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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.

  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. Effects of selected polybrominated diphenyl ether flame retardants on lake trout (Salvelinus namaycush).

    PubMed

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

    2005-06-01

    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.

  4. Polybrominated diphenyl ether (PBDE) flame retardants: environmental contamination, human body burden and potential adverse health effects.

    PubMed

    Costa, Lucio G; Giordano, Gennaro; Tagliaferri, Sara; Caglieri, Andrea; Mutti, Antonio

    2008-12-01

    Polybrominated diphenyl ethers (PBDEs) are an important class of flame retardants, widely used in a variety of consumer products. In the past several years, PBDEs have become widespread environmental pollutants, and have been detected in water, soil, air, animals and human tissues. Exposure occurs in particular through the diet and the indoor environment. Infants and toddlers have the highest body burden, due to exposure via maternal milk and through house dust. Tetra-, penta- and hexa-BDEs are the congeners most commonly found in humans. Recent concerns on possible adverse health effects of PBDEs are focusing on their potential endocrine disrupting effects and on developmental neurotoxicity.

  5. 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.

  6. 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.

  7. Polybrominated diphenyl ether flame retardants in lichens and mosses from King George Island, maritime Antarctica.

    PubMed

    Yogui, G T; Sericano, J L

    2008-11-01

    Lichens and mosses are considered good indicators of atmospheric pollution as they absorb contaminants directly from the air. Polybrominated diphenyl ethers (PBDEs) are man-made chemicals used as flame retardants in materials such as plastics, textiles, electronic circuitry and furnishing foam. Few studies have investigated PBDEs in the southern hemisphere including Antarctica. This paper presents the first evaluation of PBDEs in lichens (Usnea antarctica and Usnea aurantiaco-atra) and mosses (Sanionia uncinata) collected at King George Island, maritime Antarctica. PBDEs were detected at low levels in all lichen and moss samples. On average, the levels of PBDEs in mosses (818 pg g(-1) dry weight; 101 ng g(-1) lipid) were significantly higher than in lichens (168 pg g(-1) dry weight; 9.11 ng g(-1) lipid). This difference is most likely due to the differing mechanisms of PBDEs uptake from the atmosphere which are controlled by a number of chemical, environmental and plant variables. Contaminant concentrations were not statistically different at sites close to and distant from human facilities. Long-range atmospheric transport is believed to be the primary source of PBDEs to King George Island. The pattern of congeners in plants resembles those found in commercial mixtures of Penta-BDE. In addition, the presence of BDE-183 in lichens and mosses suggests that other technical formulations (e.g., Octa-BDE and Deca-BDE) have reached Antarctica. Further studies are needed to better understand the role of Antarctic vegetation as a sink for anthropogenic organic pollutants.

  8. Human Excretion of Polybrominated Diphenyl Ether Flame Retardants: Blood, Urine, and Sweat Study

    PubMed Central

    Genuis, Shelagh K.; Birkholz, Detlef

    2017-01-01

    Commonly used as flame retardants, polybrominated diphenyl ethers (PBDEs) are routinely detected in the environment, animals, and humans. Although these persistent organic pollutants are increasingly recognized as having serious health implications, particularly for children, this is the first study, to our knowledge, to investigate an intervention for human elimination of bioaccumulated PBDEs. Objectives. To determine the efficacy of blood, urine, and perspiration as PBDE biomonitoring mediums; assess excretion of five common PBDE congeners (28, 47, 99, 100, and 153) in urine and perspiration; and explore the potential of induced sweating for decreasing bioaccumulated PBDEs. Results. PBDE congeners were not found in urine samples; findings focus on blood and perspiration. 80% of participants tested positive in one or more body fluids for PBDE 28, 100% for PBDE 47, 95% for PBDE 99, and 90% for PBDE 100 and PBDE 153. Induced perspiration facilitated excretion of the five congeners, with different rates of excretion for different congeners. Conclusion. Blood testing provides only a partial understanding of human PBDE bioaccumulation; testing of both blood and perspiration provides a better understanding. This study provides important baseline evidence for regular induced perspiration as a potential means for therapeutic PBDE elimination. Fetotoxic and reproductive effects of PBDE exposure highlight the importance of further detoxification research. PMID:28373979

  9. 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.

