorption of polyelectrolyte amino-functionalized multiwall carbon nanotube (MWNT-NH2) and ammonium polyphosphate (APP) onto flexible and porous ramie fabric. Scanning electron microscopy indicates that the adsorbed carbon nanotube coating is a randomly oriented and overlapped network structure, which is a promising candidate for flame retardancy applications. Attenuated total reflection Fourier transform infrared spectroscopy and energy-dispersive X-ray analysis confirm that the APP is successfully incorporated into the multilayers sequentially. Assessment of the thermal and flammability properties for the pristine and nanocoated ramie fabrics shows that the thermal stability, flame retardancy and residual char are enhanced as the concentration of MWNT-NH2 suspension and number of deposition cycles increases. The enhancements are mostly attributed to the barrier effect of intumescent network structure, which is composed of MWNT-NH2 and the absorbed APP. PMID:23459988

  17. Developmental exposure of zebrafish larvae to organophosphate flame retardants causes neurotoxicity.

    PubMed

    Sun, Liwei; Xu, Wenbin; Peng, Tao; Chen, Haigang; Ren, Lin; Tan, Hana; Xiao, Dan; Qian, Haifeng; Fu, Zhengwei

    2016-01-01

    With the gradual ban on brominated flame retardants (FRs), the application of organophosphate flame retardants (OPFRs) has increased remarkably. Considering the structural similarity between OPFRs and organophosphate pesticides, hypotheses that OPFRs may interfere with neurodevelopment as organophosphate pesticides are reasonable. In this study, the neurotoxicity of three OPFRs, including tri-n-butyl phosphate (TNBP), tris (2-butoxyethyl) phosphate (TBOEP) and tris (2-chloroethyl) phosphate (TCEP), was evaluated in zebrafish larvae and then compared with the neurotoxicity of organophosphate pesticide chlorpyrifos (CPF). The results showed that similar to CPF, exposure to OPFRs for 5days resulted in significant changes in locomotor behavior, either in free swimming or in photomotor response. However, given the transcriptional changes that occur in nervous system genes in response to OPFRs and CPF, as well as the altered enzyme activity of AChE and its mRNA level, the underlying mechanisms for neurotoxicity among these organophosphate chemicals might be varied. In summary, the results confirm the potential neurodevelopmental toxicity of OPFRs and underscore the importance of identifying the mechanistic targets of the OPFRs with specific moieties. Furthermore, as the neurobehavioral responses are well conserved among vertebrates and the exposure of children to OPFRs is significant, a thorough assessment of the risk of OPFRs exposure during early development should be highly emphasized in future studies. PMID:27018022

  18. A Versatile and Scalable Approach toward Robust Superhydrophobic Porous Materials with Excellent Absorbency and Flame Retardancy.

    PubMed

    Ruan, Changping; Shen, Mengxia; Ren, Xiaoyan; Ai, Kelong; Lu, Lehui

    2016-01-01

    The frequent oil spillages and the industrial discharge of organic contaminants have not only created severe environmental and ecological crises, but also cause a risk of fire and explosion. These environmental and safety issues emphasize the urgent need for materials that possess superior sorption capability and less flammability and thus can effectively and safely clean up the floating oils and water-insoluble organic compounds. Here we present the successful hydrophobic modification of the flame retardant melamine sponge with a commercial fluorosilicone, by using a facile one-step solvent-free approach and demonstrate that the resultant superhydrophobic sponge not only exhibits extraordinary absorption efficiency (including high capacity, superior selectivity, good recyclability, and simple recycling routes), but also retains excellent flame retardancy and robust stability. In comparison to conventional methods, which usually utilize massive organic solvents, the present approach does not involve any complicated process or sophisticated equipment nor generates any waste liquids, and thus is a more labor-saving, environment-friendly, energy-efficient and cost-effective strategy for the hydrophobic modification. Taking into account the critical role of hydrophobic porous materials, especially in the field of environmental remediation, the approach presented herein would be highly valuable for environmental remediation and industrial applications. PMID:27501762

  19. Understanding the Mechanism of Action of Triazine-Phosphonate Derivatives as Flame Retardants for Cotton Fabric.

    PubMed

    Nguyen, Monique M; Al-Abdul-Wahid, M Sameer; Fontenot, Krystal R; Graves, Elena E; Chang, SeChin; Condon, Brian D; Grimm, Casey C; Lorigan, Gary A

    2015-01-01

    Countless hours of research and studies on triazine, phosphonate, and their combination have provided insightful information into their flame retardant properties on polymeric systems. However, a limited number of studies shed light on the mechanism of flame retardancy of their combination on cotton fabrics. The purpose of this research is to gain an understanding of the thermal degradation process of two triazine-phosphonate derivatives on cotton fabric. The investigation included the preparation of diethyl 4,6-dichloro-1,3,5-triazin-2-ylphosphonate (TPN1) and dimethyl (4,6-dichloro-1,3,5-triazin-2-yloxy) methyl phosphonate (TPN3), their application on fabric materials, and the studies of their thermal degradation mechanism. The studies examined chemical components in both solid and gas phases by using attenuated total reflection infrared (ATR-IR) spectroscopy, thermogravimetric analysis coupled with Fourier transform infrared (TGA-FTIR) spectroscopy, and 31P solid state nuclear magnetic resonance (31P solid state NMR), in addition to the computational studies of bond dissociation energy (BDE). Despite a few differences in their decomposition, TPN1 and TPN3 produce one common major product that is believed to help reduce the flammability of the fabric. PMID:26096432

  20. A Versatile and Scalable Approach toward Robust Superhydrophobic Porous Materials with Excellent Absorbency and Flame Retardancy

    PubMed Central

    Ruan, Changping; Shen, Mengxia; Ren, Xiaoyan; Ai, Kelong; Lu, Lehui

    2016-01-01

    The frequent oil spillages and the industrial discharge of organic contaminants have not only created severe environmental and ecological crises, but also cause a risk of fire and explosion. These environmental and safety issues emphasize the urgent need for materials that possess superior sorption capability and less flammability and thus can effectively and safely clean up the floating oils and water-insoluble organic compounds. Here we present the successful hydrophobic modification of the flame retardant melamine sponge with a commercial fluorosilicone, by using a facile one-step solvent-free approach and demonstrate that the resultant superhydrophobic sponge not only exhibits extraordinary absorption efficiency (including high capacity, superior selectivity, good recyclability, and simple recycling routes), but also retains excellent flame retardancy and robust stability. In comparison to conventional methods, which usually utilize massive organic solvents, the present approach does not involve any complicated process or sophisticated equipment nor generates any waste liquids, and thus is a more labor-saving, environment-friendly, energy-efficient and cost-effective strategy for the hydrophobic modification. Taking into account the critical role of hydrophobic porous materials, especially in the field of environmental remediation, the approach presented herein would be highly valuable for environmental remediation and industrial applications. PMID:27501762

  1. Characterizing Flame Retardant Applications and Potential Human Exposure in Backpacking Tents.

    PubMed

    Gomes, Genna; Ward, Peyton; Lorenzo, Amelia; Hoffman, Kate; Stapleton, Heather M

    2016-05-17

    Flame retardant (FR) chemicals are applied to products to meet flammability standards; however, exposure to some additive FRs has been shown to be associated with adverse health effects. Previous research on FR exposure has primarily focused on chemicals applied to furniture and electronics; however, camping tents sold in the United States, which often meet flammability standard CPAI-84, remain largely unstudied in regards to their chemical treatments. In this study, FRs from five brands of CPAI-84-compliant, two-person backpacking tents were measured and potential exposure was assessed. Dermal and inhalation exposure levels were assessed by collecting hand wipes from 20 volunteers before and after tent setup and by using active air samplers placed inside assembled tents, respectively. Organophosphate flame retardants (OPFRs) were the most commonly detected FR in the tent materials and included triphenyl phosphate (TPHP), tris(1,3-dichloro-2-propyl)phosphate (TDCIPP) and tris(2-chloroethyl)phosphate (TCEP). Levels of OPFRS measured on hand wipes were significantly higher post-tent setup compared to pre setup, and in the case of TDCIPP, levels were 29 times higher post setup. OPFRs were also detected at measurable concentrations in the air inside of treated tents. Significant, positive correlations were found between FR levels in treated textiles and measures of dermal and inhalation exposure. These results demonstrate that dermal exposure to FRs occurs from handling camping tents and that inhalation exposure will likely occur while inside a tent. PMID:27082445

  2. Urinary biomonitoring of phosphate flame retardants: levels in California adults and recommendations for future studies.

    PubMed

    Dodson, Robin E; Van den Eede, Nele; Covaci, Adrian; Perovich, Laura J; Brody, Julia Green; Rudel, Ruthann A

    2014-12-01

    Phosphate flame retardants (PFRs) are abundant and found at the highest concentrations relative to other flame retardant chemicals in house dust; however, little is known about the biological levels of PFRs and their relationship with house dust concentrations. These relationships provide insight into major exposure pathways and potential health risks. We analyzed urine samples from 16 California residents in 2011 for 6 chlorinated and nonchlorinated dialkyl or diaryl phosphates (DAPs), the expected major metabolites of the most prominent PFRs, and qualitatively screened for 18 other metabolites predicted from in vitro studies. We detected all 6 DAPs within the range of previously reported levels, although very few comparisons are available. We found weakly positive nonsignificant correlations between urine and dust concentrations and maxima urine corresponding to maxima dust for the pairs bis(1,3-dichloro-2-propyl) phosphate (BDCIPP)-tris(1,3-dichloro-isopropyl) phosphate (TDCIPP) and bis(2-chloroethyl) phosphate (BCEP)-tris(2-chloroethyl) phosphate (TCEP). Metabolite levels of PFRs were correlated for many PFR combinations, suggesting they commonly co-occur. As far as we know, this is the first study to measure these 6 DAP metabolites simultaneously and to detect other PFR metabolites in US urine samples. We recommend biomonitoring studies include these 6 DAPs as well as several additional compounds detected through qualitative screening and previous ADME studies. PFRs represent a class of poorly studied commercial chemicals with widespread exposure and raise concerns for health effects including carcinogenicity and neurotoxicity. PMID:25388620

  3. Organophosphorus flame retardants (PFRs) in human breast milk from several Asian countries.

    PubMed

    Kim, Joon-Woo; Isobe, Tomohiko; Muto, Mamoru; Tue, Nguyen Minh; Katsura, Kana; Malarvannan, Govindan; Sudaryanto, Agus; Chang, Kwang-Hyeon; Prudente, Maricar; Viet, Pham Hung; Takahashi, Shin; Tanabe, Shinsuke

    2014-12-01

    In this study, the concentrations of 10 organophosphorus flame retardants (PFRs) were determined in 89 human breast milk samples collected from Japan, the Philippines and Vietnam. Among the targeted PFRs, tris(2-chloroexyl) phosphate (TCEP) and triphenyl phosphate (TPHP) were the predominant compounds and were detected in more than 60% of samples in all three countries. The concentrations of PFRs in human breast milk were significantly higher (p<0.05) in the Philippines (median 70 ng g(-1) lipid wt.) than those in Japan (median 22 ng g(-1) lipid wt.) and Vietnam (median 10 ng g(-1) lipid wt.). The present results suggest that the usage of products containing PFRs in the Philippines is higher than those of Japan and Vietnam. Comparing with a previous literature survey in Sweden, the levels of PFRs in human breast milk from the Philippines were 1.5-2 times higher, whereas levels in Japan and Vietnam were 4-20 times lower, suggesting that these differences might be due to their variation in the usage of flame-retarded products utilized in each country. When daily intake of PFRs to infants via human breast milk was estimated, some individuals accumulated tris(2-butoxyethyl) phosphate (TBOEP) and TCEP were close to reference dose (RfD). This is the first report to identify PFRs in human breast milk samples from Asian countries. PMID:24630247

  4. Analytical and environmental aspects of the flame retardant tetrabromobisphenol-A and its derivatives.

    PubMed

    Covaci, Adrian; Voorspoels, Stefan; Abdallah, Mohamed Abou-Elwafa; Geens, Tinne; Harrad, Stuart; Law, Robin J

    2009-01-16

    The present article reviews the available literature on the analytical and environmental aspects of tetrabromobisphenol-A (TBBP-A), a currently intensively used brominated flame retardant (BFR). Analytical methods, including sample preparation, chromatographic separation, detection techniques, and quality control are discussed. An important recent development in the analysis of TBBP-A is the growing tendency for liquid chromatographic techniques. At the detection stage, mass-spectrometry is a well-established and reliable technology in the identification and quantification of TBBP-A. Although interlaboratory exercises for BFRs have grown in popularity in the last 10 years, only a few participating laboratories report concentrations for TBBP-A. Environmental levels of TBBP-A in abiotic and biotic matrices are low, probably due to the major use of TBBP-A as reactive FR. As a consequence, the expected human exposure is low. This is in agreement with the EU risk assessment that concluded that there is no risk for humans concerning TBBP-A exposure. Much less analytical and environmental information exists for the various groups of TBBP-A derivatives which are largely used as additive flame retardants. PMID:18760795

  5. A Versatile and Scalable Approach toward Robust Superhydrophobic Porous Materials with Excellent Absorbency and Flame Retardancy

    NASA Astrophysics Data System (ADS)

    Ruan, Changping; Shen, Mengxia; Ren, Xiaoyan; Ai, Kelong; Lu, Lehui

    2016-08-01

    The frequent oil spillages and the industrial discharge of organic contaminants have not only created severe environmental and ecological crises, but also cause a risk of fire and explosion. These environmental and safety issues emphasize the urgent need for materials that possess superior sorption capability and less flammability and thus can effectively and safely clean up the floating oils and water-insoluble organic compounds. Here we present the successful hydrophobic modification of the flame retardant melamine sponge with a commercial fluorosilicone, by using a facile one-step solvent-free approach and demonstrate that the resultant superhydrophobic sponge not only exhibits extraordinary absorption efficiency (including high capacity, superior selectivity, good recyclability, and simple recycling routes), but also retains excellent flame retardancy and robust stability. In comparison to conventional methods, which usually utilize massive organic solvents, the present approach does not involve any complicated process or sophisticated equipment nor generates any waste liquids, and thus is a more labor-saving, environment-friendly, energy-efficient and cost-effective strategy for the hydrophobic modification. Taking into account the critical role of hydrophobic porous materials, especially in the field of environmental remediation, the approach presented herein would be highly valuable for environmental remediation and industrial applications.

  6. Are some "safer alternatives" hazardous as PBTs? The case study of new flame retardants.

    PubMed

    Gramatica, Paola; Cassani, Stefano; Sangion, Alessandro

    2016-04-01

    Some brominated flame retardants (BFRs), as PBDEs, are persistent, bioaccumulative, toxic (PBT) and are restricted/prohibited under various legislations. They are replaced by "safer" flame retardants (FRs), such as new BFRs or organophosphorous compounds. However, informations on the PBT behaviour of these substitutes are often lacking. The PBT assessment is required by the REACH regulation and the PBT chemicals should be subjected to authorization. Several new FRs, proposed and already used as safer alternatives to PBDEs, are here screened by the cumulative PBT Index model, implemented in QSARINS (QSAR-Insubria), new software for the development/validation of QSAR models. The results, obtained directly from the chemical structure for the three studied characteristics altogether, were compared with those from the US-EPA PBT Profiler: the two different approaches are in good agreement, supporting the utility of a consensus approach in these screenings. A priority list of the most harmful FRs, predicted in agreement by the two modelling tools, has been proposed, highlighting that some supposed "safer alternatives" are detected as intrinsically hazardous for their PBT properties. This study also shows that the PBT Index could be a valid tool to evaluate appropriate and safer substitutes, a priori from the chemical design, in a benign by design approach, avoiding unnecessary synthesis and tests. PMID:26742016

  7. Urinary Biomonitoring of Phosphate Flame Retardants: Levels in California Adults and Recommendations for Future Studies

    PubMed Central

    2014-01-01

    Phosphate flame retardants (PFRs) are abundant and found at the highest concentrations relative to other flame retardant chemicals in house dust; however, little is known about the biological levels of PFRs and their relationship with house dust concentrations. These relationships provide insight into major exposure pathways and potential health risks. We analyzed urine samples from 16 California residents in 2011 for 6 chlorinated and nonchlorinated dialkyl or diaryl phosphates (DAPs), the expected major metabolites of the most prominent PFRs, and qualitatively screened for 18 other metabolites predicted from in vitro studies. We detected all 6 DAPs within the range of previously reported levels, although very few comparisons are available. We found weakly positive nonsignificant correlations between urine and dust concentrations and maxima urine corresponding to maxima dust for the pairs bis(1,3-dichloro-2-propyl) phosphate (BDCIPP)-tris(1,3-dichloro-isopropyl) phosphate (TDCIPP) and bis(2-chloroethyl) phosphate (BCEP)-tris(2-chloroethyl) phosphate (TCEP). Metabolite levels of PFRs were correlated for many PFR combinations, suggesting they commonly co-occur. As far as we know, this is the first study to measure these 6 DAP metabolites simultaneously and to detect other PFR metabolites in US urine samples. We recommend biomonitoring studies include these 6 DAPs as well as several additional compounds detected through qualitative screening and previous ADME studies. PFRs represent a class of poorly studied commercial chemicals with widespread exposure and raise concerns for health effects including carcinogenicity and neurotoxicity. PMID:25388620

  8. Body burdens of brominated flame retardants and other persistent organo-halogenated compounds and their descriptors in US girls

    SciTech Connect

    Windham, Gayle C.; Pinney, Susan M.; Sjodin, Andreas; Lum, Raymond; Jones, Richard S.; Needham, Larry L.; Biro, Frank M.; Hiatt, Robert A.; Kushi, Lawrence H.

    2010-04-15

    Background: Levels of brominated flame retardants are increasing in US populations, yet little data are available on body burdens of these and other persistent hormonally active agents (HAAs) in school-aged children. Exposures to such chemicals may affect a number of health outcomes related to development and reproductive function. Objective: Determine the distribution of biomarkers of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organo-chlorinated pesticides (OCPs), such as DDT/DDE, in children, and their variation by key descriptor variables. Methods: Ethnically diverse cohorts of girls 6-8 y old at baseline are being followed for growth and pubertal development in a multi-site, longitudinal study. Nearly 600 serum samples from the California and Ohio sites were analyzed for lipids, 35 PCB congeners, 11 PBDE congeners, and 9 OCPs. The biomarker distributions were examined and geometric means compared for selected analytes across categories of age, race, site, body mass index (BMI), parental education, maternal age at delivery, and breast feeding in adjusted models. Results: Six PBDE congeners were detected among greater than 70% of samples, with BDE-47 having the highest concentration (median 42.2, range 4.9-855 ng/g lipid). Girls in California had adjusted geometric mean (GM) PBDE levels significantly higher than girls in Ohio. Furthermore, Blacks had significantly higher adjusted GMs of all six PBDE congeners than Whites, and Hispanics had intermediate values. GMs tended to be lower among more obese girls, while other variables were not strongly associated. In contrast, GMs of the six PCB congeners most frequently detected were significantly lower among Blacks and Hispanics than Whites. PCBs and the three pesticides most frequently detected were also consistently lower among girls with high BMI, who were not breast-fed, whose mothers were younger, or whose care-givers (usually parents) were less educated. Girls in California had

  9. Brominated Flame Retardants and Other Persistent Organohalogenated Compounds in Relation to Timing of Puberty in a Longitudinal Study of Girls

    PubMed Central

    Pinney, Susan M.; Voss, Robert W.; Sjödin, Andreas; Biro, Frank M.; Greenspan, Louise C.; Stewart, Susan; Hiatt, Robert A.; Kushi, Lawrence H.

    2015-01-01

    Background Exposure to hormonally active chemicals could plausibly affect pubertal timing, so we are investigating this in the Breast Cancer and the Environment Research Program. Objectives Our goal was to examine persistent organic pollutants (POPs) in relation to pubertal onset. Methods Ethnically diverse cohorts of 6- to 8-year-old girls (n = 645) provided serum for measure of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and lipids. Tanner stages [breast (B) and pubic hair (PH)], and body mass index (BMI) were measured at up to seven annual clinic visits. Using accelerated failure time models, we calculated time ratios (TRs) for age at Tanner stages 2 or higher (2+) and POPs quartiles (Q1–4), adjusting for confounders (race/ethnicity, site, caregiver education, and income). We also calculated prevalence ratios (PRs) of Tanner stages 2+ at time of blood sampling. Results Cross-sectionally, the prevalence of B2+ and PH2+ was inversely related to chemical serum concentrations; but after adjustment for confounders, only the associations with B2+, not PH2+, were statistically significant. Longitudinally, the age at pubertal transition was consistently older with greater chemical concentrations; for example: adjusted TR for B2+ and Q4 for ΣPBDE = 1.05; 95% CI: 1.02, 1.08, for ΣPCB = 1.05; 95% CI: 1.01, 1.08, and for ΣOCP = 1.10; 95% CI: 1.06, 1.14, indicating median ages of about 6 and 11 months older than least exposed, and with similar effect estimates for PH2+. Adjusting for BMI attenuated associations for PCBs and OCPs but not for PBDEs. Conclusions This first longitudinal study of puberty in girls with serum POPs measurements (to our knowledge) reveals a delay in onset with higher concentrations. Citation Windham GC, Pinney SM, Voss RW, SjÖdin A, Biro FM, Greenspan LC, Stewart S, Hiatt RA, Kushi LH. 2015. Brominated flame retardants and other persistent organohalogenated compounds in relation to

  10. Multifunctional cyclotriphosphazene/hexagonal boron nitride hybrids and their flame retarding bismaleimide resins with high thermal conductivity and thermal stability.

    PubMed

    Jin, Wenqin; Yuan, Li; Liang, Guozheng; Gu, Aijuan

    2014-09-10

    A novel hybridized multifunctional filler (CPBN), cyclotriphosphazene/hexagonal boron nitride (hBN) hybrid, was synthesized by chemically coating hBN with hexachlorocyclotriphosphazene and p-phenylenediamine, its structure was systemically characterized. Besides, CPBN was used to develop new flame retarding bismaleimide/o,o'-diallylbisphenol A (BD) resins with simultaneously high thermal conductivity and thermal stability. The nature of CPBN has a strong influence on the flame behavior of the composites. With the addition of only 5 wt % CPBN to BD resin, the thermal conductivity increases 2 times; meanwhile the flame retardancy of BD resin is remarkably increased, reflected by the increased limited oxygen index, much longer time to ignition, significantly reduced heat release rate. The thermogravimetric kinetics, structures of chars and pyrolysis gases, and cone calorimeter tests were investigated to reveal the unique flame retarding mechanism of CPBN/BD composites. CPBN provides multieffects on improving the flame retardancy, especially in forming a protective char layer, which means a more thermally stable and condensed barrier for heat and mass transfer, and thus protecting the resin from further combustion. PMID:25140735

  11. Brominated flame retardants and polychlorinated biphenyls in human breast milk from several locations in India: potential contaminant sources in a municipal dumping site.

    PubMed

    Devanathan, Gnanasekaran; Subramanian, Annamalai; Sudaryanto, Agus; Takahashi, Shin; Isobe, Tomohiko; Tanabe, Shinsuke

    2012-02-01

    This study investigated the status of contamination of organohalogen compounds (OCs) such as polychlorinated biphenyls (PCBs) and brominated flame retardant (BFRs), including polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in human milk samples from several locations in India. The levels of OCs were significantly higher in the milk of mothers living in and near municipal dumping site than other locations indicating that the open dumping sites for municipal wastes act as potential sources of these contaminants in India. The PCB concentrations observed in this study tended to decrease compared to those in the matched locations reported previously, probably due to the restriction of technical PCB usage in India. PBDE levels in human milk were two to three folds lower than those of PCBs in all the sampling locations investigated. Congener profiles of PCBs and PBDEs were different between samples from the dumping site mothers and general populations in other areas suggesting the presence of region-specific sources and pathways. HBCDs were detected in human milk from only two sites, with much lower concentrations and detection frequencies compared to PCBs and PBDEs. When hazard quotients (HQs) of PCBs and PBDEs were estimated for infant health risk, the HQs in some milk samples from the dumping site exceeded the threshold value (HQ>1) of PCBs, indicating the potential risk for infants in the specific site. PMID:22208746

  12. Low concentrations of the brominated flame retardants BDE-47 and BDE-99 induce synergistic oxidative stress-mediated neurotoxicity in human neuroblastoma cells.