  10. 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.

  11. Determination of brominated flame retardants, with emphasis on polybrominated diphenyl ethers (PBDEs) in environmental and human samples--a review.

    PubMed

    Covaci, Adrian; Voorspoels, Stefan; de Boer, Jacob

    2003-09-01

    Analytical methods for the determination of brominated flame retardants (BFRs), with a special emphasis on polybrominated diphenyl ethers (PBDEs) are reviewed. A number of procedures, which can be applied to the analysis of PBDEs and polybrominated biphenyls (PBBs), and in some cases for hexabromocyclododecane (HBCD), in environmental and human samples are described. Because several BFRs, such as tetrabromobisphenol-A (TBBP-A), BDE 209 and, to some extent, HBCD, may require a different approach, specific advice on their analysis is given separately when needed. Sample pretreatment, extraction, cleanup and fractionation, injection techniques, chromatographic separation, detection methods, quality control and method validation are discussed. For each topic, an overview is given of the current status of the field and recommendations for an appropriate analytical approach are presented.

  12. 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...

  13. 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...

  14. 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...

  15. 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

  16. Levels and trends of polybrominated diphenylethers and other brominated flame retardants in wildlife.

    PubMed

    Law, Robin J; Alaee, Mehran; Allchin, Colin R; Boon, Jan P; Lebeuf, Michel; Lepom, Peter; Stern, Gary A

    2003-09-01

    In this paper, we review the available data for polybrominated diphenylethers (PBDEs) and other flame retardants in wildlife, with the exception of fishes from Europe and North America which are covered in more detail elsewhere. More data are available for PBDEs than for other compounds, and these show that some of these compounds have become widely distributed in the environment, being found in samples from Europe, Australia, Azerbaijan, North America and the Arctic. Most available data relate to birds and their eggs and marine mammals, but the results of two food web studies are also included. The detection of PBDEs in pelagic marine mammals which feed in deep offshore waters, including baleen whales, indicate that these compounds have found their way into deep-water, oceanic food webs as well as the coastal/shallow sea examples described in detail. In the North Sea study, the most marked increase in lipid-normalised concentrations of six BDE congeners occurred during transfer from predatory fish to marine mammals. In the St. Lawrence Estuary study, marked differences in the ratios observed between species suggested that some fish species may be able to metabolise BDE99.A number of time trend studies have also been conducted, notably in guillemot eggs from Sweden (1969-2000), beluga whales from the Canadian Arctic (1982-1997 and 1989-2001) and from the St. Lawrence Estuary (1988-1999), and ringed seals from the Canadian Arctic (1981-2000). In the temperate latitudes, from these and other studies (e.g. in dated sediment cores), PBDE concentrations began to rise earlier than in those from high latitudes, in line with data for production and use. These trends have now slowed in many cases. Declines could be expected in Europe for many congeners following the cessation of manufacture and use of the penta-mix formulation in the EU, though these are not yet apparent in environmental samples. In Arctic biota, however, the rapidly rising concentrations seen currently in

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

    USDA-ARS?s Scientific Manuscript database

    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...

  18. Optimization of microwave-assisted extraction with saponification (MAES) for the determination of polybrominated flame retardants in aquaculture samples.