    PubMed

    Tagliaferri, Sara; Caglieri, Andrea; Goldoni, Matteo; Pinelli, Silvana; Alinovi, Rossella; Poli, Diana; Pellacani, Claudia; Giordano, Gennaro; Mutti, Antonio; Costa, Lucio G

    2010-02-01

    Polybrominated diphenyl ether (PBDE) flame retardants have become widespread environmental contaminants. The highest body burden has been found in toddlers and infants, due to their exposure through breast milk and house dust, and the current concern for potential adverse health effects of PBDEs relates to their developmental neurotoxicity. The mechanisms underlying the neurotoxicity of PBDEs are largely not understood, though there is evidence that PBDEs may elicit oxidative stress. In this study, two different mathematical models were used to evaluate the interaction between BDE-47 and BDE-99 on viability of neuronal cells. The combined exposure to these compounds induced synergistic effects at concentrations of BDE-47 below its threshold doses, and in a wide range of BDE-99 concentrations below its IC(50). In contrast, at concentrations of BDE-47 near its IC(50) value, and in a wide range of BDE-99 concentrations, antagonistic effects were observed. The interactions observed on cell viability were confirmed by an assessment of induction of oxidative stress. The finding that co-exposure to BDE-47 and BDE-99 could induce synergistic neurotoxic effects, in particular at low doses of BDE-47, is of much toxicological interest, as humans are exposed to mixtures of PBDEs, most notably tetra- and penta-BDE congeners. PMID:19720130

  13. Comparative antioxidant status in freshwater fish Carassius auratus exposed to six current-use brominated flame retardants: a combined experimental and theoretical study.

    PubMed

    Feng, Mingbao; Qu, Ruijuan; Wang, Chao; Wang, Liansheng; Wang, Zunyao

    2013-09-15

    Decabromodiphenyl ether (BDE-209) and several non-polybrominated diphenyl ether (PBDE) brominated flame retardants (BFRs), such as tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB) and pentabromotoluene (PBT), are persistent halogenated contaminants ubiquitously detected in aquatic systems. However, data on comparative toxicological effects of these BFRs are lacking for fish. In this study, a combined experimental and theoretical approach was used to compare and analyze the effects of these BFRs on biochemical biomarkers in liver of Carassius auratus injected intraperitoneally with different doses (10 and 100mg/kg) for 7, 14 and 30 days. Oxidative stress was evoked evidently for the prolonged exposure, represented by the significantly altered indices (superoxide dismutase, catalase, glutathione peroxidase, reduced glutathione, and malondialdehyde). The integrated biomarker response (IBR) index ranked biotoxicity as: PBT>HBB>HBCD>TBBPA>BDE-209>DBDPE. Quantum chemical calculations (electronic parameters, frontier molecular orbitals, and Wiberg bond order) were performed for theoretical analysis. Notably, some descriptors were correlated with the toxicity order, probably implying the existence of a potential structure-activity relationship when more BFRs were included. Besides, theoretical calculations also provided some valuable information regarding the molecular characteristics and metabolic pathways of these current-use BFRs, which may facilitate the understanding on their environmental behavior and fate. Overall, this study adopted a combined experimental and theoretical method for the toxicological determination and analysis of the BFRs, which may also be considered in future ecotoxicological studies. PMID:23880106

  14. Brominated flame retardants and organochlorine contaminants in winter flounder, harp and hooded seals, and North Atlantic right whales from the Northwest Atlantic Ocean.

    PubMed

    Montie, Eric W; Letcher, Robert J; Reddy, Christopher M; Moore, Michael J; Rubinstein, Belinda; Hahn, Mark E

    2010-08-01

    Various brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs) and current-use, non-PBDE BFRs, as well as organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs), were measured in winter flounder, harp and hooded seals, and North Atlantic right whales from the Eastern United States and Canada. The concentrations of PBDEs in winter flounder and right whales were similar in magnitude to the levels of PCBs, which was unlike the pattern observed in seals. In these marine mammals, the levels of PBDEs were orders of magnitude lower than the levels of OCs and PCBs detected. Evidence existed for the accumulation of methoxylated (MeO)-PBDEs of natural origin in seals and right whales. Current-use, non-PBDE BFRs (including hexabromocyclododecane, pentabromoethylbenzene, hexabromobenzene, and pentabromotoluene) were detected in winter flounder and marine mammals. Future research should focus on monitoring PBDEs, current-use, non-PBDE BFRs, and MeO-BDEs of natural origin in marine organisms from Massachusetts and Cape Cod Bays. PMID:20434733

  15. Towards development of a rapid and effective non-destructive testing strategy to identify brominated flame retardants in the plastics of consumer products.

    PubMed

    Gallen, Christie; Banks, Andrew; Brandsma, Sicco; Baduel, Christine; Thai, Phong; Eaglesham, Geoff; Heffernan, Amy; Leonards, Pim; Bainton, Paul; Mueller, Jochen F

    2014-09-01

    Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs) once extensively used in the plastics of a wide range of consumer products. The listing of certain congeners that are constituents of commercial PBDE mixtures (including c-octaBDE) in the Stockholm Convention and tightening regulation of many other BFRs in recent years have created the need for a rapid and effective method of identifying BFR-containing plastics. A three-tiered testing strategy comparing results from non-destructive testing (X-ray fluorescence (XRF)) (n=1714), a surface wipe test (n=137) and destructive chemical analysis (n=48) was undertaken to systematically identify BFRs in a wide range of consumer products. XRF rapidly identified bromine in 92% of products later confirmed to contain BFRs. Surface wipes of products identified tetrabromobisphenol A (TBBPA), c-octaBDE congeners and BDE-209 with relatively high accuracy (>75%) when confirmed by destructive chemical analysis. A relationship between the amounts of BFRs detected in surface wipes and subsequent destructive testing shows promise in predicting not only the types of BFRs present but also estimating the concentrations present. Information about the types of products that may contain persistent BFRs will assist regulators in implementing policies to further reduce the occurrence of these chemicals in consumer products. PMID:24529451

  16. Flame retardant brominated styrene-based polymers. V. Synthesis and characterization of dibromostyrene and butyl acrylate latices with and without itaconic acid

    SciTech Connect

    Wang, J.L.; Favstritsky, N.A.; Hemmerly, D.M.

    1995-12-01

    Dibranostyrene and butyl acrylate lattices with and without itaconic acid having desirable physical properties in combination with flame retardancy are prepared by an emulsion polymerization techniques Both lattices were characterized in terms of glass transition temperature (Tg), residual monomer, solids, Brookfield viscosity, UV stability and flame retardancy.

  17. Fire self-extinguishing cotton fabric: development of piperazine derivatives containing phosphorous-sulfur-nitrogen and their flame retardant and thermal behaviors

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Recent studies have shown interest in flame retardants containing phosphorus, nitrogen and sulfur a combination small molecule with a promising new approach in preparing an important class of flame retardant materials. Tetraethyl piperazine-1,4-diyldiphosphonate (TEPP) and O,O,O',O'-tetramethyl pip...

  18. Occupational exposure of air crews to tricresyl phosphate isomers and organophosphate flame retardants after fume events.

    PubMed

    Schindler, Birgit Karin; Weiss, Tobias; Schütze, Andre; Koslitz, Stephan; Broding, Horst Christoph; Bünger, Jürgen; Brüning, Thomas

    2013-04-01

    Aircraft cabin air can possibly be contaminated by tricresyl phosphates (TCP) from jet engine oils during fume events. o-TCP, a known neurotoxin, has been addressed to be an agent that might cause the symptoms reported by cabin crews after fume events. A total of 332 urine samples of pilots and cabin crew members in common passenger airplanes, who reported fume/odour during their last flight, were analysed for three isomers of tricresyl phosphate metabolites as well as dialkyl and diaryl phosphate metabolites of four flame retardants. None of the samples contained o-TCP metabolites above the limit of detection (LOD 0.5 μg/l). Only one sample contained metabolites of m- and p-tricresyl phosphates with levels near the LOD. Median metabolite levels of tributyl phosphate (TBP), tris-(2-chloroethyl) phosphate (TCEP) and triphenyl phosphate (TPP) (DBP 0.28 μg/l; BCEP 0.33 μg/l; DPP 1.1 μg/l) were found to be significantly higher than in unexposed persons from the general population. Median tris-(2-chloropropyl) phosphate (TCPP) metabolite levels were significantly not higher in air crews than in controls. Health complaints reported by air crews can hardly be addressed to o-TCP exposure in cabin air. Elevated metabolite levels for TBP, TCEP and TPP in air crews might occur due to traces of hydraulic fluid in cabin air (TBP, TPP) or due to release of commonly used flame retardants from the highly flame protected environment in the airplane. A slight occupational exposure of air crews to organophosphates was shown. PMID:23179756

  19. Intumescent multilayer nanocoating, made with renewable polyelectrolytes, for flame-retardant cotton.

    PubMed

    Laufer, Galina; Kirkland, Christopher; Morgan, Alexander B; Grunlan, Jaime C

    2012-09-10

    Thin films of fully renewable and environmentally benign electrolytes, cationic chitosan (CH) and anionic phytic acid (PA), were deposited on cotton fabric via layer-by-layer (LbL) assembly in an effort to reduce flammability. Altering the pH of aqueous deposition solutions modifies the composition of the final nanocoating. CH-PA films created at pH 6 were thicker and had 48 wt % PA in the coating, while the thinnest films (with a PA content of 66 wt %) were created at pH 4. Each coating was evaluated at both 30 bilayers (BL) and at the same coating weight added to the fabric. In a vertical flame test, fabrics coated with high PA content multilayers completely extinguished the flame, while uncoated cotton was completely consumed. Microcombustion calorimetry confirmed that all coated fabric reduces peak heat release rate (pkHRR) by at least 50% relative to the uncoated control. Fabric coated with pH 4 solutions shows the greatest reduction in pkHRR and total heat release of 60% and 76%, respectively. This superior performance is believed to be due to high phosphorus content that enhances the intumescent behavior of these nanocoatings. These results demonstrate the first completely renewable intumescent LbL assembly, which conformally coats every fiber in cotton fabric and provides an effective alternative to current flame retardant treatments. PMID:22897635

  20. Bioaccumulation and biomagnification of classical flame retardants, related halogenated natural compounds and alternative flame retardants in three delphinids from Southern European waters.

    PubMed

    Barón, E; Giménez, J; Verborgh, P; Gauffier, P; De Stephanis, R; Eljarrat, E; Barceló, D

    2015-08-01

    Occurrence and behaviour of classical (PBDEs) and alternative (HNs, HBB, PBEB, DBDPE and HBCD) flame retardants, together with naturally produced MeO-PBDEs, were studied in short-beaked common dolphin (Delphinus delphis), bottlenose dolphin (Tursiops truncatus) and long-finned pilot whale (Globicephala melas) in two sampling locations from Southern European waters. PBDEs, Dec 602, Dec 603, DP, α-HBCD and two MeO-PBDEs were detected in all three species. ∑PBDEs were between 17 and 2680 ng/g lw; ∑HNs were between 1.1 and 59 ng/g lw; α-HBCD levels ranged between 3.2 and 641 ng/g lw; ∑MeO-PBDEs were between 34 and 1966 ng/g lw. Bottlenose dolphins were the most contaminated species and some individuals could present health risk for endocrine disruption since levels found were above the reported threshold (1500 ng/g lw). Stable isotope analysis was used to evaluate the biomagnification capacity of these compounds. PBDEs, MeO-PBDEs and Dec 602 showed a significant positive correlation with trophic position. PMID:25875161

  1. Photochemical degradation of a brominated flame retardant (tetrabromobisphenol A) in ice under field and laboratory conditions

    NASA Astrophysics Data System (ADS)

    Waligroski, G.; Grannas, A. M.

    2013-12-01

    Studies of brominated flame retardants have raised awareness of their potential environmental impact as toxic compounds. Because these compounds are now globally distributed, including in the Polar Regions, it is important to assess their potential fate in the environment. It has been shown that active photochemistry occurs in sunlit snow and ice, but there is little information regarding potential photochemical degradation of brominated flame retardants in snow and ice. The purpose of this research is to investigate the direct and indirect photochemical transformation pathways of a widely used brominated flame retardant, tetrabromobisphenol A (TBBPA). We have conducted field-based experiments in Barrow, Alaska to investigate the potential photochemical degradation of TBBPA in snow and ice under environmentally-relevant conditions. Field-based results show that TBBPA is efficiently degraded under direct photolysis conditions in frozen aqueous samples under natural Barrow sunlight. In aqueous solution the light absorption properties of TBBPA are pH dependent. Therefore, the photodegradation of TBBPA in snow and ice will be highly pH dependent. Reactions that are pH dependent may be affected by the nature of the liquid-like layers in snow/ice as well as the presence of other solutes that may indirectly affect the local pH experienced by TBBPA in snow and ice samples. In order to establish how the effective pH of liquid-like regions in ice might impact the degradation of TBBPA, various salts (sodium chloride, sodium fluoride, sodium bromide, ammonium chloride, ammonium acetate and ammonium sulfate) were added to aqueous solutions of TBBPA. Upon freezing, these different salts will induce pH differences in the liquid-like regions of the sample due to a phenomenon known as the freezing potential. Observed reactivity differences upon addition of these salts will be evaluated and discussed. Additionally, the presence of natural dissolved organic matter (DOM), an effective

  2. IN VITRO EFFECTS OF BROMINATED FLAME RETARDANS ON CALCIUM BUFFERING MECHANISMS IN RAT BRAINS.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are widely used as additive flame-retardants and have been detected in human blood, adipose tissue, and breast milk. Developmental and long-term exposures to these chemicals may pose a human health risk, especially to children. It has been d...

  3. Use of Mass Spectrometry for Identification of Biomarkers of Exposure to the Flame Retardant DI(2-Ethylhexyl)-2,3,4,5-Tetrabromophthlate

    EPA Science Inventory

    Di-(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH) is one component in the technical formulation of Firemaster 550, a fire retardant used after phasing out certain polybrominated diphenyl ethers. Firemaster 550 is used widely and its use may result in human exposure to TBPH. To...

  4. Studies of flammability and thermal degradation for flame retardant cotton fabric with P-N containing derivatives

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The effectiveness of a phosphoramidate Tetraethyl piperazine-1,4- diyldiphosphoramidate (TEPP) as a flame retardant (FR) on cotton twill fabrics was compared with that of a previously studied Diethyl 4- methylpiperazin-1-ylphosphoramidate (DEPP). TEPP was formed in a reaction between two phosphonat...

  5. Toxicokinetics of the Sterioisomer Specific Flame Retardant Hexabromocyclododecane (HBCD) Gamma: Effect of Dose, Time, and Repeated Exposure

    EPA Science Inventory

    Hexabromocyclododecanes (HBCDs) are high production volume brominated aliphatic cyclic hydrocarbons used as flame-retardants in foams, plastics and textiles. Commercial HBCD is a mixture of three main stereoisomers, alpha (α), beta (β) and gamma (γ). A shift from the high percent...

  6. Development of an environmentally friendly halogen-free phosphorous-nitrogen bond flame retardant for cotton fabrics

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A novel flame retardant Diethyl 4-methylpiperazin-1-ylphosphoramidate, CN-3, containing phosphorous and nitrogen was prepared. Its chemical structure was confirmed by nuclear magnetic resonance (1H, 13C, 31P NMR), Fourier transform infrared spectrometry (FTIR), and elemental analysis. Print cloth an...

  7. Application of a phosphazene derivative as a flame retardant for cotton fabric using conventional method and supercritical CO2

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Conventional pad-dry-cure (non-scCO2) and supercritical carbon dioxide (scCO2) application methods were investigated to study the effectiveness of a phosphazene derivative as a flame retardant on cotton fabric. 1,1',4,5-tetrahydrotrispiro[1,3,2-diazaphosphole-2,2'-[1,3,5,2,4,6]triazatriphosphinine-4...

  8. Synthesis and characterization of a novel phosphorus-nitrogen containing flame retardant and its application for textile

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The economic and environmentally friendly flame retardant compound, tetramethyl (6-chloro-1,3,5-triazine-2,4-diyl)bis(oxy)bis (methylene)diphosphonate (FR-1) was synthesized by a simple 2 step procedure from dimethyl phosphate, and its chemical structure was characterized by 1H, 13C, and 31P nuclea...

  9. Preparation of candidate reference materials for the determination of phosphorus containing flame retardants in styrene-based polymers.

    PubMed

    Roth, Thomas; Urpi Bertran, Raquel; Latza, Andreas; Andörfer-Lang, Katrin; Hügelschäffer, Claudia; Pöhlein, Manfred; Puchta, Ralph; Placht, Christian; Maid, Harald; Bauer, Walter; van Eldik, Rudi

    2015-04-01

    Candidate reference materials (RM) for the analysis of phosphorus-based flame retardants in styrene-based polymers were prepared using a self-made mini-extruder. Due to legal requirements of the current restriction for the use of certain hazardous substances in electrical and electronic equipment, focus now is placed on phosphorus-based flame retardants instead of the brominated kind. Newly developed analytical methods for the first-mentioned substances also require RMs similar to industrial samples for validation and verification purposes. Hence, the prepared candidate RMs contained resorcinol-bis-(diphenyl phosphate), bisphenol A bis(diphenyl phosphate), triphenyl phosphate and triphenyl phosphine oxide as phosphorus-based flame retardants. Blends of polycarbonate and acrylonitrile-co-butadiene-co-styrene as well as blends of high-impact polystyrene and polyphenylene oxide were chosen as carrier polymers. Homogeneity and thermal stability of the candidate RMs were investigated. Results showed that the candidate RMs were comparable to the available industrial materials. Measurements by ICP/OES, FTIR and NMR confirmed the expected concentrations of the flame retardants and proved that analyte loss and degradation, respectively, was below the uncertainty of measurement during the extrusion process. Thus, the candidate RMs were found to be suitable for laboratory use. PMID:25410641

  10. Structural effect of alkyl substituent on oxygen atom for the thermal and flame retardant behaviors of phosphoramidates

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The present research is aimed at studying the structural effect of two phosphoramidate derivatives EHP Diethyl 3-hydroxypropylphosphoramidate and MHP Dimethyl 3-hydroxypropylphosphoramidate as flame retardants (FRs) for cotton cellulose. EHP and MHP were obtained in very high yield and purity by on...

  11. Advances in Instrumental Analysis of Brominated Flame Retardants: Current Status and Future Perspectives

    PubMed Central

    2014-01-01

    This review aims to highlight the recent advances and methodological improvements in instrumental techniques applied for the analysis of different brominated flame retardants (BFRs). The literature search strategy was based on the recent analytical reviews published on BFRs. The main selection criteria involved the successful development and application of analytical methods for determination of the target compounds in various environmental matrices. Different factors affecting chromatographic separation and mass spectrometric detection of brominated analytes were evaluated and discussed. Techniques using advanced instrumentation to achieve outstanding results in quantification of different BFRs and their metabolites/degradation products were highlighted. Finally, research gaps in the field of BFR analysis were identified and recommendations for future research were proposed. PMID:27433482

  12. Effect of Nitrogen Additives on Flame Retardant Action of Tributyl Phosphate: Phosphorus – Nitrogen Synergism

    SciTech Connect

    Gaan, Sabyasachi; Sun, Gang; Hutches, Katherine; Engelhard, Mark H.

    2008-01-01

    The effect of nitrogen additives like urea, guanidine carbonate and melamine formaldehyde on the flame retardant efficacy of tributyl phosphate (TBP) has been investigated. From the LOI tests on treated cotton it is clear that the nitrogen additives have synergistic action. Estimation of activation energy of decomposition of treated cotton indicated that nitrogen additives enhance the thermal stability during the burning process. SEM pictures of chars formed after LOI test showed the formation of protective polymeric coating on the surface. The surface of chars formed were evaluated using FTIR-ATR and XPS analysis which showed that the coating was composed of Phosphorus-Nitrogen-Oxygen containing species. Formation of this coating during the burning process could lead to the synergistic interaction of phosphorus and nitrogen. Based on the experimental data we have further proposed several reaction mechanisms which could contribute to synergistic action and formation of protective coating on the surface of char.

  13. One-step synthesis and flame retardancy of sheaf-like microcrystal antimony oxychloride.

    PubMed

    Zhou, Jing; Zhao, Hewei; Li, Lidong; Tian, Ming; Han, Jibing; Zhang, Liqun; Guo, Lin

    2011-10-01

    A mild and facile solution route has been developed for large-scale synthesis of sheaf-like antimony oxychloride Sb8O11CI2 (H2O)6 microcrystal at room temperature. The morphologies and structures of the as-prepared products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A mechanism for the formation of the sheaf-like microstructure was tentatively proposed. The shape regulation was attributed to the capping mode of the PVP-directed antimony oxychloride crystal. The thermogravimetric and differential thermal analysis (TG/DTA) were employed to investigate thermal decomposition mechanism and temperature-dependent phase transition of antimony oxychloride Sb8O11CI2 (H2O)6 in the air. The flammable property determined by the cone calorimeter showed excellent flame retardancy when applied this antimony oxychloride in poly (vinyl chloride) (PVC) polymer. PMID:22400215

  14. Lithium-Ion Electrolytes Containing Phosphorous-Based, Flame-Retardant Additives

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Smith, Kiah A.; Bugga, Ratnakumar V.; Prakash, G. K. Surya

    2010-01-01

    Future NASA missions aimed at exploring Mars, the Moon, and the outer planets require rechargeable batteries that can operate over a wide temperature range (-60 to +60 C) to satisfy the requirements of various applications. In addition, many of these applications will require improved safety, due to their use by humans. Currently, the state-of-the-art lithium-ion (Li-ion) system has been demonstrated to operate over a wide range of temperatures (-40 to +40 C); however, abuse conditions can often lead to cell rupture and fire. The nature of the electrolyte can greatly affect the propensity of the cell/battery to catch fire, given the flammability of the organic solvents used within. Li-ion electrolytes have been developed that contain a flame-retardant additive in conjunction with fluorinated co-solvents to provide a safe system with a wide operating temperature range. Previous work incorporated fluorinated esters into multi-component electrolyte formulations, which were demonstrated to cover a temperature range from 60 to +60 C. This work was described in Fluoroester Co-Solvents for Low-Temperature Li+ Cells (NPO-44626), NASA Tech Briefs, Vol. 33, No. 9 (September 2009), p. 37; and Optimized Li-Ion Electrolytes Con tain ing Fluorinated Ester Co-Solvents (NPO-45824), NASA Tech Briefs, Vol. 34, No. 3 (March 2010), p. 48. Other previous work improved the safety characteristics of the electrolytes by adding flame-retardant additives such as triphenyl phosphate (TPhPh), tri-butyl phosphate (TBuPh), triethyl phosphate (TEtPh), and bis(2,2,2-trifluoroethyl) methyl phosphonate (TFMPo). The current work involves further investigation of other types of flame-retardant additives, including tris(2,2,2-trifluoroethyl) phosphate, tris(2,2,2-trifluoroethyl) phosphite, triphenylphosphite, diethyl ethylphosphonate, and diethyl phenylphosphonate added to an electrolyte composition intended for wide operating temperatures. In general, many of the formulations investigated in this

  15. Classification and toxicity mechanisms of novel flame retardants (NFRs) based on whole genome expression profiling.

    PubMed

    Guan, Miao; Su, Guanyong; Giesy, John P; Zhang, Xiaowei

    2016-02-01

    Recently some novel alternative flame retardants (NFRs), which have been widely applied to meet demands for mandated flame retardation of products, have been detected in various matrices of the environment. However, knowledge on toxic effects and associated molecular mechanisms of these chemicals was limited. Here, toxic mechanisms of action of six NFRs, bis (2-ethylhexyl) phosphate (BEHP), chlorendic acid (Het acid), 2,2-bis (bromomethyl)-1,3-propanediol (BMP), tris (2-butoxyethyl) phosphate (TBEP), triethyl phosphate (TEP), tributyl phosphate (TBP) were investigated by use of a library containing ∼1820 modified green fluorescent protein (GFP) expressing promoter reporter vectors constructed from Escherichia coli K12(E.coli). BEHP, Het acid, BMP, TBEP, TEP, TBP inhibited growth of E. coli with 4 h 10%-inhibition concentrations of 53.0-3102.3 μM. A total of 119, 44, 26, 131, 62, 103 genes out of 336 genes selected during preliminary screening were significantly altered with fold-changes greater than 1.5 by BEHP, Het acid, BMP, TBEP, TEP and TBP, respectively. GO analyses of responsive genes suggested that RNA and primary metabolism process were involved in molecular mechanisms of toxicity. Chemical clustering based on expression of 62 multi-responsive genes showed that BEHP, TBP and TBEP were grouped together, which is consistent with similarity of their chemical structures, especially for BEHP and TBP. Clustering by molecular descriptors and molecular activity by use of the multivariate classification system ToxCast was consistent with that by profiles of multi-responsive genes. The results of this study demonstrated the utility of the E. coli, whole-cell assay for determining mechanisms of toxic action of chemicals. PMID:26588597

  16. Use of alternative assays to identify and prioritize organophosphorus flame retardants for potential developmental and neurotoxicity.

    PubMed

    Behl, Mamta; Hsieh, Jui-Hua; Shafer, Timothy J; Mundy, William R; Rice, Julie R; Boyd, Windy A; Freedman, Jonathan H; Hunter, E Sidney; Jarema, Kimberly A; Padilla, Stephanie; Tice, Raymond R

    2015-01-01

    Due to their toxicity and persistence in the environment, brominated flame retardants (BFRs) are being phased out of commercial use, leading to the increased use of alternative chemicals such as the organophosphorus flame retardants (OPFRs). There is, however, limited information on the potential health effects of OPFRs. Due to the structural similarity of the OPFRs to organophosphorus insecticides, there is concern regarding developmental toxicity and neurotoxicity. In response, we evaluated a set of OPFRs (triphenyl phosphate [TPHP]), isopropylated phenyl phosphate [IPP], 2-ethylhexyl diphenyl phosphate [EHDP], tert-butylated phenyl diphenyl phosphate [BPDP], trimethyl phenyl phosphate [TMPP], isodecyl diphenyl phosphate [IDDP], (tris(1,3-dichloroisopropyl) phosphate [TDCIPP], and tris(2-chloroethyl)phosphate [TCEP]) in a battery of cell-based in vitro assays and alternative model organisms and compared the results to those obtained for two classical BFRs (3,3',5,5'-tetrabromobisphenol A [TBBPA] and 2,2'4,4'-brominated diphenyl ether [BDE-47]). The assays used evaluated the effects of chemicals on the differentiation of mouse embryonic stem cells, the proliferation and growth of human neural stem cells, rat neuronal growth and network activity, and development of nematode (Caenorhabditis elegans) and zebrafish (Danio rerio). All assays were performed in a concentration-response format, allowing for the determination of the point of departure (POD: the lowest concentration where a chemically-induced response exceeds background noise). The majority of OPFRs (8/9) were active in multiple assays in the range of 1-10 μM, most of which had comparable activity to the BFRs TBBPA and BDE-47. TCEP was negative in all assays. The results indicate that the replacement OPFRs, with the exception of TCEP, showed comparable activity to the two BFRs in the assays tested. Based on these results, more comprehensive studies are warranted to further characterize the potential hazard

  17. Distribution of copper, silver and gold during thermal treatment with brominated flame retardants

    SciTech Connect

    Oleszek, Sylwia; Grabda, Mariusz; Shibata, Etsuro; Nakamura, Takashi

    2013-09-15

    Highlights: • Copper, silver and gold during thermal treatment with brominated flame retardants. • Distribution of copper, silver and gold during thermal processing. • Thermodynamic considerations of the bromination reactions. - Abstract: The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition. In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000 °C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is

  18. Clay-chitosan nanobrick walls: completely renewable gas barrier and flame-retardant nanocoatings.

    PubMed

    Laufer, Galina; Kirkland, Christopher; Cain, Amanda A; Grunlan, Jaime C

    2012-03-01

    Thin films prepared via a layer-by-layer (LbL) assembly of renewable materials exhibit exceptional oxygen barrier and flame-retardant properties. Positively charged chitosan (CH), at two different pH levels (pH 3 and pH 6), was paired with anionic montmorillonite (MMT) clay nanoplatelets. Thin-film assemblies prepared with CH at high pH are thicker, because if the low polymer charge density. A 30-bilayer (CH pH 6-MMT) nanocoating (~100 nm thick) reduces the oxygen permeability of a 0.5-mm-thick polylactic acid film by four orders of magnitude. This same coating system completely stops the melting of a flexible polyurethane foam, when exposed to direct flame from a butane torch, with just 10 bilayers (~30 nm thick). Cone calorimetry confirms that this coated foam exhibited a reduced peak heat-release rate, by as much as 52%, relative to the uncoated control. These environmentally benign nanocoatings could prove beneficial for new types of food packaging or a replacement for environmentally persistent antiflammable compounds. PMID:22339671

  19. Layer-by-Layer Assembly of Multifunctional Flame Retardant Based on Brucite, 3-Aminopropyltriethoxysilane, and Alginate and Its Applications in Ethylene-Vinyl Acetate Resin.

    PubMed

    Wang, Yiliang; Yang, Xiaomei; Peng, Hui; Wang, Fang; Liu, Xiu; Yang, Yunguo; Hao, Jianwei

    2016-04-20

    An efficient and multifunctional brucite/3-aminopropyltriethoxysilane (APTES)/nickel alginate/APTES (B/A/Nia/A) hybrid flame retardant was fabricated via the layer-by-layer assembly technique with brucite, silane coupling agents, nickel chloride, and sodium alginate. The morphology, chemical composition, and structure of the hybrid flame retardant were characterized. The results confirmed the multilayer structure and indicated that the assembled driving forces were electrostatic interactions, dehydration condensation, hydrogen bonds, and coordination bonds. When used in ethylene-vinyl acetate (EVA) resin, the multifunctional flame retardant had better performance than brucite in improving the flame retardancy, smoke suppression, and mechanical properties. With 130 phr loading, the multifunctional flame retardant achieved a limiting oxygen index value of 32.3% and a UL 94 V-0 rating, whereas the brucite achieved only 31.1% and a V-2 rating, respectively. The peak heat release rate and total heat released decreased by 41.5% and 8.9%, respectively. The multifunctional flame retardant had an excellent performance in reducing the smoke, CO, and CO2 production rates. These improvements could be attributed to the catalyzing carbonization of nickel compounds and the formation of more protective char layers. Moreover, the elongation at break increased by 97.5%, which benefited from the improved compatibility and the sacrificial bonds in the nickel alginate. The mechanism of flame retardant, smoke suppression, and toughening is proposed. PMID:27002922

  20. Development of flame retardant PV module encapsulants: Volume 1. Final report

    SciTech Connect

    Galica, J.P.

    1998-06-01

    This Phase 1 final report covers the work performed by Springborn Testing and Research, Inc., for the period October 1, 1997 to June 30, 1998 under the Department of Energy Cooperative Agreement Number DE-FC36-97GO10255, entitled Development of Flame Retardant PV Module Encapsulants. While use of roof-mounted arrays has always been an attractive means of deploying PV, only within recent years have such building integrated concepts (BIPV) found renewed interest among module makers and end-users. Prior to building integrated and rooftop applications, flammability requirements for modules have not been a great industry concern. However, with growing interest in BIPV and the requirement for building code requirements for commercial and industrial structures, flammability issues have become a barrier to entry for many module constructions into this potentially huge domestic market for PV. The overall goal of the 3 phase PV BONUS two project is to develop and commercialize a line of fire retardant encapsulation materials to serve the emerging building integrated and building mounted PV market. The objectives of the Phase 1 effort are limited to concept development and business planning activities.

  1. Health risk characterization for resident inhalation exposure to particle-bound halogenated flame retardants in a typical e-waste recycling zone.

    PubMed

    Luo, Pei; Bao, Lian-Jun; Wu, Feng-Chang; Li, Shao-Meng; Zeng, Eddy Y

    2014-01-01

    Inhalation of pollutants is an important exposure route for causing human health hazards, and inhalation exposure assessment must take into account particle size distribution because particle-bound pollutants are size-dependent. Such information is scarce, particularly for residents dwelling within e-waste recycling zones where abundant atmospheric halogenated flame retardants (HFRs) commonly used in electronic/electrical devices have been widely reported. Atmospheric size-fractioned particle samples were collected using a 10-stage Micro-Orifice Uniform Deposit Impactor from an e-waste recycling zone in South China. The deposition efficiencies and fluxes of size-fractioned HFRs including polybrominated diphenyl ethers (PBDEs), alternative brominated flame retardants, and Dechlorane Plus in the human respiratory tract were estimated using the International Commission on Radiological Protection deposition model. The majority of HFRs was found to deposit in the head airways, with coarse particles (aerodynamic diameter (Dp) > 1.8 μm) contributing the most (69-91%). Conversely, fine particles (Dp < 1.8 μm) were dominant in the alveolar region (62-80%). The inhalation intake of PBDEs within the e-waste recycling zone was 44 ng/d (95% confidence interval (CI): 30-65 ng/d), close to those through food consumption in non-e-waste recycling regions. The estimated total hazard quotient of particle-bound HFRs was 5.6 × 10(-4) (95% CI: 3.8 × 10(-4)-8.8 × 10(-4)). In addition, incremental lifetime cancer risk induced by BDE-209 was 1.36 × 10(-10) (95% CI: 7.3 × 10(-11)-2.3 × 10(-10)), much lower than the Safe Acceptable Range (1.0 × 10(-6)-1.0 × 10(-4)) established by the United States Environmental Protection Agency. These results indicate that the potential health risk from inhalation exposure to particle-bound HFRs for residents dwelling in the e-waste recycling zone was low. PMID:24992563

  2. A study of the dynamic flammability of radiation cross-linked flame-retardant HDPE/EPDM/silicon-elastomer compound

    NASA Astrophysics Data System (ADS)

    Jia, Shaojin; Zhang, Zhicheng; Du, Zhiwen; Teng, Renrui; Wang, Zhengzhou

    2003-04-01

    A dynamic flammability study of flame-retardant compound consisting of HDPE, EPDM and silicon elastomer blended with additives, as wire and cable insulation was made before and after irradiation. The data of RHR, EHC, SEC and the concentration of CO and CO 2 from cone colorimeter shown in the burning process were accessed. By blending silicon elastomer, CO release rate was reduced and the thermal endurance was improved. Oxygen index, mechanical property, morphology of the char formed in dynamical flame and thermal stability were also investigated.

  3. Aryl organophosphate flame retardants induced cardiotoxicity during zebrafish embryogenesis: by disturbing expression of the transcriptional regulators.

    PubMed

    Du, Zhongkun; Wang, Guowei; Gao, Shixiang; Wang, Zunyao

    2015-04-01

    As a result of the ban on some brominated flame retardants (BFRs), the use of organophosphate flame retardants (OPFRs) increases, and they are detected in multi-environment media at higher frequency and concentrations. However, the toxicity data of OPFRs, especially those on developmental toxicology are quite limited, which prevents an accurate evaluation of their environmental and health risk. Because a previous study reported that two aryl-OPFRs induced cardiotoxicity during zebrafish embryogenesis, we designed experiments to compare the heart developmental toxicity of a series of aryl-OPFRs with alkyl-OPFRs and explored possible internal mechanism. First, acute toxicity of 9 frequently used OPFRs were studied with zebrafish embryos (2-96 hpf). By comparing the LC50 and EC50 (pericardium edema) data, two aryl-OPFRs, triphenyl phosphate (TPhP) and cresyl diphenyl phosphate (CDP) showed greater heart developmental toxicity than the others. It was also found that the acute toxicity of OPFRs varied mainly depending on their hydrophobicity. Further study on the cardiotoxicity of TPhP and CDP showed that the cardiac looping progress can be impeded by 0.10mg/L TPhP or CDP exposure. Bradycardia and reduction of myocardium were also observed in 0.50 and 1.0mg/L TPhP groups and 0.10, 0.50, and 1.0mg/L CDP groups. 0-48 hpf is the vulnerable window of zebrafish cardiogenesis that can be easily affected by TPhP and CDP. RT-qPCR measurement on the expressions of key transcriptional regulators in cardiogenesis showed that BMP4, NKX2-5, and TBX5 were significantly inhibited at the exposure points of 12 hpf and 24 hpf which may be the internal factors related to the heart developmental toxicity. As zebrafish is a good model organism for human health study, the present results call for a greater attention to the health risk of fetus in pregnant women exposed to such OPFRs. PMID:25661707

  4. Enhancement of flame retardancy and mechanical properties of HDPE/EPM based radiation shielding composites by electron beam irradiation

    NASA Astrophysics Data System (ADS)

    Seo, Duckbong; Kim, Jaewoo; Kang, Phil-Hyun; Seo, Chang Eui; Lee, Jun-Hyung; Kim, Hyun-Jin

    2012-10-01

    Radiation shielding materials based on polymer or its composites require higher material properties to endure the harsh radiation environments. In this investigation, electron beam (E-beam) irradiation and/or cross-linking agent triallyl cyanurate (TAC) were applied into the composites of a high density polyethylene (HDPE)/ethylene propylene monomer (EPM) blend containing B2O3 and/or PbO. The tensile strength increased as much as twice while the elongation enhanced more than 5 times by irradiation of 150 kGy with 10 MeV E-beam. Further enhancement of the tensile and elongation properties was achieved by applying both 1 wt.% TAC and E-beam irradiation, while use of 1 wt.% TAC alone decreased the mechanical properties. Flame retardancy of the polymer composites by mean of limit oxygen index (LOI) also achieved to higher than 21 without using any flame retardant additive.

  5. Preparation and properties of flexible flame-retardant neutron shielding material based on methyl vinyl silicone rubber

    NASA Astrophysics Data System (ADS)

    Chai, Hao; Tang, Xiaobin; Ni, Minxuan; Chen, Feida; Zhang, Yun; Chen, Da; Qiu, Yunlong

    2015-09-01

    Flexible flame-retardant composites were prepared using high-functional methyl vinyl silicone rubber matrix with B4C, hollow beads, and zinc borate (ZB) as filler materials. As filler content increased, the tensile strength, elongation, and tear strength of the composites initially increased and then decreased. The shore hardness of the composites increased with increasing filler content with a maximum value of 30 HA. The heat insulation properties of the composites with hollow beads were higher than that of the ordinary composites with the same filler mass fraction. When ZB content exceeded 12 wt%, the limit of oxygen index of the composites was higher than 27.1%. With Am-Be neutron as the test radiation source, the transmission of neutron for a 2 cm sample was only 47.8%. Powder surface modification improved the mechanical properties, thermal conductivity, flame retardancy, and neutron shielding performance of the composites, but did not affect shore hardness.

  6. The chemistry of dimethacrylate-styrene networks, and, Development of flame retardant, halogen-free fiber reinforced vinyl ester composites

    NASA Astrophysics Data System (ADS)

    Rosario, Astrid Christa

    One of the major classes of polymer matrix resins under consideration for structural composite applications in the infrastructure and construction industries is vinyl ester resin. Vinyl ester resin is comprised of low molecular weight poly(hydroxyether) oligomers with methacrylate endgroups diluted with styrene monomer. The methacrylate endgroups cure with styrene via free radical copolymerization to yield thermoset networks. The copolymerization behavior of these networks was monitored by Fourier Transform Infrared Spectroscopy (FTIR) at various cure conditions. Reactions of the carbon-carbon double bonds of the methacrylate (943 cm-1) and styrene (910 cm-1 ) were followed independently. Oligomers possessing number average molecular weights of 700 g/mole were studied with systematically increasing levels of styrene. The Mortimer-Tidwell reactivity ratios indicated that at low conversion more styrene was incorporated into the network at lower cure temperatures. The experimental vinyl ester-styrene network compositions deviated significantly from those predicted by the Meyer-Lowry integrated copolymer equation at higher conversion, implying that the reactivity ratios for these networks may change with conversion. The kinetic data were used to provide additional insight into the physical and mechanical properties of these materials. In addition to establishing the copolymerization kinetics of these materials, the development of halogen free fiber reinforced vinyl ester composites exhibiting good flame properties was of interest. Flame retardant vinyl ester resins are used by many industries for applications requiring good thermal resistance. The current flame-retardant technology is dependent on brominated vinyl esters, which generate high levels of smoke and carbon monoxide. A series of halogen free binder systems has been developed and dispersed in the vinyl ester to improve flame retardance. The binder approach enables the vinyl ester resin to maintain its low

  7. Contamination of indoor dust and air by polychlorinated biphenyls and brominated flame retardants and relevance of non-dietary exposure in Vietnamese informal e-waste recycling sites.

    PubMed

    Tue, Nguyen Minh; Takahashi, Shin; Suzuki, Go; Isobe, Tomohiko; Viet, Pham Hung; Kobara, Yuso; Seike, Nobuyasu; Zhang, Gan; Sudaryanto, Agus; Tanabe, Shinsuke

    2013-01-01

    This study investigated the occurrence of polychlorinated biphenyls (PCBs), and several additive brominated flame retardants (BFRs) in indoor dust and air from two Vietnamese informal e-waste recycling sites (EWRSs) and an urban site in order to assess the relevance of these media for human exposure. The levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), 1,2-bis-(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenyl ethane (DBDPE) in settled house dust from the EWRSs (130-12,000, 5.4-400, 5.2-620 and 31-1400 ng g(-1), respectively) were significantly higher than in urban house dust but the levels of PCBs (4.8-320 ng g(-1)) were not higher. The levels of PCBs and PBDEs in air at e-waste recycling houses (1000-1800 and 620-720 pg m(-3), respectively), determined using passive sampling, were also higher compared with non-e-waste houses. The composition of BFRs in EWRS samples suggests the influence from high-temperature processes and occurrence of waste materials containing older BFR formulations. Results of daily intake estimation for e-waste recycling workers are in good agreement with the accumulation patterns previously observed in human milk and indicate that dust ingestion contributes a large portion of the PBDE intake (60%-88%), and air inhalation to the low-chlorinated PCB intake (>80% for triCBs) due to their high levels in dust and air, respectively. Further investigation of both indoor dust and air as the exposure media for other e-waste recycling-related contaminants and assessment of health risk associated with exposure to these contaminant mixtures is necessary. PMID:23228866

  8. Brominated flame retardants in U.S. biosolids from the EPA national sewage sludge survey and chemical persistence in outdoor soil mesocosms.

    PubMed

    Venkatesan, Arjun K; Halden, Rolf U

    2014-05-15

    We determined national baseline levels and release inventories of 77 traditional and novel brominated flame retardants (BFRs) in biosolids composites (prepared from 110 samples) from the U.S. Environmental Protection Agency's 2001 national sewage sludge survey (NSSS). Additionally, analyses were performed on archived samples from a 3-year outdoor mesocosm study to determine the environmental persistence of BFRs in biosolids-amended soil. The total polybrominated diphenylether (PBDE) concentration detected in biosolids composites was 9400 ± 960 μg/kg dry weight, of which deca-BDE constituted 57% followed by nona- and penta-BDE at 18 and 13%, respectively. The annual mean loading rate estimated from the detected concentrations and approximate annual biosolids production and disposal numbers in the U.S., of the sum of PBDEs and non-BDE BFRs was calculated to be 47,900-60,100 and 12,900-16,200 kg/year, of which 24,000-36,000 and 6400-9700 kg/year are applied on land, respectively. Mean concentration of PBDEs were higher in the 2001 samples compared to levels reported in EPA's 2006/7 Targeted NSSS, reflecting on-going efforts in phasing-out PBDEs in the U.S. In outdoor soil mesocosms, >99% of the initial BFRs mass in the biosolids/soil mixtures (1:2) persisted over the monitoring duration of three years. Estimates of environmental releases may be refined in the future by analyzing individual rather than composited samples, and by integrating currently unavailable data on disposal of biosolids on a plant-specific basis. This study informs the risk assessment of BFRs by furnishing national inventories of BFR occurrence and environmental release via biosolids application on land. PMID:24607311

  9. Toxicity of the Flame-Retardant BDE-49 on Brain Mitochondria and Neuronal Progenitor Striatal Cells Enhanced by a PTEN-Deficient Background

    PubMed Central

    Giulivi, Cecilia

    2013-01-01

    Polybrominated diphenyl ethers (PBDEs) represent an important group of flame retardants extensively used, tonnage of which in the environment has been steadily increasing over the past 25 years. PBDEs or metabolites can induce neurotoxicity and mitochondrial dysfunction (MD) through a variety of mechanisms. Recently, PBDEs with < 5 Br substitutions (i.e., 2,2′,4,4′-tetrabromodiphenyl ether [BDE-47] and 2,2′,4,5′-tetrabromodiphenyl ether [BDE-49]) have gained interest because of their high bioaccumulation. In particular, congeners such as BDE-49 arise as one of the most biologically active, with concentrations typically lower than those observed for BDE-47 in biological tissues; however, its potential to cause MD at biologically relevant concentrations is unknown. To this end, the effect of BDE-49 was studied in brain mitochondria and neuronal progenitor striatal cells (NPC). BDE-49 uncoupled mitochondria at concentrations < 0.1 nM, whereas at > 1 nM, it inhibited the electron transport at Complex V (mixed type inhibition; IC50 = 6 nM) and Complex IV (noncompetitive inhibition; IC50 = 40 nM). These concentrations are easily achieved in plasma concentrations considering that BDE-49 (this study, 400-fold) and other PBDEs accumulate 1–3 orders of magnitude in the cells, particularly in mitochondria and microsomes. Similar effects were observed in NPC and exacerbated with PTEN (negative modulator of the PI3K/Akt pathway) deficiency, background associated with autism-like behavior, schizophrenia, and epilepsy. PBDE-mediated MD per se or enhanced by a background that confers susceptibility to this exposure may have profound implications in the energy balance of brain. PMID:23288049

  10. Effects of Chronic Exposure to an Environmentally Relevant Mixture of Brominated Flame Retardants on the Reproductive and Thyroid System in Adult Male Rats

    PubMed Central

    Ernest, Sheila R.; Wade, Michael G.; Lalancette, Claudia; Ma, Yi-Qian; Berger, Robert G.; Robaire, Bernard; Hales, Barbara F.

    2012-01-01

    Brominated flame retardants (BFRs) are incorporated into a wide variety of consumer products, are readily released into home and work environments, and are present in house dust. Studies using animal models have revealed that exposure to polybrominated diphenyl ethers (PBDEs) may impair adult male reproductive function and thyroid hormone physiology. Such studies have generally characterized the outcome of acute or chronic exposure to a single BFR technical mixture or congener but not the impact of environmentally relevant BFR mixtures. We tested whether exposure to the BFRs found in house dust would have an adverse impact on the adult male rat reproductive system and thyroid function. Adult male Sprague Dawley rats were exposed to a complex BFR mixture composed of three commercial brominated diphenyl ethers (52.1% DE-71, 0.4% DE-79, and 44.2% decaBDE-209) and hexabromocyclododecane (3.3%), formulated to mimic the relative congener levels in house dust. BFRs were delivered in the diet at target doses of 0, 0.02, 0.2, 2, or 20 mg/kg/day for 70 days. Compared with controls, males exposed to the highest dose of BFRs displayed a significant increase in the weights of the kidneys and liver, which was accompanied by induction of CYP1A and CYP2B P450 hepatic drug–metabolizing enzymes. BFR exposure did not affect reproductive organ weights, serum testosterone levels, testicular function, or sperm DNA integrity. The highest dose caused thyroid toxicity as indicated by decreased serum thyroxine (T4) and hypertrophy of the thyroid gland epithelium. At lower doses, the thickness of the thyroid gland epithelium was reduced, but no changes in hormone levels (T4 and thyroid-stimulating hormone) were observed. Thus, exposure to BFRs affected liver and thyroid physiology but not male reproductive parameters. PMID:22387749

  11. Non-invasive biomonitoring for PFRs and PBDEs: new insights in analysis of human hair externally exposed to selected flame retardants.