    PubMed

    Fajar, N M; Carro, A M; Lorenzo, R A; Fernandez, F; Cela, R

    2008-08-01

    The efficiency of microwave-assisted extraction with saponification (MAES) for the determination of seven polybrominated flame retardants (polybrominated biphenyls, PBBs; and polybrominated diphenyl ethers, PBDEs) in aquaculture samples is described and compared with microwave-assisted extraction (MAE). Chemometric techniques based on experimental designs and desirability functions were used for simultaneous optimization of the operational parameters used in both MAES and MAE processes. Application of MAES to this group of contaminants in aquaculture samples, which had not been previously applied to this type of analytes, was shown to be superior to MAE in terms of extraction efficiency, extraction time and lipid content extracted from complex matrices (0.7% as against 18.0% for MAE extracts). PBBs and PBDEs were determined by gas chromatography with micro-electron capture detection (GC-muECD). The quantification limits for the analytes were 40-750 pg g(-1) (except for BB-15, which was 1.43 ng g(-1)). Precision for MAES-GC-muECD (%RSD < 11%) was significantly better than for MAE-GC-muECD (%RSD < 20%). The accuracy of both optimized methods was satisfactorily demonstrated by analysis of appropriate certified reference material (CRM), WMF-01.

  19. 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.

  20. Concentrations of organophosphorus, polybromobenzene, and polybrominated diphenyl ether flame retardants in human serum, and relationships between concentrations and donor ages.

    PubMed

    Li, Peng; Jin, Jun; Wang, Ying; Hu, Jicheng; Xu, Meng; Sun, Yiming; Ma, Yulong

    2017-03-01

    Organophosphorus flame retardants, polybromobenzenes, and polybrominated diphenyl ethers (PBDEs) were determined in pooled human serum samples collected in an area in which these chemicals are produced in North China. Tri (2-chloroethyl) phosphate (TCEP) was found at a higher concentration than the other chemicals, and the mean TCEP concentration was 480.4 ng/g lipid. This is the first time TCEP has been detected in human serum from China. The PBDE concentration in serum was found to have decreased between 2007 and 2013. BDE-209 remained the dominant PBDE congener, and its mean concentration was 91.3 ng/g lipid in this study. The polybromobenzene concentrations were relatively low, but pentabromobenzene and pentabromotoluene were found in very many of the samples. The highest TCEP, tris(2-butoxyethyl)phosphate, pentabromobenzene, and pentabromotoluene concentrations were found in samples from young people (<30 y old). This suggests that the risks posed by these alternative flame retardants also need more concerns.

  1. 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.

  2. Bioavailability of polybrominated diphenyl ether flame retardants in biosolids and spiked sediment to the aquatic oligochaete, Lumbriculus variegatus.

    PubMed

    Ciparis, Serena; Hale, Robert C

    2005-04-01

    Polybrominated diphenyl ether (PBDE) flame retardants have become distributed ubiquitously in the environment. High concentrations have been reported in U.S. sewage sludge (biosolids). The burgeoning practice of land-applying biosolids as fertilizer creates an avenue for reintroduction of PBDEs to surface waters and aquatic sediments. Bioavailability of biosolids- and sediment-associated PBDEs was assessed using the freshwater oligochaete, Lumbriculus variegatus. Oligochaetes were exposed to composted biosolids (1,600 ng/g total PBDEs) and artificial sediment spiked with penta- and deca-brominated diphenyl ether (BDE) formulations (1,300 ng/g total PBDEs). Uptake (28-d exposure) and depuration (21 d) of eight congeners were studied. Polybrominated diphenyl ethers in both substrates were bioavailable, but bioaccumulation was 5 to 10 times greater from spiked artificial sediment. The congeners BDE 47 and BDE 99 were the most prevalent congeners in oligochaetes after exposure. Congener BDE 47 was more bioaccumulative, possibly due to the threefold greater depuration rate of BDE 99. Bioaccumulation of penta- and hexa-brominated congeners appeared to be affected more strongly by substitution pattern than degree of bromination. Uptake of BDE 209, the dominant congener in deca-BDE, was minimal. Accumulation of certain PBDE congeners from biosolids and sediments by benthos provides a pathway for transfer to higher trophic levels, and congener discrimination may increase with each trophic transfer.

  3. 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.

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

    PubMed

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

    2014-07-01

    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 6h post fertilization to 5 days post fertilization to either PBDE 47 (0.1μM), PBDE 99 (0.1μM) or PBDE 153 (0.1μM), 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.