    PubMed

    Kucharska, Agnieszka; Covaci, Adrian; Vanermen, Guido; Voorspoels, Stefan

    2015-02-01

    In this study, we investigated the hypothesis whether externally adsorbed and internally deposited flame retardants (FRs) in hair could be distinguished. To this extent, hair samples collected from one volunteer were exposed under controlled conditions to phosphate FR (PFR) and polybrominated diphenyl ether (PBDE) standards to mimic external contamination. Afterwards, suitable washing procedures to selectively remove contaminants from the hair surface were investigated. The samples were measured by GC-(ECNI)-MS for PBDEs and LC-(ESI+)-MS/MS for PFRs. All investigated compounds were transferred onto the hair surface. One of the most important finding was that dust particles are not mandatory to transfer compounds on the hair surface and to be able to measure high levels of compounds in human hair. To assess different protocols to selectively remove external contamination, the exposed hair samples were washed in different media before analysis: water, methanol, hexane:dichloromethane (1:1, v/v), acetone and shampoo. Results indicated that there is no washing medium able to entirely and exclusively remove external contamination. Among investigated media, methanol removed a meaningful part of the external contamination (42-105%), but the removal efficiencies differed among compounds. We therefore concluded that hair should not be washed prior to analysis and in case of visible contamination (e.g. with cosmetic products), water would be the recommended agent. Organic solvents should not be used for the washing step. Although it is impossible to distinguish external from internal exposure, hair samples may be used as valuable biomarker of human exposure, providing a measure of integral exposure. To the best of our knowledge, this is the first study which has used externally exposed hair samples to PBDEs and PFRs. PMID:25461107

  12. New perspective on the determination of flame retardants in sewage sludge by using ultrahigh pressure liquid chromatography-tandem mass spectrometry with different ion sources.

    PubMed

    Mascolo, G; Locaputo, V; Mininni, G

    2010-07-01

    Analysis of 11 polybrominated diphenyl ethers (PBDEs), tetrabromobisphenol A bis 2,3-dibromopropylether (TBBPA-bis), tetrachlorobisphenol A (TCBPA), tetrabromobisphenol A (TBBPA) and hexabromocyclododecanes (HBCDs) was optimized by ultrahigh pressure liquid chromatography/tandem mass spectrometry (UPLC-MS/MS) operating in negative ion (NI) mode. Electrospray ionization (ESI), atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization (APCI) sources were tested and for PBDEs APCI gave higher sensitivity than APPI while for TBBPA-bis APCI and APPI showed similar performance. ESI was the best option for TCBPA, TBBPA and HBCDs. Detection limits were between 20 and 59 fg for the compounds analyzed by ESI, 0.10 and 0.72 pg for PBDEs and 6 pg for TBBPA-bis. The matrix effect of sewage sludge extract was also tested showing negligible ion suppression for APCI and an increase of the background level of all investigated pollutants leading to a worsening of the limits of quantification by a factor between 1.2 and 3.3. The UPLC-APCI/MS/MS method for PBDEs, after pressurized liquid extraction (PLE), was validated by comparison with the concentration values from the NIST 1944 standard reference material. The advantages of the methods include low detection limits, PBDE congeners specificity using selected multiple reaction monitoring (MRM) transitions, and the absence of thermal degradation of higher PBDE congeners, especially BDE-209. The methods were applied for the determination of the above reported flame retardants in sewage sludge in order to get more information about the degradation on PBDEs (in particular BDE-209) during municipal wastewater treatments. PMID:20564801

  13. Brominated flame retardants in U.S. biosolids from the EPA national sewage sludge survey and chemical persistence in outdoor soil mesocosms

    PubMed Central

    Venkatesan, Arjun K.; Halden, Rolf U.

    2014-01-01

    We determined national baseline levels and release inventories of 77 traditional and novel brominated flame retardants (BFRs) in biosolids composites (prepared from 110 samples) from the U.S. Environmental Protection Agency’s 2001 national sewage sludge survey (NSSS). Additionally, analyses were performed on archived samples from a 3-year outdoor mesocosm study to determine the environmental persistence of BFRs in biosolids-amended soil. The total polybrominated diphenylether (PBDE) concentration detected in biosolids composites was 9,400±960 μg/kg dry weight, of which deca-BDE constituted 57% followed by nona- and penta-BDE at 18 and 13%, respectively. The annual mean loading rate estimated from the detected concentrations and approximate annual biosolids production and disposal numbers in the U.S., of the sum of PBDEs and non-BDE BFRs was calculated to be 47,900–60,100 and 12,900–16,200 kg/year, of which 24,000–36,000 and 6,400–9,700 kg/year are applied on land, respectively. Mean concentration of PBDEs were higher in the 2001 samples compared to levels reported in EPA’s 2006/7 Targeted NSSS, reflecting on-going efforts in phasing-out PBDEs in the U.S. In outdoor soil mesocosms, >99% of the initial BFRs mass in the biosolids/soil mixtures (1:2) persisted over the monitoring duration of three years. Estimates of environmental releases may be refined in the future by analyzing individual rather than composited samples, and by integrating currently unavailable data on disposal of biosolids on a plant-specific basis. This study informs the risk assessment of BFRs by furnishing national inventories of BFR occurrence and environmental release via biosolids application on land. PMID:24607311

  14. Evaluation of spatial distribution and accumulation of novel brominated flame retardants, HBCD and PBDEs in an Italian subalpine lake using zebra mussel (Dreissena polymorpha).

    PubMed

    Poma, Giulia; Binelli, Andrea; Volta, Pietro; Roscioli, Claudio; Guzzella, Licia

    2014-01-01

    Because of the reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD), novel brominated flame retardants (NBFRs), including 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB), started to be marketed as alternatives to the banned formulations. In this study, the spatial distribution and accumulation of NBFRs, PBDEs, and HBCD in the biota have been investigated in the littoral compartment of a large and deep subalpine lake (Lake Maggiore, Northern Italy), using zebra mussel Dreissena polymorpha and roach (Rutilus rutilus) as bioindicators. To our knowledge, this is the first study reporting the contamination of NBFRs in the freshwater invertebrate D. polymorpha. Contamination of zebra mussel due to PBEB, HBB, and BTBPE was low, ranging from 0.9 to 2.9 ng/g lipid weight, from 1.1 to 2.9 ng/g l.w., and from 3.5 to 9.5 ng/g l.w., respectively. PBEB and BTBPE in roach were always below the detection limit, while the contamination of HBB ranged from < limits of detection (LOD) to 1.74 ng/g l.w., indicating a weak contamination. DBDPE was < LOD in all the considered biological samples. Finally, HBCD was detected in all organic tissues with mean concentrations up to 74.4 ng/g l.w. PBDE results, supported by principal component analysis elaboration, suggested a possible contamination due to the congeners composing the penta- and deca-BDE technical formulations, which are present in the Lake Maggiore basin. The biomagnification factor values showed that tetra- and penta-BDE biomagnified, while octa-, nona-, and deca-BDE were still bioavailable and detectable in the fish muscles, but they do not biomagnified. Considering the other BFRs, only HBCD showed a moderate biomagnification potential. PMID:24756669

  15. Advanced Morphological — Behavioral Test Platform Reveals Neurodevelopmental Defects in Embryonic Zebrafish Exposed to Comprehensive Suite of Halogenated and Organophosphate Flame Retardants

    PubMed Central

    Noyes, Pamela D.; Haggard, Derik E.; Gonnerman, Greg D.; Tanguay, Robert L.

    2015-01-01

    The increased use of flammable plastics and electronic devices along with stricter fire safety standards has led to the heavy use of flame retardant chemicals in many consumer, commercial, and industrial products. Although flame retardant use has increased, a great deal of uncertainty surrounds their safety with some evidence showing toxicity and risk to human and environmental health. Recent efforts have focused on designing high-throughput biological platforms with nonmammalian models to evaluate and prioritize chemicals with limited hazard information. To complement these efforts, this study used a new morphological and behavioral testing platform with embryonic zebrafish to characterize the developmental toxicity of 44 halogenated and organophosphate flame retardants, including several of their known metabolites. Zebrafish were exposed to flame retardants from 6 to 120 h post fertilization (hpf) across concentrations spanning 4 orders of magnitude (eg, 6.4 nM to 64 µM). Flame retardant effects on survival and development were evaluated at 24 and 120 hpf, and neurobehavioral changes were measured using 2 photomotor response (PMR) assays. Compared to controls, 93% (41/44) of flame retardants studied elicited adverse effects among one or more of the bioassays and concentrations tested with the aryl phosphate ester (APE)-based mono-isopropylated triaryl phosphate and the brominated-bisphenol-A analog tetrabromobisphenol-A producing the greatest array of malformations. Hierarchical clustering showed that APE flame retardants with isopropyl, butyl, and cresyl substituents on phenyl rings clustered tightly and were particularly potent. Both PMR assays were highly predictive of morphological defects supporting their use as nonlethal means of evaluating teratogenicity that could allow for additional evaluations of long-term or delayed effects in older animals. Taken together, evidence presented here indicates that zebrafish neurodevelopment is highly sensitive to

  16. Advanced morphological - behavioral test platform reveals neurodevelopmental defects in embryonic zebrafish exposed to comprehensive suite of halogenated and organophosphate flame retardants.

    PubMed

    Noyes, Pamela D; Haggard, Derik E; Gonnerman, Greg D; Tanguay, Robert L

    2015-05-01

    The increased use of flammable plastics and electronic devices along with stricter fire safety standards has led to the heavy use of flame retardant chemicals in many consumer, commercial, and industrial products. Although flame retardant use has increased, a great deal of uncertainty surrounds their safety with some evidence showing toxicity and risk to human and environmental health. Recent efforts have focused on designing high-throughput biological platforms with nonmammalian models to evaluate and prioritize chemicals with limited hazard information. To complement these efforts, this study used a new morphological and behavioral testing platform with embryonic zebrafish to characterize the developmental toxicity of 44 halogenated and organophosphate flame retardants, including several of their known metabolites. Zebrafish were exposed to flame retardants from 6 to 120 h post fertilization (hpf) across concentrations spanning 4 orders of magnitude (eg, 6.4 nM to 64 µM). Flame retardant effects on survival and development were evaluated at 24 and 120 hpf, and neurobehavioral changes were measured using 2 photomotor response (PMR) assays. Compared to controls, 93% (41/44) of flame retardants studied elicited adverse effects among one or more of the bioassays and concentrations tested with the aryl phosphate ester (APE)-based mono-isopropylated triaryl phosphate and the brominated-bisphenol-A analog tetrabromobisphenol-A producing the greatest array of malformations. Hierarchical clustering showed that APE flame retardants with isopropyl, butyl, and cresyl substituents on phenyl rings clustered tightly and were particularly potent. Both PMR assays were highly predictive of morphological defects supporting their use as nonlethal means of evaluating teratogenicity that could allow for additional evaluations of long-term or delayed effects in older animals. Taken together, evidence presented here indicates that zebrafish neurodevelopment is highly sensitive to

  17. Synthesis of a Novel Phosphorus-Containing Flame Retardant Curing Agent and Its Application in Epoxy Resins.

    PubMed

    Zhang, Hongkun; Xu, Miaojun; Li, Bin

    2016-03-01

    A novel phosphorus-containing compound diphenyl-(2,5-dihydroxyphenyl)-phosphine oxide defined as DPDHPPO was synthesized and used as flame retardant and curing agent for epoxy resins (EP). The chemical structure was well characterized by Fourier transform infrared (FTIR) spectroscopy, 1H, 13C and 31P nuclear magnetic resonance. The flame retardant properties, combusting performances and thermal degradation behaviors of the cured epoxy resins were investigated by limiting oxygen index (LOI), vertical burning tests (UL-94), cone calorimeter and thermogravimetric analysis (TGA) tests. The morphologies and chemical compositions of char residues for cured epoxy resins were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS), respectively. The water resistant properties were evaluated by putting the samples into distilled water at 70 degrees C for 168 h. The results revealed that the EP/40 wt% DPDHPPO/60 wt% PDA thermosets successfully passed UL-94 V-0 flammability rating and the LOI value was as high as 31.9%. The cone tests results revealed that the incorporation of DPDHPPO efficiently reduced the combustion parameters of epoxy resins thermosets, such as heat release rate (HRR), total heat release (THR) and so on. The TGA results indicated that the introduction of DPDHPPO promoted epoxy resins matrix decomposed ahead of time compared with that of pure EP and led to a higher char yield and thermal stability at high temperature. The morphological structures and analysis of XPS of char residues revealed that DPDHPPO benefited to the formation of a sufficient, compact and homogeneous char layer with rich flame retardant elements on the epoxy resins materials surface during combustion. After water resistance tests, EP/40 wt% DPDHPPO/60 wt% PDA thermosets still remained excellent flame retardancy, the moisture absorption of epoxy resins thermosets decreased with the increase of DPDHPPO contents in the thermosets due to the existing

  18. Phosphorus-containing flame retardant modified layered double hydroxides and their applications on polylactide film with good transparency.

    PubMed

    Ding, Peng; Kang, Bai; Zhang, Jin; Yang, Jingwen; Song, Na; Tang, Shengfu; Shi, Liyi

    2015-02-15

    Polylactide (PLA)/layered double hydroxide (LDH) films with good flame retardant property and transparency were synthesized by solution exfoliation and film casting method. The organic-inorganic interfacial interaction between PLA and NiAl-LDH was carefully modified by 2-carboxylethyl-phenyl-phosphinic acid (CEPPA) to well solve the dispersion problem of NiAl-LDH nanolayers and get enhanced flame retardancy of PLA composites. The results showed the NiAl-LDH/CEPPA (LC) nanolayers had exfoliated structures and were homogenously dispersed in PLA matrixes. All the PLA/LDH films had good transparency even LC content was up to 10 wt%. The PLA/LDH films absorbed the ultraviolet light, which alleviates the embrittlement of PLA films in the using procedure. The flame retardant effect characterized by microscale combustion calorimeter was observed when LC contents increased. The total heat release value of the sample with 10 wt% LC decreased to 9.7 kJ/g from 12.0 kJ/g of virgin PLA. PMID:25460688

  19. Sustainable, heat-resistant and flame-retardant cellulose-based composite separator for high-performance lithium ion battery.

    PubMed

    Zhang, Jianjun; Yue, Liping; Kong, Qingshan; Liu, Zhihong; Zhou, Xinhong; Zhang, Chuanjian; Xu, Quan; Zhang, Bo; Ding, Guoliang; Qin, Bingsheng; Duan, Yulong; Wang, Qingfu; Yao, Jianhua; Cui, Guanglei; Chen, Liquan

    2014-01-01

    A sustainable, heat-resistant and flame-retardant cellulose-based composite nonwoven has been successfully fabricated and explored its potential application for promising separator of high-performance lithium ion battery. It was demonstrated that this flame-retardant cellulose-based composite separator possessed good flame retardancy, superior heat tolerance and proper mechanical strength. As compared to the commercialized polypropylene (PP) separator, such composite separator presented improved electrolyte uptake, better interface stability and enhanced ionic conductivity. In addition, the lithium cobalt oxide (LiCoO2)/graphite cell using this composite separator exhibited better rate capability and cycling retention than that for PP separator owing to its facile ion transport and excellent interfacial compatibility. Furthermore, the lithium iron phosphate (LiFePO4)/lithium cell with such composite separator delivered stable cycling performance and thermal dimensional stability even at an elevated temperature of 120°C. All these fascinating characteristics would boost the application of this composite separator for high-performance lithium ion battery. PMID:24488228

  20. Sustainable, heat-resistant and flame-retardant cellulose-based composite separator for high-performance lithium ion battery

    PubMed Central

    Zhang, Jianjun; Yue, Liping; Kong, Qingshan; Liu, Zhihong; Zhou, Xinhong; Zhang, Chuanjian; Xu, Quan; Zhang, Bo; Ding, Guoliang; Qin, Bingsheng; Duan, Yulong; Wang, Qingfu; Yao, Jianhua; Cui, Guanglei; Chen, Liquan

    2014-01-01

    A sustainable, heat-resistant and flame-retardant cellulose-based composite nonwoven has been successfully fabricated and explored its potential application for promising separator of high-performance lithium ion battery. It was demonstrated that this flame-retardant cellulose-based composite separator possessed good flame retardancy, superior heat tolerance and proper mechanical strength. As compared to the commercialized polypropylene (PP) separator, such composite separator presented improved electrolyte uptake, better interface stability and enhanced ionic conductivity. In addition, the lithium cobalt oxide (LiCoO2)/graphite cell using this composite separator exhibited better rate capability and cycling retention than that for PP separator owing to its facile ion transport and excellent interfacial compatibility. Furthermore, the lithium iron phosphate (LiFePO4)/lithium cell with such composite separator delivered stable cycling performance and thermal dimensional stability even at an elevated temperature of 120°C. All these fascinating characteristics would boost the application of this composite separator for high-performance lithium ion battery. PMID:24488228

  1. Trophic magnification of chlorinated flame retardants and their dechlorinated analogs in a fresh water food web.

    PubMed

    Wang, De-Gao; Guo, Ming-Xing; Pei, Wei; Byer, Jonathan D; Wang, Zhuang

    2015-01-01

    Chlorinated flame retardants, particularly dechlorane plus (DP), were widely used in commercial applications and are ubiquitous in the environment. A total of seven species of aquatic organisms were collected concurrently from the region of a chemical production facility in Huai’an, China. DP and structurally related compounds including mirex, dechloranes 602, 603, 604, chlordene plus (CP), DP monoadduct (DPMA), and two dechlorinated breakdown products of DP, decachloropentacyclooctadecadiene (anti-Cl(10)-DP) and undecachloropentacyclooctadecadiene (anti-Cl(11)-DP), were detected in these aquatic organisms. Nitrogen stable isotope ratios were also measured to determine the trophic levels of the organisms. Trophic magnification factors (TMFs) for these chemicals were calculated with values ranging from 1.0 to 3.1. TMFs for CP, mirex, anti-DP, and ∑DP were statistically greater than 1, showing evidence of biomagnification in the food web. Concentration ratios of anti-Cl(11)-DP to anti-DP showed a significant relationship with trophic level, implying that anti-Cl(11)-DP had a higher food-web magnification potential than its precursor. The biota-sediment accumulation factors and TMFs for DP demonstrated stereoselectivity, with syn-DP having a greater bioaccumulation potential than anti-DP in the aquatic environment. PMID:25463253

  2. Risk migration and scientific advance: the case of flame-retardant compounds.

    PubMed

    Alcock, Ruth E; Busby, Jerry

    2006-04-01

    It is a common experience that attempts to mitigate a risk lead to new risks, and that risks formerly thought to be of one kind become another kind as technical knowledge evolves. This phenomenon of risk migration suggests that we should take processes over time, rather than specific risks or specific technologies, as a unit of analysis. Several of our existing models of the social management of risks-such as that of social risk amplification-are process models of a kind but are still oriented around the playing out of a particular event or issue. A case study of risk in a group of flame-retardant compounds was used as the basis of a grounded, exploratory analysis of migration processes, the phenomena that influence them, and their consequences. This illustrated how migration naturally occurs from risks that are understood, in which risk bearers have at least some agency, to risks that are not understood and not capable of being influenced by risk bearers. It illustrated how the simultaneous improvement in measuring technology, which detects potential toxins at increasingly small concentrations, combines with intuitive models that ignore concentration to produce conditions likely to generate anxiety. And it illustrated how pressure groups and commercial interests exploit this effect. It also showed how migration makes precautionary action problematic, and how more generally it tends to undermine a society's capacity to cope with risk. PMID:16573627

  3. Organophosphate ester flame retardants and plasticizers in human placenta in Eastern China.

    PubMed

    Ding, Jinjian; Xu, Zemin; Huang, Wei; Feng, Limin; Yang, Fangxing

    2016-06-01

    Organophosphate esters (OPEs) have been widely used in various products as alternatives to brominated flame retardants. Although widespread OPE exposure is expected in humans, the accumulation of OPEs has seldom been studied in the human body. In this study, 12 OPE analogs were analyzed in 50 human placentas collected in Eastern China. The concentrations of the 9 most frequently detected OPEs (Σ9OPEs) ranged from 34.4 to 862ng/g lipid weight (lw), with a median of 301ng/g lw. Tri(2-chloroethyl) phosphate (TCEP) was identified as the most abundant analog, with a median concentration of 142ng/g lw, followed by tributoxyethyl phosphate (TBEP) and triphenyl phosphate (TPhP). Statistical analysis showed no analog of OPEs or Σ9OPEs was positively correlated with the lipid content of the placentas. There were no correlations observed between the OPE concentrations and maternal characteristics. Food consumption habits exhibited weak effects on OPE levels in the placentas. Further investigation is required to determine the effects of OPEs on fetuses due to the expected increase in maternal exposure to these esters. PMID:26950635

  4. Distribution of organophosphorus flame retardants in sediments from the Pearl River Delta in South China.

    PubMed

    Tan, Xiao-Xin; Luo, Xiao-Jun; Zheng, Xiao-Bo; Li, Zong-Rui; Sun, Run-Xia; Mai, Bi-Xian

    2016-02-15

    Twelve organophosphorus flame retardants (PFRs) were identified in the sediments and the sediment core collected from the rivers and the estuary in the Pearl River Delta, with the aim of investigating their spatial and vertical distributions. The concentrations of PFRs ranged from 8.3 to 470 ng/g dry weight with high levels of PFRs in the urban area and the e-waste recycling region. Generally, TPhP, TCPP, TEHP, TCEP, and TBEP were the dominant compounds of the PFRs, the composition of which varied across the different regions, reflecting the different sources of PFRs. In the estuary, the PFRs mainly derived from the Xijiang River and the Shunde sections. Increased concentrations of halogen-containing PFRs have been observed in the upper layers of the sediment core. Conversely, relatively high concentrations of halogen-free PFRs were observed in the lower layers of the sediment core, indicating different usage patterns or environmental behaviors between the halogen and the non-halogen PFRs in the study area. PMID:26657357

  5. Synthesis of hydrophobic zinc borate nanoflakes and its effect on flame retardant properties of polyethylene

    SciTech Connect

    Li Shengli; Long Beihong; Wang Zichen; Tian Yumei; Zheng Yunhui; Zhang Qian

    2010-04-15

    Zinc borate (2ZnO.3B{sub 2}O{sub 3}.3.5H{sub 2}O) has relatively high dehydration on-set temperature which property permits processing in a wide range of polymer system. But zinc borate particles are hardly dispersed in a polymer matrix so that they prevent their using in industry. To address this problem, we synthesized hydrophobic zinc borate (2ZnO.3B{sub 2}O{sub 3}.3.5H{sub 2}O) nanoflakes by employing solid-liquid reaction of zinc oxide (ZnO) and boric acid (H{sub 3}BO{sub 3}) in the presence of oleic acid. This method does not bring pollution. By conducting morphological and microscopic analyses, we found that this compound displayed nanoflake morphology with particle size of around 100-200 nm, thickness less than 100 nm and there were uniform mesopores with the diameter about 10 nm within the particles. Furthermore, our products had an effect on flame retardant of polyethylene, especially when the zinc borate was modified by oleic acid. - Graphical abstract: The contact angle of hydrophobic zinc borate nanoflakes is 129.02 deg. with added 2.0 wt% of oleic acid.

  6. Microbial degradation of the brominated flame retardant TBNPA by groundwater bacteria: laboratory and field study.

    PubMed

    Balaban, Noa; Bernstein, Anat; Gelman, Faina; Ronen, Zeev

    2016-08-01

    In the present study, the biodegradation of the brominated flame retardant tribromoneopentylalcohol (TBNPA) by a groundwater enrichment culture was investigated using a dual carbon ((13)C/(12)C)- bromine ((81)Br/(79)Br) stable isotope analysis. An indigenous aerobic bacterial consortium was enriched from the polluted groundwater underlying an industrial site in the northern Negev Desert, Israel, where TBNPA is an abundant pollutant. Aerobic biodegradation was shown to be rapid, with complete debromination within a few days, whereas anaerobic biodegradation was not observed. Biodegradation under aerobic conditions was accompanied by a significant carbon isotope effect with an isotopic enrichment factor of ɛCbulk = -8.8‰ ± 1.5‰, without any detectable bromine isotope fractionation. It was found that molecular oxygen is necessary for biodegradation to occur, suggesting an initial oxidative step. Based on these results, it was proposed that H abstraction from the C-H bond is the first step of TBNPA biodegradation under aerobic conditions, and that the C-H bond cleavage results in the formation of unstable intermediates, which are rapidly debrominated. A preliminary isotopic analysis of TBNPA in the groundwater underlying the industrial area revealed that there are no changes in the carbon and bromine isotope ratio values downstream of the contamination source. Considering that anoxic conditions prevail in the groundwater of the contaminated site, the lack of isotope shifts in TBNPA indicates the lack of TBNPA biodegradation in the groundwater, in accordance with our findings. PMID:27183339

  7. Potential genotoxicity and risk assessment of a chlorinated flame retardant, Dechlorane Plus.

    PubMed

    Dou, Jing; Jin, Yuan; Li, Yajie; Wu, Bing; Li, Mei

    2015-09-01

    Dechlorane Plus (DP) is a chlorinated flame retardants that is globally ubiquitous. It is a potentially persistent organic pollutant (POPs) and an environmental toxin. However, the toxicity data is still limited and cannot provide a comprehensive environmental ecological risk assessment for DP. In this study, luminous bacteria, Vicia faba and Tetrahymena thermophila were chosen as testing organisms to investigate the acute toxicity and mutagenicity of DP. The concentration gradient of DP used in this study was chosen based on its environmental levels (experiments of luminous bacteria: 0.591, 2.95, 14.8, 73.8, 369 μg L(-1); micronucleus tests: 2.4, 12, 60, 300, 1500 μg L(-1); comet assay: 2.4, 12, 60, 300, 1500 μg L(-1)). For luminous bacteria, the relative luminosities were around 100% in treated groups, which suggested that there is no acute toxicity to luminous bacteria under the studied DP concentrations. The micronucleus test showed no significant difference between treatment and control groups, indicating no genotoxicity of DP. However the comet assay conducted with T. thermophila was relatively sensitive as there was a significant increase in DNA damage when the concentrations of DP increased from 300 to 1500 μg L(-1), while the lower concentrations failed to show any treatment-related differences. Therefore, DP may pose a potential risk at concentration⩾300 μg L(-1). The results provide scientific information on the ecological risk assessment of DP. PMID:25585867

  8. Advances in enantioselective analysis of chiral brominated flame retardants. Current status, limitations and future perspectives.

    PubMed

    Badea, Silviu-Laurentiu; Niculescu, Violeta Carolina; Ionete, Roxana-Elena; Eljarrat, Ethel

    2016-10-01

    Enantioselective analysis is a powerful tool for the discrimination of biotic and abiotic transformation processes of chiral environmental contaminants because their environmental biodegradation is mostly stereospecific. However, it is challenging when applied to new contaminants since enantioselective analysis methods are currently available only for a limited number of compounds. The enantioselective analysis of chiral novel brominated flame retardants (NBFRs) either using gas chromatography (GC) or liquid chromatography (LC) with various chiral stationary phases (CSP) coupled with various mass spectrometric techniques was extensively discussed. The elution order of hexabromocyclododecane (HBCD) enantiomers in chiral LC was reviewed using the experimental LC data combined also with predictions from a multi-mode Hamiltonian dynamics simulation model based on interaction energies of HBCD enantiomers with β-permethylated cyclodextrin. The further development of analytical methodologies for new chiral BFRs using advanced hyphenated analytical techniques, but also the next generation mass spectrometer analyzers (i.e. GC-Qrbitrap MS-MS, LC-Qrbitrap MS-MS), will contribute to a better characterization of the transformation pathways of chiral BFRs. PMID:27265736

  9. Rice ingestion is a major pathway for human exposure to organophosphate flame retardants (OPFRs) in China.

    PubMed

    Zhang, Xingli; Zou, Wei; Mu, Li; Chen, Yuming; Ren, Chaoxiu; Hu, Xiangang; Zhou, Qixing

    2016-11-15

    Although organophosphate flame retardants (OPFRs) have been shown to accumulate in abiotic and biotic environmental compartments, data about OPFRs concentrations in various foods are limited and are none in humans through diets. In this work, the concentrations of 6 typical OPFRs were investigated in 50 rice samples, 75 commonly consumed foods and 45 human hair samples from China. The dietary intakes of OPFRs for adult people via food ingestion were estimated. The concentrations of ΣOPFRs in foods ranged from 0.004ng/g to 287ng/g. OPFRs were detected in 53.3% of the human hair samples. The highest OPFRs concentrations were found in rice and vegetables. Tri(2-chloroethyl)phosphate(TCEP), tris(2-chloroisopropyl)phosphate(TCIPP), and tri(2-ethyltexyl)phosphate(TEHP) were predominant in all food samples. OPFRs concentrations in foods were not significantly affected by the packaging materials. The mean dietary intakes of ΣOPFRs for adult males and females were 539 and 601ng/kg body weight/day, respectively. The greatest contribution to these values is from rice, accounting for approximately 60% of the total intake, particularly from rice protein. Rice ingestion was considered a potential major pathway for human exposure to OPFRs, and regional differences in the levels of OPFRs in foods and dietary differences should be given more attention in the future. PMID:27484948

  10. A new brominated polymeric additive for flame retardant glass-filled polybutylene terephthalate

    NASA Technical Reports Server (NTRS)

    Nir, Z.; Kourtides, D. A.; Parker, J. A.; Bar-Yaacov, Y.; Minke, R.; Touval, I.

    1982-01-01

    Attention is called to the undesirable effects (poor ultraviolet light stability and blooming) sometimes introduced by brominated flame retarders. A brominated polymeric additive (BPA) with little or none of these undesirable side effects is compared with decabromobiphenyl oxide (DBBPO). The additive bears the product name F-2300. It is found to be more easily dispersed than DBBPO. The F-2300 is as effective as the DBBPO in the oxygen index test. The improved efficiency of the F-2300 may be explained by its better dispersion in polybutylene terephthalate (PBT). Glass-filled PBT containing F-2300 is found to be more resistant to UV degradation than DBBPO-containing formulas. Formulations with F-2300 therefore have a longer useful outdoor life. F-2300 is a diglycidyl-type polymer containing 50 percent aromatically bound bromine. Its melting point is 112 C, and it is stable up to 372 C. It is pointed out that since its melts at a relatively low temperature, it can be introduced into the formulation as a large agglomerate and still be dispersed evenly throughout the polymer.

  11. Characterization of organophosphorus flame retardants' sorption on building materials and consumer products

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoyu; Allen, Matthew R.; Roache, Nancy F.

    2016-09-01

    Better understanding the transport mechanisms of organophosphorus flame-retardants (OPFRs) in the residential environment is important to more accurately estimate their indoor exposure and develop risk management strategies that protect human health. This study describes an improved dual small chamber testing method to characterize the sorption of OPFRs on indoor building materials and consumer products. The OPFRs studied were tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCIPP). The test materials and products used as sinks include concrete, ceiling tile, vinyl flooring, carpet, latex painted gypsum wallboard, open cell polyurethane foam, mattress pad and liner, polyester clothing, cotton clothing, and uniform shirt. During the tests, the amount of OPFRs absorbed by the materials at different exposure times was determined simultaneously. OPFRs air concentrations at the inlet and inside the test chamber were monitored. The data were used to rank the sorption strength of the OPFRs on different materials. In general, building materials exhibited relatively stronger sorption strength than clothing textiles. The material-air partition and material phase diffusion coefficients were estimated by fitting a sink model to the sorption concentration data for twelve materials with three OPFRs. They are in the range of 2.72 × 105 to 3.99 × 108 (dimensionless) for the material-air partition coefficients and 1.13 × 10-14 to 5.83 × 10-9 (m2/h) for the material phase diffusion coefficients.

  12. High Exposure to Organophosphate Flame Retardants in Infants: Associations with Baby Products.

    PubMed

    Hoffman, Kate; Butt, Craig M; Chen, Albert; Limkakeng, Alexander T; Stapleton, Heather M

    2015-12-15

    Infant products containing polyurethane foam are commonly treated with organophosphate flame retardants (PFRs), including tris(1,3-dichloro-2-propyl)phosphate (TDCIPP) and triphenyl phosphate (TPHP). Infants may have greater exposure due to greater contact with these products, yet little is known about levels of exposure or the factors contributing to higher exposure. We recruited children age 2-18 months from North Carolina to investigate PFR exposure (n = 43; recruited 2014-2015). Parents provided information on potential sources and modifiers of exposure, and reported whether they owned common infant products. We measured five PFR metabolites in urine samples collected from children. TDCIPP and TPHP metabolites (bis(1,3-dichloro-2-propyl) phosphate (BDCIPP) and diphenyl phosphate (DPHP)) were most commonly detected (>93% detect). Other metabolites were detected infrequently (<35% detect). Although we did not observe a clear age trend for infants, BDCIPP levels were substantially higher than those reported for adults (geometric mean = 7.3 ng/mL). The number of infant products owned was strongly associated with BDCIPP; children with >16 products had BDCIPP levels that were 6.8 times those with <13 (p = 0.02). Infants attending daycare centers also had higher BDCIPP levels (3.7 times those of others; p = 0.07), suggesting time spent in this microenvironment contributes to higher exposure. In contrast, DPHP levels were not related to products owned, time in different microenvironments, or behavior. PMID:26551726

  13. Atmospheric occurrence and fate of organophosphorus flame retardants and plasticizer at the German coast

    NASA Astrophysics Data System (ADS)

    Wolschke, Hendrik; Sühring, Roxana; Mi, Wenying; Möller, Axel; Xie, Zhiyong; Ebinghaus, Ralf

    2016-07-01

    This study reports the occurrence and distribution of organophosphor esters (OPEs), used as flame retardants and plasticizer, in the marine atmosphere of the German Coast. From August 2011 to October 2012, 58 high volume air samples (gas/particle phase separately) were collected at the German North Sea coast town Büsum. With the use of a GC-MS/MS System for instrumental analysis, detection limits for OPEs in air samples could be significantly improved compared to the previously used single GC-MS method. The concentration (gas + particle phase) of total OPEs was on average 5 pg/m3, with eight of the nine investigated compounds detectable in over 50% of the samples. A focus of this investigation concerned the partioning of OPEs between the particle and the gas phase. The observed partitioning of OPEs in this study was distinguished from previous studies. While previous studies reported OPEs exclusively in the particle phase, a significant part of the sum OPE concentration (55%) was detected in the gas phase. The contribution of the gas phase even reached up to as high as 88% for individual compounds such as tri-iso-butyl phosphate.

  14. From Clothing to Laundry Water: Investigating the Fate of Phthalates, Brominated Flame Retardants, and Organophosphate Esters.

    PubMed

    Saini, Amandeep; Thaysen, Clara; Jantunen, Liisa; McQueen, Rachel H; Diamond, Miriam L

    2016-09-01

    The accumulation of phthalate esters, brominated flame retardants (BFRs) and organophosphate esters (OPEs) by clothing from indoor air and transfer via laundering to outdoors were investigated. Over 30 days cotton and polyester fabrics accumulated 3475 and 1950 ng/dm(2) ∑5phthalates, 65 and 78 ng/dm(2) ∑10BFRs, and 1200 and 310 ng/dm(2) ∑8OPEs, respectively. Planar surface area concentrations of OPEs and low molecular weight phthalates were significantly greater in cotton than polyester and similar for BFRs and high molecular weight phthalates. This difference was significantly and inversely correlated with KOW, suggesting greater sorption of polar compounds to polar cotton. Chemical release from cotton and polyester to laundry water was >80% of aliphatic OPEs (log KOW < 4), < 50% of OPEs with an aromatic structure, 50-100% of low molecular weight phthalates (log KOW 4-6), and < detection-35% of higher molecular weight phthalates (log KOW > 8) and BFRs (log KOW > 6). These results support the hypothesis that clothing acts an efficient conveyer of soluble semivolatile organic compounds (SVOCs) from indoors to outdoors through accumulation from air and then release during laundering. Clothes drying could as well contribute to the release of chemicals emitted by electric dryers. The results also have implications for dermal exposure. PMID:27507188

  15. Organophosphate ester (OPE) flame retardants and plasticizers in the open Mediterranean and Black Seas atmosphere.

    PubMed

    Castro-Jiménez, Javier; Berrojalbiz, Naiara; Pizarro, Mariana; Dachs, Jordi

    2014-03-18

    The presence of organophosphate ester (OPE) flame retardants and plasticizers has been confirmed for the first time in the atmosphere over the Mediterranean and Black Seas. Atmospheric aerosol samples were collected during two West-East oceanographic cruises across the Mediterranean and in the southwest Black Sea. This comprehensive assessment of baseline concentrations of aerosol phase OPEs, spatial distribution, and related deposition fluxes reveals levels ranging from 0.4 to 6.0 ng m(-3) for the ∑14OPEs and a lack of significant differences among sub-basins. Levels measured across the Mediterranean Sea and in the Black Sea are in the upper range or higher than those from previous reports for the marine atmosphere, presumably due to proximity to sources. From 13 to 260 tons of OPEs are estimated to be annually loaded to the Mediterranean Sea open waters from the atmosphere. Tris-(1-chloro-2-propyl)phosphate (TCPP) was the most abundant compound over the atmosphere of all the Mediterranean and Black Sea sub-basins, and therefore the chemical reaching surface waters at a higher extent by dry deposition. The atmospheric deposition fluxes of phosphorus due to OPE deposition is a significant fraction of known atmospheric inputs of new organic phosphorus (P), suggesting the relevant role that anthropogenic organic pollutants could play in the P cycle. PMID:24564832

  16. Halogenated Natural Products in Dolphins: Brain-Blubber Distribution and Comparison with Halogenated Flame Retardants.

    PubMed

    Barón, E; Hauler, C; Gallistl, C; Giménez, J; Gauffier, P; Castillo, J J; Fernández-Maldonado, C; de Stephanis, R; Vetter, W; Eljarrat, E; Barceló, D

    2015-08-01

    Halogenated natural products (MHC-1, TriBHD, TetraBHD, MeO-PBDEs, Q1, and related PMBPs) and halogenated flame retardants (PBDEs, HBB, Dec 602, Dec 603, and DP) in blubber and brain are reported from five Alboran Sea delphinids (Spain). Both HNPs and HFRs were detected in brain, implying that they are able to surpass the blood-brain barrier and reach the brain, which represents a new finding for some compounds, such as Q1 and PMBPs, MHC-1, TriBHD, TetraBHD, or Dec 603. Moreover, some compounds (TetraBHD, BDE-153, or HBB) presented higher levels in brain than in blubber. This study evidence the high concentrations of HNPs in the marine environment, especially in top predators. It shows the importance of further monitoring these natural compounds and evaluating their potential toxicity, when most studies focus on anthropogenic compounds only. While no bioaccumulation was found for ∑HNPs, ∑HFRs increased significantly with body size for both common and striped dolphins. Studies evaluating BBB permeation mechanisms of these compounds together with their potential neurotoxic effects in dolphins are recommended. PMID:26148182

  17. Health effects of haloalkyl phoshpate flame retardants and potential metabolic products

    SciTech Connect

    Holleman, J.W.

    1984-01-01

    The purpose of this study was to produce a state-of-the-art review and assessment of the health effects associated with tris(1,3-dichloro-2-propyl) phosphate (TDCP) and related compounds which find widespread use as flame retardants. It was intended to support an ongoing evaluation of TDCP within the Office of Toxic Substances. TDCP was demonstrated to be a potent oncogen in a 2-year chronic study in rats. It is probable that the oncogenicity of TDCP is due, in part or in total, to the production of reactive metabolic intermediates which are well-known mutagens. As an example, 1,3-dichloro-2-propanone is a bifunctional alkylating agent with intercalating properties. Its carbonyl functional group is potentially reactive as well. Therefore, it is not surprising that it has been shown to be a very potent in vitro mutagen. This examination of the metabolic pathways of TDCP with emphasis on oxidative processes common to organophosphate compounds, and documentation of the health effects of halogenated carbonyl-containing compounds, which may be generated metabolically, will assist in the assessment of health hazards made in the absence of extensive further testing.

  18. Presence and select determinants of organophosphate flame retardants in public swimming pools.

    PubMed

    Teo, Tiffany L L; Coleman, Heather M; Khan, Stuart J

    2016-11-01

    The occurrence of five organophosphate flame retardants (PFRs) consisting of tributyl phosphate (TNBP), tris(2-chloroethyl) phosphate (TCEP), tris(1-chloro-2-propyl) phosphate (TCIPP), tris(1.3-dichloro-2-propyl) phosphate (TDCIPP) and triphenyl phosphate (TPHP) in swimming pools were investigated. Fifteen chlorinated public swimming pools were sampled, including indoor pools, outdoor pools and spa pools. The analyses were carried out using isotope dilution gas chromatography tandem mass spectrometry. All five PFRs were detected in swimming pool waters with concentrations ranging from 5-27ng/L (TNBP), 7-293ng/L (TCEP), 62-1180ng/L (TCIPP), 10-670ng/L (TDCIPP) and 8-132ng/L (TPHP). The concentrations of PFRs were generally higher in indoor swimming pools compared to outdoor swimming pools. In municipal water supplies, used to fill the swimming pools in three of the sampling locations, the five PFRs were all below the limit of quantifications, eliminating this as the source. Potential leaching of PFRs from commonly used swimming equipment, including newly purchased kickboards and swimsuits was investigated. These experiments revealed that PFRs leached from swimsuits, and may be a source of PFRs in swimming pools. A quantitative risk assessment revealed that the health risk to PFRs via swimming pools was generally low and below commonly applied health risk benchmarks. PMID:27355519

  19. Chemical characterization of brominated flame retardants and identification of structurally representative compounds.

    PubMed

    Andersson, Patrik L; Oberg, Kjell; Orn, Ulrika

    2006-05-01

    Three training sets were selected, each consisting of 10 structurally diverse compounds representative of brominated flame retardants (BFRs) that are either in use or have been used. Just three compounds account for nearly all the total production volume of BFRs. In the present study, however, the physicochemical characteristics of a far more structurally diverse set of 65 BFRs was explored using 15 molecular descriptors (including log P, constitutional counts, and semiempirical quantum mechanical parameters) and principal component analysis (PCA). The PCA generated an overview of the structural variation among BFRs, and certain compounds with unique physicochemical properties and specific clusters of compounds with distinct properties were identified. The training-set compounds were selected by applying the condensed information obtained from the PCA and statistical experimental design. The three training sets, which were designated as optimal, practical, and alternative, were selected either to maximize the structural variation (optimal) or to combine structural variation with practical advantages, such as ease of experimental handling and commercial availability (practical and alternative). Inclusion of the suggested compounds in assessments of the persistence, bioaccumulation, and toxicity properties of BFRs and related programs should help to increase our understanding of the effects and environmental fate of these compounds. PMID:16704058

  20. Organophosphorus flame retardants and plasticizers in air from various indoor environments.

    PubMed

    Marklund, Anneli; Andersson, Barbro; Haglund, Peter

    2005-08-01

    Eleven organophosphorus compounds (OPs) that are used as plasticizers and flame retardants were analysed in duplicate samples of indoor air from 17 domestic and occupational environments. Solid-phase extraction (SPE) columns were used as adsorbents and analysis was performed using GC with a nitrogen phosphorus selective detector. The total amounts of OPs in the air samples ranged between 36 and 950 ng m(-3); tris(chloropropyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) being the most abundant (0.4 to 730 ng m(-3)), followed by tributyl phosphate (0.5-120 ng m(-3)). Public buildings tended to have about 3-4 times higher levels of OPs than domestic buildings. The relative amounts of individual OPs varied between the sites and generally reflected the building materials, furniture and consumer products used in the sampled environments. Potential sources of these compounds include, inter alia, acoustic ceilings, upholstered furniture, wall coverings, floor polish and polyvinylchloride floor coverings. A correlation was observed between the TCEP concentrations in the air in the sampled environments and previously reported concentrations in dust, but no such correlation was seen for the heavier and less volatile tris(2-butoxyethyl) phosphate (TBEP). Based on estimated amounts of indoor air inhaled and dust ingested, adults and children in the sampled environments would be exposed to up to 5.8 microg kg(-1) day(-1) and 57 microg kg(-1) day(-1) total OPs, respectively. PMID:16049584

  1. Cyanuric Chloride and Hexachlorocyclotriphosphazene Derivatives as Flame Retardants in Cotton Textile Applications

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In a series of experiments cyanuric chloride and hexachlorocyclotriphosphazene derivatives were synthesized and characterized using spectroscopic, thermogravimetric, limiting oxygen index, and vertical flame analyses. Standardized test results have determined these compounds are promising flame reta...

  2. Effect of cellulose acetate butyrate microencapsulated ammonium polyphosphate on the flame retardancy, mechanical, electrical, and thermal properties of intumescent flame-retardant ethylene-vinyl acetate copolymer/microencapsulated ammonium polyphosphate/polyamide-6 blends.

    PubMed

    Wang, Bibo; Tang, Qinbo; Hong, Ningning; Song, Lei; Wang, Lei; Shi, Yongqian; Hu, Yuan

    2011-09-01

    Ammonium polyphosphate (APP), a widely used intumescent flame retardant, has been microencapsulated by cellulose acetate butyrate with the aim of enhancing the water resistance of APP and the compatibility between the ethylene-vinyl acetate copolymer (EVA) matrix and APP. The structure of microencapsulated ammonium polyphosphate (MCAPP) was characterized by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and water contact angle (WCA). The flame retadancy and thermal stability were investigated by a limiting oxygen index (LOI) test, UL-94 test, cone calorimeter, and thermogravimetric analysis (TGA). The WCA results indicated that MCAPP has excellent water resistance and hydrophobicity. The results demonstrated that MCAPP enhanced interfacial adhesion, mechanical, electrical, and thermal stability of the EVA/MCAPP/polyamide-6 (PA-6) system. The microencapsulation not only imparted EVA/MCAPP/PA-6 with a higher LOI value and UL-94 rating but also could significantly improve the fire safety. Furthermore, the microencapsulated EVA/MCAPP/PA-6 composites can still pass the UL-94 V-0 rating after treatment with water for 3 days at 70 °C, indicating excellent water resistance. This investigation provides a promising formulation for the intumescent flame retardant EVA with excellent properties. PMID:21859130

  3. Flame retardant BDE-47 effectively activates nuclear receptor CAR in human primary hepatocytes

    EPA Science Inventory

    Polybrominated diphenyl ether BDE-47 (2,2’,4,4’-tetrabromodiphenyl ether) is a thyroid hormone disruptor in mice; hepatic induction of various metabolic enzymes and transporters has been suggested as the mechanism for this disruption. Utilizing Car-/- and Pxr-/- mice as well as h...

  4. Brominated flame retardants in offices in Michigan, U.S.A.

    PubMed Central

    Batterman, Stuart; Godwin, Christopher; Chernyak, Sergei; Jia, Chunrong; Charles, Simone

    2015-01-01

    Brominated flame retardants (BFRs) are now ubiquitous contaminants with large reservoirs and high concentrations in buildings. Most of the information documenting BFR levels has been obtained in residences, and other environments that can lead to exposure have received relatively little attention, including offices that contain numerous BFR sources and where individuals spend considerable time. The aim of this study is to characterize BFR concentrations, potential emission sources, and migration pathways in office environments. We measure BFR levels in floor dust, indoor air, ventilation filter dust, and carpets in ten commercial and institutional buildings in Michigan, U.S.A. The median concentration of total BDEs in settled dust was 8754 ng g−1, at the upper range of levels previously reported. Especially elevated levels were found in offices in buildings that contained known or likely BFR sources, e.g., computer servers. A trends analysis in a newly constructed building showed remarkable increases in concentrations of BFRs in settled dust and indoor air, and apparent steady-state levels were reached 5 to 8 months after building completion, a particularly striking finding given that the building was constructed and furnished several years after the voluntary phase-out of the penta- and octa-mixtures. Airborne particulate matter collected in a building's HVAC system filters contained PBDEs, including BDE-209, at levels exceeding the concentration of floor dust. In conjunction with estimates of building air flow rates, filter efficiency and other parameters, mass balance calculations for this building were used to estimate the emission rates and reservoirs of PBDEs. The widespread distribution of BFRs found in offices in both new and old buildings suggests the significance of workplace exposures, the need for controls to minimize human exposure, intra-building migration, and environmental releases of these chemicals, and the need for monitoring in new buildings

  5. Distribution of copper, silver and gold during thermal treatment with brominated flame retardants.

    PubMed

    Oleszek, Sylwia; Grabda, Mariusz; Shibata, Etsuro; Nakamura, Takashi

    2013-09-01

    The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition. In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000°C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is resistant to HBr and remains unchanged in the residue. PMID:23746984

  6. Transformation of Flame Retardant Tetrabromobisphenol A by Aqueous Chlorine and the Effect of Humic Acid.

    PubMed

    Gao, Yuan; Pang, Su-Yan; Jiang, Jin; Ma, Jun; Zhou, Yang; Li, Juan; Wang, Li-Hong; Lu, Xue-Ting; Yuan, Li-Peng

    2016-09-01

    In this work, it was found that the most widely used brominated flame retardant tetrabromobisphenol A (TBrBPA) could be transformed by free chlorine over a wide pH range from 5 to 10 with apparent second-order rate constants from 138 to 3210 M(-1)·s(-1). A total of eight products, including one quinone-like compound (i.e., 2,6-dibromoquinone), two dimers, and several simple halogenated phenols (e.g., 4-(2-hydroxyisopropyl)-2,6-dibromophenol, 2,6-dibromohydroquinone, and 2,4,6-tribromophenol), were detected by high-performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) using a novel precursor ion scan (PIS) approach. A tentative reaction pathway was proposed: chlorine initially oxidized TBrBPA leading to the formation of a phenoxy radical, and then this primary radical and its secondary intermediates (e.g., 2,6-dibromo-4-isopropylphenol carbocation) formed via beta-scission subsequently underwent substitution, dimerization, and oxidation reactions. Humic acid (HA) considerably inhibited the degradation rates of TBrBPA by chlorine even accounting for oxidant consumption. A similar inhibitory effect of HA was also observed in permanganate and ferrate oxidation. This inhibitory effect was possibly attributed to the fact that HA competitively reacted with the phenoxy radical of TBrBPA and reversed it back to parent TBrBPA. This study confirms that chlorine can transform phenolic compounds (e.g., TBrBPA) via electron transfer rather than the well-documented electrophilic substitution, which also have implications on the formation pathway of halo-benzoquinones during chlorine disinfection. These findings can improve the understanding of chlorine chemistry in water and wastewater treatment. PMID:27487036

  7. Thermal Recycling of Brominated Flame Retardants with Fe2O3.

    PubMed

    Altarawneh, Mohammednoor; Ahmed, Oday H; Jiang, Zhong-Tao; Dlugogorski, Bogdan Z

    2016-08-01

    Plastics containing brominated flame retardants (BFRs) constitute the major fraction of nonmetallic content in e-waste. Co-pyrolysis of BFRs with hematite (Fe2O3) represents a viable option for the thermal recycling of BFRs. Consensus of experimental findings confirms the excellent bromine fixation ability of Fe2O3 and the subsequent formation of iron bromides. This contribution provides a comprehensive mechanistic account of the primary reactions between a cluster model of Fe2O3 and major bromine-bearing products from the decomposition of tetrabromobisphenol A (TBBA), the most commonly deployed BFR. We estimate the thermo-kinetic parameters for interactions of Fe2O3 with HBr, brominated alkanes and alkenes, bromobenzene, and bromophenol. Dissociative addition of HBr at a Fe-O bond proceeds through a trivial barrier of 8.2 kcal/mol with fitted parameters in the Arrhenius equation of k(T) = 7.96 × 10(11) exp(-6400/RT) s(-1). The facile and irreversible nature for HBr addition to Fe2O3 accords with the experimentally reported 90% reduction in HBr emission when Fe2O3 interacts with TBBA pyrolysates. A detailed kinetic analysis indicates that, transformation of Fe2O3 into iron bromides and oxybromides occurs via successive addition of HBr to Fe(Br)-O(H) entities. Elimination of a water molecule proceeds through an intramolecular H transfer. A direct elimination one-step mechanism operates in the dehydrohalogenation of bromoethane into ethene over Fe2O3. Dissociative decomposition and direct elimination channels assume comparable reaction rates in formation of acetylene from vinyl bromide. Results from this study provide an atomic-based insight into a promising thermal recycling route of e-waste. PMID:27366936

  8. Plastics additives in the indoor environment--flame retardants and plasticizers.

    PubMed

    Wensing, M; Uhde, E; Salthammer, T

    2005-03-01

    Phthalic acid esters and phosphororganic compounds (POC) are generally known as semivolatile organic compounds (SVOCs) and are frequently utilized as plasticizers and flame retardants in commercial products. In the indoor environment, both compound groups are released from a number of sources under normal living conditions and accumulate in air and dust. Therefore, inhalation of air and ingestion of house dust have to be considered as important pathways for the assessment of exposure in living habitats. Especially in the case of very young children, the oral and dermal uptake from house dust might be of relevance for risk assessment. A critical evaluation of indoor exposure to phthalates and POC requires the determination of the target compounds in indoor air and house dust as well as emission studies. The latter are usually carried out under controlled conditions in emission test chambers or cells. Furthermore, chamber testing enables the determination of condensable compounds by fogging sampling. In the case of automobiles, specific scenarios have been developed to study material emissions on a test stand or to evaluate the exposure of users while the vehicle is driving. In this review, results from several studies are summarized and compared for seven phthalic esters and eight POC. The available data for room air and dust differ widely depending on investigated compound and compartment. Room air studies mostly include only a limited number of measurements, which makes a statistical evaluation difficult. The situation is much better for house dust measurements. However, the composition of house dust is very inhomogeneous and the result is strongly dependent on the particle size distribution used for analysis. Results of emission studies are presented for building products, electronic equipment, and automobiles. Daily rates for inhalation and dust ingestion of phthalic esters and POC were calculated from 95-percentiles or maximum values. A comparison of the data

  9. Measurements of Selected Brominated Flame Retardants in Nursing Women: Implications for Human Exposure

    PubMed Central

    2014-01-01

    We have examined several emerging brominated flame retardants (BFRs) including 2-ethyl-1-hexyl-2,3,4,5-tetrabromobenzoate (TBB), bis(2-ethylhexyl) tetrabromophthalate (TBPH), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), 4,5,6,7-tetrabromo-1,1,3-trimethyl-3-(2,3,4,5-tetrabromophenyl)-indane (OBIND), and decabromodiphenyl ethane (DBDPE) in paired human maternal serum (n = 102) and breast milk (n = 105) collected in 2008–2009 in the Sherbrooke region in Canada. Three legacy BFRs were also included in the study for comparison: decabromobiphenyl (BB-209), 2,2′,4,4′,5,5′-hexabromobiphenyl (BB-153), and 2,2′,4,4′,5,5′-hexabromodiphenyl ethers (BDE-153). TBB, BB-153, and BDE-153 had detection frequencies greater than 55% in both serum and milk samples. Their lipid weight (lw) adjusted median concentrations (ng g–1 lw) in serum and milk were 1.6 and 0.41 for TBB, 0.48 and 0.31 for BB-153, and 1.5 and 4.4 for BDE-153, respectively. The detection frequencies for the other BFRs measured in serum and milk were 16.7% and 32.4% for TBPH, 3.9% and 0.0% for BTBPE, 2.0% and 0.0% for BB-209, 9.8% and 1.0% for OBIND, and 5.9% and 8.6% for DBDPE. The ratio of TBB over the sum of TBB and TBPH (fTBB) in serum (0.23) was lower than that in milk (0.46), indicating TBB has a larger tendency than TBPH to be redistributed from blood to milk. Overall, these data confirm the presence of non-PBDE BFRs in humans, and the need to better understand their sources, routes of exposure, and potential human health effects. PMID:24992303

  10. Reproductive changes in American kestrels (Falco sparverius) in relation to exposure to technical hexabromocyclododecane flame retardant.

    PubMed

    Fernie, Kim J; Marteinson, Sarah C; Bird, David M; Ritchie, Ian J; Letcher, Robert J

    2011-11-01

    Recently, the ban of hexabromocyclododecane (HBCD), a high-production-volume flame retardant, was announced in Europe and North America. However, the effects of HCBD remain understudied in birds. The objectives of the present comparative effects study were to determine whether exposure to an HBCD technical mixture (HBCD-TM) altered avian reproductive measures at an environmentally relevant concentration. American kestrels were exposed daily by food to HBCD-TM, i.e., 0.51 µg HBCD/g kestrel/d; exposed kestrels laid eggs that had α-HBCD concentrations (163.5 ± 75.1 ng/g wet wt) tenfold greater than β- and γ-HBCD isomers, an isomer profile and concentrations similar to those of eggs of wild peregrine falcons (Falco peregrinus). Concentrations of HBCD were not detected in the control kestrel eggs. In comparison with controls, the kestrels exposed to HBCD began to lay their eggs 6 d earlier and laid larger clutches of smaller eggs. The size of the eggs was inversely correlated with the in ovo α-HBCD concentrations. The smaller eggs of the HBCD exposed kestrels also lost more weight by midincubation, suggesting increased eggshell porosity since eggshell thickness was comparable. Generally birds that lay more eggs and lay earlier in the breeding season gain the advantage of better hatching and fledging success, yet the kestrels exposed to HBCD failed to have better reproductive success than the control birds. These reproductive changes were a function of HBCD exposure, likely through changes in food consumption, with possible impacts on, for example, reproductive behavior and/or alterations in thyroid hormones. PMID:21898552

  11. Organophosphorus flame retardants and plasticizers in marine and fresh water biota and in human milk.

    PubMed

    Sundkvist, Anneli Marklund; Olofsson, Ulrika; Haglund, Peter

    2010-04-01

    The levels and relative proportions of 11 organophosphorus flame retardants and plasticizers (OPs), some of which are reportedly toxic to aquatic organisms, were investigated in human breast milk and samples of fish and mussels from Swedish lakes and coastal areas in order to assess spatial differences in environmental exposure and spatial and temporal differences in human exposure. Some of the biota samples were collected at locations with known potential sources of OPs, but most were collected in background locations. Tris-2-chloroisopropyl phosphate (TCPP) and triphenyl phosphate (TPP) dominated in the biota with levels ranging from 170 to 770 ng g(-1) for TCPP in perch and between 21 and 180 ng g(-1) for TPP. In milk samples, TCPP (median 45 ng g(-1)) and tributyl phosphate (median 12 ng g(-1)) were the most frequently occurring OPs. Among samples of fish from background locations, the concentrations and profiles of most OPs were quite similar, indicating that their sources were diffuse. However, in fish from sample locations near known sources, there were marked differences in OP concentrations and profiles. Fish from a stream receiving surface water from Arlanda airport displayed high levels of OPs (10 200 ng g(-1)) that are commonly used in aircraft hydraulic fluids. Fish collected at points 1 or 2 km downstream of sewage treatment plants showed significantly higher levels of tris(2-butoxyethyl) phosphate (TBEP), one of the most typically abundant OP in effluents from such plants. In the milk samples obtained from women in different towns no distinct differences were detected in OP concentrations or profiles. However, the levels of TBEP tended to be higher in milk collected 10 years ago than in milk collected more recently. However, human exposure to OPs through eating fish or to breastfeeding babies seems to be of minor importance in relation to other potential sources, such as indoor dust inhalation and ingestion. PMID:20383376

  12. Levels of Blood Organophosphorus Flame Retardants and Association with Changes in Human Sphingolipid Homeostasis.

    PubMed

    Zhao, Fanrong; Wan, Yi; Zhao, Haoqi; Hu, Wenxin; Mu, Di; Webster, Thomas F; Hu, Jianying

    2016-08-16

    While a recent toxicological study has shown that organophosphorus flame retardants (OPFRs) may disrupt sphingolipid homeostasis, epidemiologic evidence is currently lacking. In this study, a total of 257 participants were recruited from Shenzhen, China. Eleven OPFRs were for the first time simultaneously determined in the human blood samples by ultraperformance liquid chromatography and tandem mass spectrometry. Six OPFRs, tributyl phosphate (TNBP), 2-ethylhexyl diphenyl phosphate (EHDPP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(2-butoxyethyl) phosphate (TBOEP), triethyl phosphate (TEP), and TPHP, were detectable in at least 90% of participants, with median concentrations of 37.8, 1.22, 0.71, 0.54, 0.49, and 0.43 ng/mL, respectively. Sphingomyelin (SM) levels in the highest quartile of EHDPP, TPHP, TNBP, TBOEP, TEP, and TCIPP were 45.3% [95% confidence interval; 38.1%, 53.0%], 51.9% (45.5%, 58.6%), 153.6% (145.1%, 162.3%), 20.6% (14.5%, 27.0%), 59.0% (52.1%, 66.2%), and 62.8% (55.2%, 70.6%) higher than those in the lowest quartile, respectively, after adjusting for covariates. Sphingosine 1-phosphate (S1P) levels in the highest quartile of EHDPP, TPHP, and TNBP were 36% (-39%, -33%), 16% (-19%, -14%), and 36% (-38%, -33%) lower than those in the lowest quartile, respectively. A similar pattern emerged when exposures were modeled continuously. We for the first time found the associations between OPFRs and changes in human sphingolipid homeostasis. PMID:27434659

  13. Non-PBDE halogenated flame retardants in Canadian indoor house dust: sampling, analysis, and occurrence.

    PubMed

    Fan, Xinghua; Kubwabo, Cariton; Rasmussen, Pat E; Wu, Fang

    2016-04-01

    An analytical method was developed for the measurement of 18 novel halogenated flame retardants in house dust. Sample preparation was based on ultrasound-assisted solvent extraction and clean up with solid phase extraction (SPE). Sample extracts were analyzed by gas chromatography-mass spectrometry (GC/MS) operated in electron capture negative ion (ECNI) chemical ionization mode. Baseline data from 351 fresh (active) dust samples collected under the Canadian House Dust Study (CHDS) revealed that five out of 18 target chemicals were present with detection frequencies higher than 90 %. Median (range) concentrations for these five compounds were as follows: 104 (<1.5-13,000) ng/g for 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTBB), 8.5 (<1.7-2390) ng/g for 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), 10.2 (<1.7-430) ng/g for hexabromobenzene (HBB), 2.9 (<1.2-1410) ng/g for syn-dechlorane plus (syn-DP) and 5.6 (<1.9-1570) ng/g for anti-dechlorane plus (anti-DP). A comparison of two sampling methods in a subset of 40 homes showed significant positive correlations between samples of "active" dust and samples taken directly from the household vacuum cleaner for all target compounds having median values above their corresponding method detection limits (MDLs). In addition, the method was also applied to the analysis of the targeted compounds in National Institute of Standards and Technology (NIST) standard reference material (SRM 2585, organic contaminants in house dust). Results from the current study could contribute to the potential certification of target chemicals in SRM 2585. PMID:26780041

  14. Advanced oxidation kinetics of aqueous tri alkyl phosphate flame retardants and plasticizers

    PubMed Central

    Watts, Michael J.; Linden, Karl G.

    2009-01-01

    Tri alkyl phosphate esters are a class of anthropogenic organics commonly found in surface waters of Europe and North America, due to their frequent application as flame retardants, plasticizers, and solvents. Four tri alkyl phosphate esters were evaluated to determine second-order rates of reaction with ultraviolet- and ozone-generated •OH in water. In competition with nitrobenzene in UV irradiated hydrogen peroxide solutions tris(2-butoxyethyl) phosphate (TBEP) was fastest to react with •OH (kOH,TBEP=1.03×1010 M-1s-1), followed sequentially by tributyl phosphate (TBP), tris(2-chloroethyl) phosphate (TCEP), and tris(2-chloroisopropyl) phosphate (TCPP) (kOH,TBEP=6.40×109, kOH,TBEP=5.60×108, & kOH,TBEP=1.98×10 M-1s-1). A two-stage process was used to test the validity of the determined kOH for TBEP and the fastest reacting halogenated alkyl phosphate, TCEP. First, •OH oxidation of TCEP and TBEP, in competition with nitrobenzene, was measured in ozonated hydrogen peroxide solutions. Applying multiple regression analysis, it was determined that the UV-H2O2 and O3-H2O2 data sets were statistically identical for each compound. The subsequent validated kOH were used to predict TCEP and TBEP photodegradation in neutral pH, model surface water after chemical oxidant addition and UV irradiation (up to 1000 mJ/cm2). The insignificant difference, between the predicted TBEP and TCEP photodegradation and a best-fit of the first-order exponential decay function to the observed TBEP and TCEP concentrations with increasing UV fluence, was further evidence of the validity of the determined kOH. TBEP oxidation rates were similar in the surface waters tested. Substantial TCEP oxidation in the model surface water required a significant increase in H2O2. PMID:19475974

  15. Role of Surface Interactions in the Synergizing Polymer/Clay Flame Retardant Properties

    SciTech Connect

    Pack, S.; Kashiwagi, T; Cao, C; Korach, C; Lewin, M; Rafailovich, M

    2010-01-01

    The absorption of resorcinol di(phenyl phosphate) (RDP) oligomers on clay surfaces has been studied in detail and is being proposed as an alternative method for producing functionalized clays for nanocomposite polymers. The ability of these clays to be exfoliated or intercalated in different homopolymers was investigated using both transmission electron microscopy and small-angle X-ray scattering results, compared with contact angle measurements on Langmuir-Blodgett clay monolayers, where the interfacial energies were used as predictors of the polymer/clay interactions. We found that the contact angle between PS/RDP clay monolayer substrates was {approx}2.5{sup o}, whereas the angle for polystyrene (PS)/Cloisite 20A clays substrates was {approx}32{sup o}, consistent with the large degree of exfoliation observed in PS for the RDP-coated clays. The interfacial activity of these clays was also measured, and we found that the RDP-coated clays segregated to the interfaces of PC/poly(styrene-co-acrylonitrile) blends, while they segregated into the poly(methyl methacrylate) (PMMA) domain of PS/PMMA blends. This morphology was explained in terms of the relative energy advantage in placing the RDP versus the Cloisite clays at the interfaces. Finally, we demonstrated the effects of the relative surface energies of the clays in segregating to the blend air interface when heated to high temperatures. The segregation was shown to affect the composition and mechanical properties of the resulting chars, which in turn could determine their flame retardant response.

  16. Fabric phase sorptive extraction: Two practical sample pretreatment techniques for brominated flame retardants in water.

    PubMed

    Huang, Guiqi; Dong, Sheying; Zhang, Mengfei; Zhang, Haihan; Huang, Tinglin

    2016-09-15

    Sample pretreatment is the critical section for residue monitoring of hazardous pollutants. In this paper, using the cellulose fabric as host matrix, three extraction sorbents such as poly (tetrahydrofuran) (PTHF), poly (ethylene glycol) (PEG) and poly (dimethyldiphenylsiloxane) (PDMDPS), were prepared on the surface of the cellulose fabric. Two practical extraction techniques including stir bar fabric phase sorptive extraction (stir bar-FPSE) and magnetic stir fabric phase sorptive extraction (magnetic stir-FPSE) have been designed, which allow stirring of fabric phase sorbent during the whole extraction process. In the meantime, three brominated flame retardants (BFRs) [tetrabromobisphenol A (TBBPA), tetrabromobisphenol A bisallylether (TBBPA-BAE), tetrabromobisphenol A bis(2,3-dibromopropyl)ether (TBBPA-BDBPE)] in the water sample were selected as model analytes for the practical evaluation of the proposed two techniques using high-performance liquid chromatography (HPLC). Moreover, various experimental conditions affecting extraction process such as the type of fabric phase, extraction time, the amount of salt and elution conditions were also investigated. Due to the large sorbent loading capacity and unique stirring performance, both techniques possessed high extraction capability and fast extraction equilibrium. Under the optimized conditions, high recoveries (90-99%) and low limits of detection (LODs) (0.01-0.05 μg L(-1)) were achieved. In addition, the reproducibility was obtained by evaluating the intraday and interday precisions with relative standard deviations (RSDs) less than 5.1% and 6.8%, respectively. The results indicated that two pretreatment techniques were promising and practical for monitoring of hazardous pollutants in the water sample. Due to low solvent consumption and high repeated use performance, proposed techniques also could meet green analytical criteria. PMID:27300591

  17. Human dermal absorption of chlorinated organophosphate flame retardants; implications for human exposure.

    PubMed

    Abou-Elwafa Abdallah, Mohamed; Pawar, Gopal; Harrad, Stuart

    2016-01-15

    Tris-2-chloroethyl phosphate (TCEP), tris (1-chloro-2-propyl) phosphate (TCIPP) and tris-1,3-dichloropropyl phosphate (TDCIPP) are organophosphate flame retardants (PFRs) widely applied in a plethora of consumer products despite their carcinogenic potential. Human dermal absorption of these PFRs is investigated for the first time using human ex vivo skin and EPISKIN™ models. Results of human ex vivo skin experiments revealed 28%, 25% and 13% absorption of the applied dose (500 ng/cm(2), finite dose) of TCEP, TCIPP and TDCIPP, respectively after 24h exposure. The EPISKIN™ model showed enhanced permeability values (i.e. weaker barrier), that were respectively 16%, 11% and 9% for TCEP, TCIPP and TDCIPP compared to human ex vivo skin. However, this difference was not significant (P>0.05). Estimated permeability constants (Kp, cm/h) showed a significant negative correlation with log Kow for the studied contaminants. The effect of hand-washing on dermal absorption of PFRs was investigated. Washing reduced overall dermal absorption, albeit to varying degrees depending on the physicochemical properties of the target PFRs. Moreover, slight variations of the absorbed dose were observed upon changing the dosing solution from acetone to 20% Tween 80 in water, indicating the potential influence of the dose vehicle on the dermal absorption of PFRs. Finally, estimated dermal uptake of the studied PFRs via contact with indoor dust was higher in UK toddlers (median ΣPFRs=36 ng/kg bw day) than adults (median ΣPFRs=4 ng/kg bw day). More research is required to fully elucidate the toxicological implications of such exposure. PMID:26712466

  18. Organophosphorus flame retardants and phthalate esters in indoor dust from different microenvironments: Bioaccessibility and risk assessment.

    PubMed

    He, Ruiwen; Li, Yunzi; Xiang, Ping; Li, Chao; Zhou, Chunyang; Zhang, Shujun; Cui, Xinyi; Ma, Lena Q

    2016-05-01

    Incidental ingestion of indoor dust is an important pathway for human exposure to organophosphorus flame retardants (OPFRs) and phthalate esters (PAEs). However, little is known about their bioaccessibility in indoor dust. In this study, indoor dust samples were collected from houses, offices, public microenvironments (PMEs), and university dorms, and physiologically based extraction test (PBET) was used to measure the bioaccessibility of OPFRs and PAEs in these dust samples. Total concentrations of OPFRs in dust samples ranged from 0.01 to 63.2 μg g(-1), with significantly lower concentrations in dorm dust (median = 0.30 μg g(-1)) than those in houses (3.12), offices (5.94), and PMEs (11.6). Total PAEs ranged from 5.49 to 2161 μg g(-1) with significantly lower concentrations in dorm dust (379 μg g(-1)) than those in the other three types of dust (767, 515, and 731 μg g(-1)). When subject to PBET, the bioaccessibility of OPFRs ranged from 8.18% (triphenyl phosphate) to 54.5% (Tris(2-chloroisopropyl) phosphate) for OPFRs, and from 1.21% (di-2-ethylhexyl phthalate, DEHP) to 81.1% (dimethyl phthalate) for PAEs. Estimated exposure doses for adults and infants to OPFRs via dust ingestion were much lower than the reference doses (RfD), but intake dose of DEHP for infants was higher than the RfD of 20 μg kg(-1) d(-1). However, the DEHP intake dose did not exceed the RfD after incorporating bioaccessibility into risk assessment. Our data indicated the importance of considering contaminant bioaccessibility during risk assessment of indoor dust. PMID:26585356

  19. Fate and metabolism of the brominated flame retardant tetrabromobisphenol A (TBBPA) in rice cell suspension culture.

    PubMed

    Wang, Songfeng; Cao, Siqi; Wang, Yongfeng; Jiang, Bingqi; Wang, Lianhong; Sun, Feifei; Ji, Rong

    2016-07-01

    Tetrabromobisphenol A (TBBPA) is the brominated flame retardant with the highest production volume and its bioaccumulation in environment has caused both human health and environmental concerns, however the fate and metabolism of TBBPA in plants is unknown. We studied the fate, metabolites, and transformation of (14)C-labeled TBBPA in rice cell suspension culture. During the incubation for 14 days, TBBPA degradation occurred continuously in the culture, accompanied by formation of one anisolic metabolite [2,6-dibromo-4-(2-(2-hydroxy)-propyl)-anisole] (DBHPA) (50% of the degraded TBBPA) and cellular debris-bound residues (46.4%) as well as mineralization (3.6%). The cells continuously accumulated TBBPA in the cytoplasm, while a small amount of DBHPA (2.1% of the initially applied TBBPA) was detectable inside the cells only at the end of incubation. The majority of the accumulated residues in the cells was attributed to the cellular debris-bound residues, accounting for 70-79% of the accumulation after the first incubation day. About 5.4% of the accumulation was associated with cell organelles, which contributed 7.5% to the cellular debris-bound residues. Based on the fate and metabolism of TBBPA in the rice cell suspension culture, a type II ipso-substitution pathway was proposed to describe the initial step for TBBPA degradation in the culture and balance the fate of TBBPA in the cells. To the best of our knowledge, our study provides for the first time the insights into the fate and metabolism of TBBPA in plants and points out the potential role of type II ipso-hydroxylation substitution in degradation of alkylphenols in plants. Further studies are required to reveal the mechanisms for the bound-residue formation (e.g., binding of residues to specific cell wall components), nature of the binding, and toxicological effects of the bound residues and DBHPA. PMID:27105166

  20. A Hydroxylated Metabolite of Flame-Retardant PBDE-47 Decreases the Survival, Proliferation, and Neuronal Differentiation of Primary Cultured Adult Neural Stem Cells and Interferes with Signaling of ERK5 MAP Kinase and Neurotrophin 3

    PubMed Central

    Xia, Zhengui

    2013-01-01

    Polybrominated diphenyl ethers (PBDEs) are a group of organobromine compounds widely used as flame retardants. PBDE-47 is one of the most prominent PBDE congeners found in human tissues, and it can be transformed into several metabolites, including 6-OH-PBDE-47. Recent studies have shown that PBDE-47 is neurotoxic to animals and possibly humans. However, the basis for the neurotoxicity of PBDEs and their metabolites is unclear. For example, it is not known whether PBDEs affect adult neurogenesis, a process implicated in learning and memory and in olfactory behavior. In this study, we examined the toxicity of PBDEs for primary adult neural stem/progenitor cells (aNSCs) isolated from the subventricular zone (SVZ) of adult mice. We discovered that 6-OH-PBDE-47, but not its parent compound PBDE-47, is cytotoxic for aNCSs using MTS metabolism and cell number as a measure of cytotoxicity. Interestingly, 6-OH-PBDE-47 induced apoptosis at concentrations above 7.5μM inhibited proliferation at 2.5–5μM while suppressing neuronal and oligodendrocyte differentiation at submicromolar concentrations (≤ 1μM). The effect on proliferation was reversed upon removal of 6-OH-PBDE-47 and correlated with selective but reversible inhibition of ERK5 activation by mitogenic growth factors EGF and bFGF. 6-OH-PBDE-47 also inhibited the proneuronal differentiation effect of neurotrophin 3 (NT3) and NT3 activation of ERK5. Together, these data show that 6-OH-PBDE-47 is more toxic than its parent compound for SVZ-derived aNSCs and that it inhibits multiple aspects of adult neurogenesis. Furthermore, inhibition of ERK5 signaling may underlie the adverse effect of 6-OH-PBDE-47 on proliferation and neuronal differentiation. Our data suggest that exposure to PBDE-based flame retardants could cause neurotoxicity in the adult brain by interfering with adult neurogenesis. PMID:23564643

  1. Flame retardancy and UV protection of cotton based fabrics using nano ZnO and polycarboxylic acids.

    PubMed

    El-Hady, M M Abd; Farouk, A; Sharaf, S

    2013-01-30

    This research mainly deals with a novel flame-retardant and UV-protection for cellulosic fabrics using ZnO nanoparticles. We present the preparation and application of ZnO nanoparticles. The size of the prepared nanoparticles was analysed using dynamic light scattering (DLS). The application of nano ZnO on cellulosic fabrics (cotton 100% and cotton/cotton polyester 65/35%) was achieved by using different polycarboxilic acids (succinic acid [SA] and 1,2,3,4-butane tetracarboxilic acids [BTCA]) with sodium hypophosphite (SHP) as catalyst through conventional pad-dry-cure method. The effect of concentration of SHP on the physical properties, flammability and UV-protection of cross-linked fabrics are investigated. The effect of concentration of zinc oxide nanoparticles and the effect of curing temperature were also investigated. The results revealed the importance of SHP in increasing the flame-redundancy of the treated cellulosic fabrics. PMID:23218312

  2. Exposure assessment of organophosphorus and organobromine flame retardants via indoor dust from elementary schools and domestic houses.

    PubMed

    Mizouchi, Shigekazu; Ichiba, Masayoshi; Takigami, Hidetaka; Kajiwara, Natsuko; Takamuku, Toshiyuki; Miyajima, Toru; Kodama, Hiroki; Someya, Takashi; Ueno, Daisuke

    2015-03-01

    To assess the exposure of flame retardants (FRs) for school-children, organophosphorus flame retardants and plasticizers (PFRs) and organobromine flame retardants (BFRs) were determined in the indoor dust samples collected from elementary schools and domestic houses in Japan in 2009 and 2010. PFRs were detected in all the dust samples analyzed and the highest concentration of total PFRs was thousand-fold higher than that of BFRs. Among the PFRs, tris(butoxyethyl)phosphate (TBOEP) showed the highest concentration with a median (med.) of 270,000 ng g(-1) dry weight (3700-5,500,000 ng g(-1) dry weight), followed by tris(methylphenyl)phosphate (TMPPs)>triphenyl phosphate (TPHP)=tris(1,3-dichloro-2-propyl)phosphate (TDCIPP)=tris(2-chloroisopropyl)phosphate (TCIPP)=tris(2chloroethyl)phosphate (TCEP)>ethylhexyl diphenyl phosphate (EHDPP). Significantly higher concentrations of TBOEP, tri-n-butyl phosphate (TNBP), TPHP, TMPPs, and total-PFRs were found in dust samples from elementary schools than from domestic houses. It might be due to that higher concentrations of TBOEP (as leveling agent) were detected from the floor polisher/wax products collected in those elementary schools. On the other hand, significantly higher concentrations of TCEP, TCIPPs, and total chloroalkyl-PFRs were found in domestic houses than in elementary schools. Exposure assessments of PFRs via indoor dust from elementary schools and domestic houses were conducted by calculating the hazard quotient (HQ). Among PFRs, HQs for TBOEP exceeded 1 (higher than reference dose: RfD) and its highest value was 1.9. To reduce the intake of TBOEP by school-children, it is recommended that the use of floor polisher/wax containing TBOEP be reduced in schools. PMID:25532762

  3. Molecular Design, Graft Polymerization and Performance Evaluation of Radiation Curable Flame Retardant Monomers Derived from Phosphorus-Nitrogen Systems

    NASA Astrophysics Data System (ADS)

    Edwards, Brian Tyndall

    The textile industry is constantly seeking new technologies to make its production more efficient, economical and environmentally friendly. An exciting new strategy to impart value-added functional finishes to textiles is the use of radiation, such as ultraviolet (UV) light, to drive the polymerization of monomers onto the surface of the substrates. These grafted polymeric layers provide the fiber or fabric with interesting new properties, such as antimicrobial behavior, water and oil repellency or flame retardancy. With the aid of a photoinitiator, UV curing can take place very rapidly and the process is waterless and uses less energy than traditional textile wet processing. With these thoughts in mind, this research explores the molecular design, synthesis, UV induced graft polymerization and performance evaluation of nine phosphorus-based flame retardant monomers for cellulosic cotton substrates. All monomers in this work were easily prepared using one-pot reactions procedures. With the assistance of Irgacure 819 photoinitiator, seven of the nine monomers were shown to simultaneously graft and polymerize onto the surface of cotton fabrics under UV radiation. JMPRTM Pro 10 software was used to explore the effect of variables, such as monomer concentration, photoinitiator concentration and UV exposure time, on the yield of the grafted polymeric layer. Burn testing of the treated fabrics in the vertical, 45° and horizontal orientations showed that all nine monomers were effective flame retardants that function via the condensed phase mechanism by encouraging the formation of nonflammable char. These burn test results were validated by thermogravimetric analysis, which demonstrated quantitatively that all nine monomers strongly promote the generation of a protective char. Finally, scanning electron microscopy was used to examine the surface morphology of the treated fabrics and visualize the grafted polymeric layer.

  4. Polymeric brominated flame retardants: are they a relevant source of emerging brominated aromatic compounds in the environment?

    PubMed

    Gouteux, Bruno; Alaee, Mehran; Mabury, Scott A; Pacepavicius, Grazina; Muir, Derek C G

    2008-12-15

    A purge and trap method was used to study the release of brominated organic compounds from polymeric brominated flame retardants (BFRs), a relatively unknown class of flame retardant materials. Among the volatile brominated organics released, pentabromotoluene (PBTo), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB) were of particular interest because of their high potential to persist in the environment The impact of a thermal stress on the release of these compounds was assessed by applying different constant temperatures for one hour to a polymeric BFR sample. Release rates ranged between 22 +/- 2.1 ng g(-1) h(-1) for PBEB to 2480 +/- 500 ng g(-1) h(-1) for PBTo at room temperature. These rates of release reached 65 +/- 11 ng g(-1) h(-1) for PBEB and 42400 +/- 4700 ng g(-1) h(-1) for PBTo at 100 degrees C. This suggests that the compounding of thermoplastic polyesters done at high temperatures, up to 290 degrees C, could lead to the release of significant amounts of volatile brominated compounds in the environment when crude polymeric BFRs are used as flame retardants. To assess if this unsuspected source of volatile brominated compounds to the environment was relevant to support air concentrations in the Great Lakes area, air samples collected at Egbert (ON, Canada) were analyzed and PBTo, PBEB, and HBB were detected at low levels in some air samples (<0.01 to 0.09 pg/m3). As a second step, a Level III fugacity model was run using release rates of PBTo, PBEB, and HBB determined in this study. Results of the model indicated that prevailing PBEB and HBB air concentrations were not supported by their release from polymeric BFRs but by the use of these compounds as additive BFRs. However, these model predictions suffered from a lack of information on the actual use of polymeric BFRs. Hence, further work is needed to assess the release of potentially persistent brominated aromatic compounds from polymeric BFRs. PMID:19174868

  5. Controllable fabrication of zinc borate hierarchical nanostructure on brucite surface for enhanced mechanical properties and flame retardant behaviors.

    PubMed

    Wang, Xuesong; Pang, Hongchang; Chen, Wendan; Lin, Yuan; Zong, Lishuai; Ning, Guiling

    2014-05-28

    A novel and efficient halogen-free composite flame retardant (CFR) consisting of a brucite core and a fine zinc borate [Zn6O(OH)(BO3)3] hierarchical nanostructure shell was designed and synthesized via a facile nanoengineering route. It had been demonstrated that this unique hybrid structure possessed a high BET specific surface area (65 m(2)/g) and could significantly enhance the interfacial interaction when mixing with ethylene-vinyl acetate (EVA). This improved the transfer of stress between CFR particles and EVA matrix and increased the viscosity of EVA/EVA blends, which was beneficial for droplet inhibition and char forming. The mechanical properties and flammability behaviors of the EVA/CFR blends had been compared with the EVA/physical mixture (PM, with the given proportion of brucite and Zn6O(OH)(BO3)3). The mechanical properties of EVA/CFR blends, especially the tensile strength (TS), presented a remarkable increase reaching at least a 20% increment. Meanwhile, with the same 45 wt % of fillers, the EVA/CFR formulation could achieve a limiting oxygen index (LOI) value of 33 (37.5 % higher than that of EVA/PM blends) and UL-94 V-0 rating. Moreover, the heat release rate (HRR), peak heat release rate (PHRR), total heat released (THR), smoke production rate (SPR) and mass loss rate (MLR) were considerably reduced, especially PHRR and SPR for EVA/CFR blends were reduced to 32%. According to this study, the design of fine structure might pave the way for the future development of halogen-free flame retardants combining both enhanced mechanical properties and excellent flame retardant behaviors. PMID:24813539

  6. Mechanical property and thermal stability of polyurethane composites reinforced with polyhedral oligomeric silsesquioxanes and inorganic flame retardant filler.

    PubMed

    Kim, Ho-Joong; Kwon, Younghwan; Kim, Chang Kee

    2014-08-01

    Mechanical properties and thermal stability of polyurethane composites were investigated with a combination of polyhedral oligomeric silsesquioxane (POSS) molecules and inorganic barium sulfate. These hybrid composites were prepared using one-step method through the incorporation of flexible hydroxyl-terminated polybutadiene prepolymer, reactive POSS nanoparticles, and barium sulfate under isophorone diisocyanate curative system. In polyurethane composites, POSS and inorganic barium sulfate were utilized for mechanical reinforcement and flame retardant filler, respectively. The decomposition of POSS molecules during oxyacetylene torch exposure resulted in the formation of silica-based nanosized droplets, contributing on ablation behavior. PMID:25936054

  7. Ultra-Fast Layer-by-Layer Approach for Depositing Flame Retardant Coatings on Flexible PU Foams within Seconds.

    PubMed

    Carosio, F; Alongi, J

    2016-03-16

    In this letter, we are presenting a novel approach for the deposition of layer-by-layer (LbL) coatings capable of conferring flame retardant properties to flexible polyurethane foams exploiting subsecond deposition times. The process yields nanoscale coatings able to reduce by 33% one of the main fire safety parameters, namely the heat release rate peak, with a total treatment time of only 2.5 s. This new approach turned out to be three to 4 orders of magnitude faster than conventional LbL treatments. Such results make it possible for the exploit of LbL as a competitive, efficient and ecofriendly technology at industrial scale. PMID:26925855

  8. Optimized Li-Ion Electrolytes Containing Triphenyl Phosphate as a Flame-Retardant Additive

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Bugga, Ratnakumar V.; Prakash, G. K. Surya; Krause, Frederick C.

    2011-01-01

    A number of future NASA missions involving the exploration of the Moon and Mars will be human-rated and thus require high-specific-energy rechargeable batteries that possess enhanced safety characteristics. Given that Li-ion technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. There is also a strong desire to develop Li-ion batteries with improved safety characteristics for terrestrial applications, most notably for hybrid electric vehicle (HEV) and plug-in hybrid electric vehicle (PHEV) automotive applications. Therefore, extensive effort has been devoted recently to developing non-flammable electrolytes to reduce the flammability of the cells/battery. A number of electrolyte formulations have been developed, including systems that (1) incorporate greater concentrations of the flame-retardant additive (FRA); (2) use di-2,2,2-trifluoroethyl carbonate (DTFEC) as a co-solvent; (3) use 2,2,2- trifluoroethyl methyl carbonate (TFEMC); (4) use mono-fluoroethylene carbonate (FEC) as a co-solvent and/or a replacement for ethylene carbonate in the electrolyte mixture; and (5) utilize vinylene carbonate as a "SEI promoting" electrolyte additive, to build on the favorable results previously obtained. To extend the family of electrolytes developed under previous work, a number of additional electrolyte formulations containing FRAs, most notably triphenyl phosphate (TPP), were investigated and demonstrated in experimental MCMB (mesocarbon micro beads) carbon- LiNi(0.8)Co(0.2)O2 cells. The use of higher concentrations of the FRA is known to reduce the flammability of the electrolyte solution, thus, a concentration range was investigated (i.e., 5 to 20 percent by volume). The desired concentration of the FRA is the highest amount tolerable without adversely affecting the performance in terms of reversibility, ability to operate over a wide temperature range, and

  9. Urinary metabolites of organophosphate flame retardants and their variability in pregnant women.

    PubMed

    Hoffman, Kate; Daniels, Julie L; Stapleton, Heather M

    2014-02-01

    Organophosphate flame retardants (OPFRs) are commonly added to consumer products to reduce their flammability. Based on levels of OPFRs in indoor environments, human exposure is likely chronic and ubiquitous. Animal studies suggest that exposure to some OPFRs may result in adverse health impacts, particularly for Tris (1,3-dichloropropyl) phosphate (TDCPP); however, human data on the impacts of exposure to OPFRs are lacking. To design human studies, more information is needed on the stability of measured OPFRs in human samples over time. In this study, we sought to assess the degree of temporal variability of urinary TDCPP and triphenyl phosphate (TPP) metabolites throughout pregnancy in a cohort of women from central North Carolina. Eight pregnant women provided multiple urine samples: 3 during the 18th week of pregnancy, 1 during the 28th week, and 1 shortly after the child's birth. Bis (1,3-dichloropropyl) phosphate (BDCPP) and diphenyl phosphate (DPP), the respective metabolites of TDCPP and TPP, were measured in urine samples using liquid chromatography-tandem mass spectrometry. BDCPP and DPP were each detected in 38 of 39 urine samples and were not normally distributed. Geometric mean BDCPP and DPP concentrations were 1.3ng/mL (interquartile range (IQR): 0.8, 2.7ng/mL) and 1.9ng/mL (IQR: 0.9, 3.5ng/mL), respectively. BDCPP and DPP were moderately to strongly reliable over one week (intraclass correlation coefficient (ICC)=0.5; 95% confidence interval (CI): 0.4, 0.7 and ICC=0.7; 95% CI: 0.5, 0.8, respectively), and over the entire pregnancy (ICC=0.5 95% CI: 0.3, 0.7 and ICC=0.6; 95% CI: 0.4, 0.7, respectively). These data suggest that exposures to TDCPP and TPP are widespread and variable for pregnant women, and that a single measure of BDCPP or DPP, taken in the second trimester, likely captures information on the rank order of exposure throughout pregnancy. PMID:24316320

  10. Retrospective time-trend study of polybrominated diphenyl ether and polybrominated and polychlorinated biphenyl levels in human serum from the United States.

    PubMed Central

    Sjödin, Andreas; Jones, Richard S; Focant, Jean-François; Lapeza, Chester; Wang, Richard Y; McGahee, Ernest E; Zhang, Yalin; Turner, Wayman E; Slazyk, Bill; Needham, Larry L; Patterson, Donald G

    2004-01-01

    Six polybrominated diphenyl ethers (PBDEs), one hexabromobiphenyl [polybrominated biphenyl (PBB)], and one hexachlorobiphenyl [polychlorinated biphenyl (PCB)] were measured in 40 human serum pools collected in the southeastern United States during 1985 through 2002 and in Seattle, Washington, for 1999 through 2002. The concentrations of most of the PBDEs, which are commercially used as flame retardants in common household and commercial applications, had significant positive correlations with time of sample collection, showing that the concentrations of these compounds are increasing in serum collected in the United States. In contrast, PCB and PBB levels were negatively correlated with sample collection year, indicating that the levels of these compounds have been decreasing since their phaseout in the 1970s. PMID:15121506

  11. Analysis of Flame Retardancy in Polymer Blends by Synchrotron X-ray K-edge Tomography and Interferometric Phase Contrast Movies.

    PubMed

    Olatinwo, Mutairu B; Ham, Kyungmin; McCarney, Jonathan; Marathe, Shashidhara; Ge, Jinghua; Knapp, Gerry; Butler, Leslie G

    2016-03-10

    Underwriters Laboratories 94 test bars have been imaged with X-ray K-edge tomography between 12 and 32 keV to assess the bromine and antimony concentration gradient across char layers of partially burnt samples. Phase contrast tomography on partially burnt samples showed gas bubbles and dark-field scattering ascribed to residual blend inhomogeneity. In addition, single-shot grating interferometry was used to record X-ray movies of test samples during heating (IR and flame) intended to mimic the UL 94 plastics flammability test. The UL 94 test bars were formulated with varying concentrations of a brominated flame retardant, Saytex 8010, and a synergist, Sb2O3, blended into high-impact polystyrene (HIPS). Depending on the sample composition, samples will pass or fail the UL 94 plastics flammability test. Tomography and interferometry imaging show differences that correlate with UL 94 performance. Key features such as char layer, gas bubble formation, microcracks, and dissolution of the flame retardant in the char layer regions are used in understanding the efficiency of the flame retardant and synergist. The samples that pass the UL 94 test have a thick, highly visible char layer as well as an interior rich in gas bubbles. Growth of gas bubbles from flame-retardant thermal decomposition is noted in the X-ray phase contrast movies. Also noteworthy is an absence of bubbles near the burning surface of the polymer; dark-field images after burning suggest a microcrack structure between interior bubbles and the surface. The accepted mechanism for flame retardant activity includes free radical quenching in the flame by bromine and antimony species. The imaging supports this as well as provides a fast inspection of other parameters, such as viscosity and surface tension. PMID:26846254

  12. Occurrence and exposure assessment of organophosphate flame retardants (OPFRs) through the consumption of drinking water in Korea.

    PubMed

    Lee, Sunggyu; Jeong, Woochang; Kannan, Kurunthachalam; Moon, Hyo-Bang

    2016-10-15

    Organophosphate flame retardants (OPFRs) have been widely used as flame retardants and plasticizers in commercial products. Limited data are available on the occurrence and exposure of OPFRs via drinking water consumption. In this study, 127 drinking water samples were collected from tap water, purified water (tap water that is passed through in-house filters) and bottled water from major cities in Korea in 2014. The total concentrations of OPFRs (ΣOPFR) in all of the samples ranged from below the method detection limit (MDL) to 1660 (median: 48.7) ng/L. The predominant OPFR compounds in drinking water were tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroethyl) phosphate (TCPP), and tris(2-butoxyethyl) phosphate (TBEP). Significant differences were observed in the levels of TCPP, TBEP and ΣOPFR among various types of drinking water. TCPP is introduced in the drinking water during the water purification process. Regional differences existed in the levels and patterns of OPFRs in water samples, which indicated the existence of diverse sources of these contaminants. Purified water was a significant contributor to the total OPFR intake by humans. The estimated daily intake of OPFRs was lower than the tentative oral reference dose (RfD) values. In comparison with exposure of OPFRs via dust ingestion, water consumption was a significant source of chlorinated PFRs (99% for TCEP and 34% for TCPP to the total intakes) for Koreans. PMID:27450356

  13. Acid/vanadium-containing saponite for the conversion of propene into coke: potential flame-retardant filler for nanocomposite materials.

    PubMed

    Ostinelli, Luca; Recchia, Sandro; Bisio, Chiara; Carniato, Fabio; Guidotti, Matteo; Marchese, Leonardo; Psaro, Rinaldo

    2012-10-01

    Vanadium-containing saponite samples were synthesized in a one-pot synthetic procedure with the aim of preparing samples for potential application as fillers for polymeric composites. These vanadium-modified materials were prepared from an acid support by adopting a synthetic strategy that allowed us to introduce isolated structural V species (H/V-SAP). The physicochemical properties of these materials were investigated by XRD analysis and by DR-UV/Vis and FTIR spectroscopy of CO that was adsorbed at 100 K; these data were compared to those of a V-modified saponite material that did not contain any Brønsted acid sites (Na/V-SAP). The surface-acid properties of both samples (together with the fully acidic H-SAP material and the Na-SAP solid) were studied in the catalytic isomerization of α-pinene oxide. The V-containing solids were tested in the oxidative dehydrogenation reaction of propene to evaluate their potential use as flame-retardant fillers for polymer composites. The effect of tuning the presence of Lewis/Brønsted acid sites was carefully studied. The V-containing saponite sample that contained a marked presence of Brønsted acid sites showed the most interesting performance in the oxidative dehydrogenation (ODH) reactions because they produced coke, even at 773 K. The catalytic data presented herein indicate that the H/V-SAP material is potentially active as a flame-retardant filler. PMID:22791515

  14. Hyper-branched polymer grafting graphene oxide as an effective flame retardant and smoke suppressant for polystyrene.

    PubMed

    Hu, Weizhao; Yu, Bin; Jiang, Shu-Dong; Song, Lei; Hu, Yuan; Wang, Bibo

    2015-12-30

    A well-defined functionalized graphene oxide (FGO) grafted by hyper-branched flame retardant based on N-aminoethyl piperazine and phosphonate derivative was synthesized to reduce flammability and toxicity of polystyrene (PS). The chemical structure, morphological and thermal properties were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis, respectively. Micro combustion calorimeter and steady state tube furnace were employed to evaluate the heat and non-heat fire hazards of PS nanocomposites. The incorporation of FGO into PS matrix effectively improved the flame retardancy and restrained the toxicity of the volatiles escaped, which is attributed to that the homogeneous dispersion of FGO in the PS matrix enhanced barrier effect that reduced peak heat release rate, total heat release and toxic gas release during combustion. Furthermore, PS-FGO nanocompsites obviously decreased the amount of flammable and toxic volatiles evolved, such as the aromatic compounds, carbonyl compounds, carbon monoxide, indicating suppressed fire hazards of the PS composites. PMID:26151385

  15. Dermal uptake and percutaneous penetration of ten flame retardants in a human skin ex vivo model.

    PubMed

    Frederiksen, Marie; Vorkamp, Katrin; Jensen, Niels Martin; Sørensen, Jens Ahm; Knudsen, Lisbeth E; Sørensen, Lars S; Webster, Thomas F; Nielsen, Jesper B

    2016-11-01

    The dermal uptake and percutaneous penetration of ten organic flame retardants was measured using an ex vivo human skin model. The studied compounds were DBDPE, BTBPE, TBP-DBPE, EH-TBB, BEH-TEBP, α, β and γ-HBCDD as well as syn- and anti-DDC-CO. Little or none of the applied flame retardants was recovered in either type of the receptor fluids used (physiological and worst-case). However, significant fractions were recovered in the skin depot, particularly in the upper skin layers. The primary effect of the worst-case receptor fluid was deeper penetration into the skin. The recovered mass was used to calculate lower- and upper-bound permeability coefficients kp. Despite large structural variation between the studied compounds, a clear, significant decreasing trend of kp was observed with increasing log Kow. The results indicate that the dermis may provide a significant barrier for these highly lipophilic compounds. However, based on our results, dermal uptake should be considered in exposure assessments, though it may proceed in a time-lagged manner compared to less hydrophobic compounds. PMID:27513551

  16. Distribution pattern of legacy and "novel" brominated flame retardants in different particle size fractions of indoor dust in Birmingham, United Kingdom.

    PubMed

    Al-Omran, Layla Salih; Harrad, Stuart

    2016-08-01

    This study investigates the particle size distribution of eight polybrominated diphenyl ethers (PBDEs) and five "novel" brominated flame retardants (NBFRs) in settled house dust. Elevated surface dust (ESD) and floor dust (FD) were collected from 5 homes in Birmingham, UK, yielding a total of 10 samples. Each sample was fractionated into three different particle sizes: 125-250 μm (P1), 63-125 μm (P2) and 25-63 μm (P3). Non-fractionated bulk dust samples (BD) were also analysed. BDE-209 predominated, comprising an average 74.3%, 77.3%, 69.2%, and 62.7% ΣBFRs of BD, P1, P2 and P3 respectively. Σ5NBFRs contributed 24.2%, 21.5%, 29.0% and 35.3% ΣBFRs, while Σ7tri-hepta-BDEs represented 1.5%, 1.2%, 1.7%, and 2.0% ΣBFRs. BEH-TEBP was the predominant NBFR contributing 76.9%, 75.1%, 83.1%, and 83.9% ΣNBFRs in BD, P1, P2 and P3 respectively; followed by DBDPE which contributed 20.1%, 21.9%, 14.1% and 13.9% ΣNBFRs. EH-TBB, BTBPE and PBEB were the least abundant NBFRs. Concentrations of Σ7tri-hepta-BDEs and BEH-TEBP in P3 exceeded significantly (P < 0.05) those in P2, with those in P2 exceeding significantly those in P1. In contrast, no significant differences were found between concentrations of BDE-209, EH-TBB, BTBPE, and DBDPE in different particle size fractions. Concentrations of Σ7tri-hepta-BDEs, BDE-209, and BEH-TEBP in ESD exceeded significantly those in FD (P < 0.05). Normalising BFR concentrations to organic carbon content, did not alter these findings. This suggests that differences in BFR concentrations between different particle size fractions are caused by variations in particle surface area to volume ratio, rather than by variations in organic carbon content. PMID:27213241

  17. Dioxins, PCBs, chlorinated pesticides and brominated flame retardants in free-range chicken eggs from peri-urban areas in Arusha, Tanzania: Levels and implications for human health.

    PubMed

    Polder, A; Müller, M B; Brynildsrud, O B; de Boer, J; Hamers, T; Kamstra, J H; Lie, E; Mdegela, R H; Moberg, H; Nonga, H E; Sandvik, M; Skaare, J U; Lyche, J L

    2016-05-01

    The environment in the northern part of Tanzania is influenced by rapid population growth, and increased urbanization. Urban agriculture is common and of economic value for low income families. In Arusha, many households sell eggs from free-ranging backyard chicken. In 2011, 159 eggs from different households in five different locations in Arusha were collected, homogenized, pooled into 28 composite samples and analyzed for a wide selection of POPs. Levels of POPs varied widely within and between the locations. The levels of dieldrin and ΣDDT ranged between 2 and 98,791 and 2 and 324ng/g lipid weight (lw), respectively. EU MRLs of 0.02mg/kg dieldrin for eggs were exceeded in 4/28 samples. PCBs, HCHs, chlordanes, toxaphenes and endosulfanes were found at lower frequency and levels. Brominated flame retardants (BFRs), e.g polybrominated diphenylethers (PBDEs), hexabromocyclododecane (HBCD) and 1,2-bis(2,4,6-tribromphenoxy)ethane (BTBPE) were present in 100%, 60% and 46% of the composite samples, respectively. Octa-and deca-BDEs were the dominating PBDEs and BDE 209 levels ranged between

  18. Spatial and temporal comparisons of legacy and emerging flame retardants in herring gull eggs from colonies spanning the Laurentian Great Lakes of Canada and United States.

    PubMed

    Su, Guanyong; Letcher, Robert J; Moore, Jeremy N; Williams, Lisa L; Martin, Pamela A; de Solla, Shane R; Bowerman, William W

    2015-10-01

    In the Laurentian Great Lakes basin of North America, an increasing number of chemicals of emerging concern (CECs) are being investigated, including legacy and replacement flame retardants (FRs). In the present study, 14 polybrominated diphenyl ethers (PBDEs), 23 non-PBDEs halogenated FRs (NPHFRs) and 16 organophosphate ester FRs (OPE-FRs) were analyzed in 100 individual eggs collected in 2012 and 2013 and in 15 egg pools of herring gulls collected in 2012 from 20 colonies across the entire Laurentian Great Lakes basin. For CEC-FRs in eggs from all colonies, 14 PBDEs, 12 NPHFRs and 9 OPE-FRs were quantifiable in at least one of the 115 analyzed samples. The mean sum PBDE (Σ14PBDE) concentrations ranged from 244 to 657 ng/g wet weight (ww), and on average were 1-2 orders of magnitude greater than the Σ12NPHFR concentrations (13.8-35.6 ng/g ww), and 2-3 orders of magnitude greater than Σ9OPE-FR concentrations (0.31-2.14 ng/g ww). Mean Σ14PBDE and sum of syn- and anti-Dechlorane Plus isomer (Σ2DDC-CO) concentrations in eggs from colonies within Laurentian Great Lakes Areas of Concern (AOCs) were in most cases greater than in eggs from nearby colonies outside of AOCs. Comparing CEC-FR concentrations in eggs collected in 2012-2013 to those previously measured in eggs collected approximately 7 years earlier (2006 and 2008) showed that Σ7PBDE (BDE-28, -47, -100, -99, -154,-153 and -183) mean concentrations in eggs from 6 colonies were approximately 30% less than they were in eggs from the same colonies from the earlier time period, whereas 3 current-use FR (BDE-209, HBCDD and Σ2DDC-CO) concentrations were significantly greater (p<0.05) than previously measured. Between 2006 and 2013 there were significant changes in individual PBDE patterns for BDE-71, -138, -153, -203, -206 and -207. Among all of the examined CEC-FRs, concentrations of Σ4PBDE (BDE-47, -99, -100 and -153) and HBCDD in gull eggs from all colonies were greater than or comparable to their lowest

  19. Methodology and determination of tetradecabromo-1, 4-diphenoxybenzene flame retardant and breakdown by-products in sediments from the Laurentian Great Lakes.

    PubMed

    Trouborst, Lennart; Chu, Shaogang; Chen, Da; Letcher, Robert J

    2015-01-01

    Tetradecabromo-1,4-diphenoxybenzene (TeDB-DiPhOBz) is a brominated polyphenyl ether flame retardant (FR) that is known to photolytically degrade to produce lower brominated polybrominated-diphenoxybenzenes (PB-DiPhOBzs), which may be precursors to MeO-PB-DiPhOBzs recently reported in the Great Lakes herring gulls eggs. To our knowledge, there are no reports on TeDB-DiPhOBz or other PB-DiPhOBz by-products in any environmental sample. The present study analyzed for the presence of PB-DiPhOBzs (including TeDB-DiPhOBz) and MeO-PB-DiPhOBzs in surficial sediment from sites in Saginaw Bay in western Lake Huron (n = 7), and in comparison to southern Lake Huron (open water) (n = 5) and Lake Erie (n = 3) sediment collected in the summers of 2012 or 2013. To analyze for possible PB-DiPhOBzs (Br14–Br0), the first known analytical method was developed for extraction and cleanup of sediment samples, and analysis by HPLC–atmospheric pressure photoionization (−)-quadrupole time-of-flight-mass spectrometry. The overall recovery efficiency was optimized to on average 33–104% progressing from Br14- to Br10-PB-DiPhOBzs. Br10- to Br14-PB-DiPhOBz detection and quantification limits ranged from 0.05 to 0.15 ng g(−1) dw and 0.17 to 0.49 ng g(−1) dw, respectively. Although this is the first report, PB-DiPhOBzs (Br14–Br10) and MeO-PB-DiPhOBzs were not detectable in any sediment sample. This included a site near the mouth of the highly FR-contaminated Saginaw River, near the confined disposal facility (CDF) located in Saginaw Bay at Channel-Shelter Island, which receives dredged sediment from the Saginaw River. Our findings suggest sediments from the presently studied sites in the Great Lakes ecosystem are not a sink for TeDB-DiPhOBz and PB-DiPhOBz by-product contaminants. PMID:25463260

  20. Pollution profiles and risk assessment of PBDEs and phenolic brominated flame retardants in water environments within a typical electronic waste dismantling region.

    PubMed

    Xiong, Jukun; An, Taicheng; Zhang, Chaosheng; Li, Guiying

    2015-06-01

    The aim of this study was to assess the pollution profiles of various typical brominated flame retardants in water and surface sediment near a typical electronic waste dismantling region in southern China. We found that polybrominated diphenyl ethers (PBDEs), 2,4,6-tribromophenol (TBP), pentabromophenol (PeBP), tetrabromobisphenol A (TBBPA), and bisphenol A (BPA) were ubiquitous in the water and sediment samples collected in the study region. In water, Σ19PBDEs (sum of all 20 PBDE congeners studied except BDE-209, which was below the detection limit) levels ranged from 0.31 to 8.9 × 10(2) ng L(-1). TBP, PeBP, TBBPA, and BPA concentrations in the water samples ranged from not being detectable (nd-under the detection limit) to 3.2 × 10(2) (TBP), from nd to 37 (PeBP), from nd to 9.2 × 10(2) (TBBPA) and from nd-8.6 × 10(2) ng L(-1) (BPA). In sediment, Σ19PBDEs ranged from nd to 5.6 × 10(3) ng g(-1), while BDE-209 was the predominant congener, with a range of nd to 3.5 × 10(3) ng g(-1). Tri- to hepta-BDE concentrations were significantly (p < 0.01) correlated with each other, except for BDE-71 and BDE-183, and octa- to nona-BDEs concentrations were significantly (p < 0.05) correlated with each other, except for BDE-208. BDE-209 was not significantly correlated with tri- to nona-BDEs. Risk assessments indicated that the water and sediment across the sampling sites posed no estrogenic risk. However, different eco-toxicity risk degrees at three trophic levels did exist at most sampling sites. PMID:25503846

  1. Analytical capabilities of high performance liquid chromatography - Atmospheric pressure photoionization - Orbitrap mass spectrometry (HPLC-APPI-Orbitrap-MS) for the trace determination of novel and emerging flame retardants in fish.

    PubMed

    Zacs, D; Bartkevics, V

    2015-10-22

    A new analytical method was established and validated for the analysis of 27 brominated flame retardants (BFRs), including so called "emerging" and "novel" BFRs (EBFRs and NBFRs) in fish samples. High performance liquid chromatography (HPLC) coupled to Orbitrap mass spectrometry (Orbitrap-MS) employing atmospheric pressure photoionization (APPI) interface operated in negative mode was used for the identification/quantitation of contaminants. HPLC-Orbitrap-MS analysis provided a fast separation of selected analytes within 14 min, thus demonstrating a high throughput processing of samples. The developed methodology was tested by intralaboratory validation in terms of recovery, repeatability, linear calibration ranges, instrumental and method limits of quantitation (i-LOQ and m-LOQ), and where possible, trueness was verified by analysis of certified reference materials (CRMs). Recoveries of analytes were between 80 and 119%, while the repeatability in terms of relative standard deviations (RSDs) was in the range from 1.2 to 15.5%. The measured values for both analyzed CRMs agreed with the provided consensus values, revealing the recovery of reference concentrations in 72-119% range. The elaborated method met the sensitivity criterion according to Commission Recommendation 2014/118/EU on monitoring of BFRs in food products for majority of the compounds. The concentrations of polybrominated diphenyl ethers (PBDEs) in real samples determined by HPLC-APPI-Orbitrap-MS method and validated gas chromatography-high-resolution mass spectrometry (GC-HRMS) method were found to be in a good agreement. PMID:26526911

  2. Simultaneous determination of three alternative flame retardants (dechlorane plus, 1,2-bis(2,4,6-tribromophenoxy) ethane, and decabromodiphenyl ethane) in soils by gas chromatography-high resolution mass spectrometry.

    PubMed

    Xu, Pengjun; Tao, Bu; Ye, Zhiqiang; Qi, Li; Ren, Yue; Zhou, Zhiguang; Li, Nan; Huang, Yeru; Chen, Jiping

    2015-11-01

    A gas chromatography-high resolution mass spectrometry (GC-HRMS) method has been developed for the simultaneous determination of three alternative flame retardants, dechlorane plus (DP), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), and decabromodiphenyl ethane (DBDPE) in soils. The soil samples were extracted by accelerated solvent extraction, followed by purification with concentrated sulfuric acid partitioning combined with acid-base silica gel column separation. The gas chromatography featured with a thermostable capillary column of short length and a thin stationary phase was operated in pulse injection mode. A double-focusing magnetic sector high resolution mass spectrometer with electron impact ionization was used for quantification of the analytes. The method detection limits were 0.27-0.33 pg for DPs, 0.41 pg for BTBPE, and 36 pg for DBDPE. The mean recoveries for DPs, BTBPE, and DBDPE in spiked soils were 88-107%, 78-97%, and 74-113%, respectively, with relative standard deviations ranging from 5.2% to 18%. The recoveries of (13)C-labeled standards for DPs, BTBPE, and DBDPE in soil samples were 45-110%, 67-118%, and 27-82%, respectively. These results met the acceptable range of labeled standards for analysis of polybrominated diphenyl ethers as specified by the USEPA 1614 method. PMID:26452921

  3. Brominated flame retardant trends in aquatic birds from the Salish Sea region of the west coast of North America, including a mini-review of recent trends in marine and estuarine birds.

    PubMed

    Miller, Aroha; Elliott, John E; Elliott, Kyle H; Guigueno, Mélanie F; Wilson, Laurie K; Lee, Sandi; Idrissi, Abde

    2015-01-01

    Polybrominated diphenyl ethers (PBDEs) increased in many matrices during the 1990s and early 2000s. Since voluntary restrictions and regulations on PBDEs were implemented in North America circa early 2000s, decreases in PBDEs have occurred in many of these same matrices. To examine temporal trends in the North Pacific, we retrospectively analysed PBDEs and eight non-PBDE flame retardants (FR) in eggs of two aquatic bird species, great blue herons, Ardea herodias, and double-crested cormorants, Phalacrocorax auritus, collected along the British Columbia coast, Canada from 1979 to 2012. Increasing PBDE concentrations were observed in both species followed by significant decreases post-2000 for all dominant congeners and ΣPBDE. Non-PBDE FRs were generally undetected in cormorant eggs, or detected at very low levels in heron eggs, except for hexabromocyclododecane (HBCDD). HBCDD, currently unregulated in North America, was not detected in early sampling years; however low concentrations were observed in both species in recent sampling years (2003-2012). Dietary tracers (δ(13)C and δ(15)N) did not change significantly over time, indicating that temporal changes in PBDEs are likely caused by implemented regulations. A comparison with recently published temporal trends of ΣPBDE in marine birds from North America and Europe is given. PMID:25241209

  4. Novel chemical synthesis and characterization of copper pyrovanadate nanoparticles and its influence on the flame retardancy of polymeric nanocomposites

    PubMed Central

    Ghiyasiyan-Arani, Maryam; Masjedi-Arani, Maryam; Ghanbari, Davood; Bagheri, Samira; Salavati-Niasari, Masoud

    2016-01-01

    In this work, copper pyrovanadate (Cu3V2O7(OH)2(H2O)2) nanoparticles have been synthesized by a simple and rapid chemical precipitation method. Different copper-organic complexes were used to control the size and morphology of products. The morphology and structure of the as-synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectrum, electron dispersive X-ray spectroscopy (EDX), thermal gravimetric analysis (TGA), differential thermal analysis (DTA) and photoluminescence (PL) spectroscopy. The influence of copper pyrovanadate nanostructures on the flame retardancy of the polystyrene, poly vinyl alcohol and cellulose acetate was studied. Dispersed nanoparticles play the role of a magnetic barrier layer, which slows down product volatilization and prevents the flame and oxygen from the sample during decomposition of the polymer. Cu3V2O7(OH)2(H2O)2 is converted to Cu3V2O8 with an endothermic reaction which simultaneously releases water and decrease the temperature of the flame region. PMID:27143312

  5. Novel chemical synthesis and characterization of copper pyrovanadate nanoparticles and its influence on the flame retardancy of polymeric nanocomposites.

    PubMed

    Ghiyasiyan-Arani, Maryam; Masjedi-Arani, Maryam; Ghanbari, Davood; Bagheri, Samira; Salavati-Niasari, Masoud

    2016-01-01

    In this work, copper pyrovanadate (Cu3V2O7(OH)2(H2O)2) nanoparticles have been synthesized by a simple and rapid chemical precipitation method. Different copper-organic complexes were used to control the size and morphology of products. The morphology and structure of the as-synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectrum, electron dispersive X-ray spectroscopy (EDX), thermal gravimetric analysis (TGA), differential thermal analysis (DTA) and photoluminescence (PL) spectroscopy. The influence of copper pyrovanadate nanostructures on the flame retardancy of the polystyrene, poly vinyl alcohol and cellulose acetate was studied. Dispersed nanoparticles play the role of a magnetic barrier layer, which slows down product volatilization and prevents the flame and oxygen from the sample during decomposition of the polymer. Cu3V2O7(OH)2(H2O)2 is converted to Cu3V2O8 with an endothermic reaction which simultaneously releases water and decrease the temperature of the flame region. PMID:27143312

  6. Novel chemical synthesis and characterization of copper pyrovanadate nanoparticles and its influence on the flame retardancy of polymeric nanocomposites

    NASA Astrophysics Data System (ADS)

    Ghiyasiyan-Arani, Maryam; Masjedi-Arani, Maryam; Ghanbari, Davood; Bagheri, Samira; Salavati-Niasari, Masoud

    2016-05-01

    In this work, copper pyrovanadate (Cu3V2O7(OH)2(H2O)2) nanoparticles have been synthesized by a simple and rapid chemical precipitation method. Different copper-organic complexes were used to control the size and morphology of products. The morphology and structure of the as-synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectrum, electron dispersive X-ray spectroscopy (EDX), thermal gravimetric analysis (TGA), differential thermal analysis (DTA) and photoluminescence (PL) spectroscopy. The influence of copper pyrovanadate nanostructures on the flame retardancy of the polystyrene, poly vinyl alcohol and cellulose acetate was studied. Dispersed nanoparticles play the role of a magnetic barrier layer, which slows down product volatilization and prevents the flame and oxygen from the sample during decomposition of the polymer. Cu3V2O7(OH)2(H2O)2 is converted to Cu3V2O8 with an endothermic reaction which simultaneously releases water and decrease the temperature of the flame region.

  7. Occurrence and distribution of brominated flame retardants and perfluoroalkyl substances in Australian landfill leachate and biosolids.

    PubMed

    Gallen, C; Drage, D; Kaserzon, S; Baduel, C; Gallen, M; Banks, A; Broomhall, S; Mueller, J F

    2016-07-15

    The levels of perfluroalkyl substances (PFASs), polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCDDs) were studied in Australian landfill leachate and biosolids. Leachate was collected from 13 landfill sites and biosolids were collected from 16 wastewater treatment plants (WWTPs), across Australia. Perfluorohexanoate (PFHxA) (12-5700ng/L) was the most abundant investigated persistent, bioaccumulative and toxic (PBT) chemical in leachate. With one exception, mean concentrations of PFASs were higher in leachate of operating landfills compared to closed landfills. Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane isomers (HBCDDs) were detected typically at operating landfills in comparatively lower concentrations than the PFASs. Decabromodiphenyl ether (BDE-209) (<0.4-2300ng/g) and perfluoroctanesulfonate (PFOS) (

  8. Triclosan and Hydroxylated Polybrominated Diphenyl Ethers in Lake and Esturaine Sediments

    NASA Astrophysics Data System (ADS)

    Arnold, W. A.; Kerrigan, J. F.; McNeill, K.; Erickson, P. R.; Grandbois, M.

    2014-12-01

    Halogenated diphenyl ethers are a class of emerging contaminants that includes the antibacterial compound triclosan and the flame retardant polybrominated diphenyl ethers (PBDEs). Both triclosan and hydroxylated polybrominated diphenyl ethers (OH-BDEs) are known to form dioxins when exposed to sunlight in aqueous solution. Thus, it is important to understand the sources and presence of these compounds in the environment, especially because OH-BDEs are breakdown products of PBDEs and also naturally produced compounds. In this work, the levels of OH-BDEs were determined in lake sediments from Minnesota and esturaine sediments from San Francisco Bay. Both surface sediments over a broad spatial area and sediment cores were collected and analyzed. Triclosan was used as a marker of wastewater as a source of the targeted emerging contaminants. The relationship between triclosan and OH-BDE levels provides insight into the importance of natural and anthropogenic influences