  5. 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

    2015-08-07

    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

  6. Species-specific accumulation of polybrominated diphenyl ethers (PBDEs) and other emerging flame retardants in several species of birds from Korea.

    PubMed

    Jin, Xiangzi; Lee, Sunggyu; Jeong, Yunsun; Yu, Jae-Pyoung; Baek, Woon Kee; Shin, Kyung-Hoon; Kannan, Kurunthachalam; Moon, Hyo-Bang

    2016-12-01

    Few studies have been conducted on the alternatives to legacy flame retardants in avian species worldwide. In this study, polybrominated diphenyl ethers (PBDEs) and alternative flame retardants such as novel brominated flame retardants (NBFRs) and dechlorane plus (DP) were determined in livers of 10 species of birds from Korea to elucidate species-specific accumulation, biological factors that affect accumulation, and bioaccumulation potentials of these contaminants. Among the emerging alternative flame retardants, the highest occurrence was found for bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEHTBP), syn-DP, anti-DP, and decabromodiphenyl ethane (DBDPE). PBDE concentrations (median: 17.1 ng/g lipid wt) measured in our study were within the ranges reported in previous studies, while the concentrations of BEHTBP, BTBPE and DP were greater than those reported earlier. Residential predatory birds showed significantly greater concentrations of PBDEs and NBFRs than migratory predators and passerine birds. The concentrations of PBDEs, BEHTBP, and DP in residential predatory birds were significantly correlated with increasing stable nitrogen isotope ratio (δ(15)N), which indicated biomagnification potentials of these contaminants. Our results suggest that the concentrations and accumulation patterns of PBDEs, NBFRs, and DP depend on the feeding habits and migration patterns of avian species. This is the first report on the accumulation of emerging alternatives to PBDEs in birds from Korea. Copyright © 2016 Elsevier Ltd. All rights reserved.

  7. Biomagnification of polybrominated diphenyl ether and hexabromocyclododecane flame retardants in the polar bear food chain in Svalbard, Norway.

    PubMed

    Sørmo, Eugen Gravningen; Salmer, Maria Pettersvik; Jenssen, Bjørn Munro; Hop, Haakon; Baek, Kine; Kovacs, Kit Maureen; Lydersen, Christian; Falk-Petersen, Stig; Gabrielsen, Geir Wing; Lie, Elisabeth; Skaare, Janneche Utne

    2006-09-01

    Concentrations of brominated flame retardants (BFRs), including polybrominated diphenylethers (PBDEs) and hexabromocyclododecane (HBCD), were investigated in an arctic marine food chain consisting of four invertebrate species: polar cod (Boreogadus saida), ringed seals (Pusa hispida), and polar bears (Ursus maritimus). The most abundant BFR, brominated diphenyl ether (BDE)-47, was found in detectable concentrations even in zooplankton, the lowest trophic level examined in this study. Most of the investigated BFRs biomagnified as function of tropic level in the food chain. A noticeable exception occurred at the highest trophic level, the polar bear, in which only BDE-153 was found to increase from its main prey, the ringed seal, indicating that polar bears appear to be able to metabolize and biodegrade most BFRs. In contrast, lower-brominated PBDEs, particularly BDE-47, showed clear signs of bioaccumulation in zooplankton, polar cod, and ringed seals. We suggest that this discrepancy in the fate of BFRs among the different species may be related to greater induction of oxidative detoxification activities in the polar bear. Absorption and debromination rates may be more important for bioaccumulation rates of BFRs in zooplankton, polar cod, and ringed seals. Lipid weight-based concentrations (LWCs) and whole body-based concentrations (WBCs) of BFRs were used to assess biomagnification factors (BMFs). Whole-body concentrations gave the most realistic BMFs, as BMFs derived from LWCs seem to be confounded by the large variability in lipid content of tissues from the investigated species. This study demonstrates that PBDEs and HBCD have reached measurable concentrations even in the lower trophic levels (invertebrates and fish) in the Arctic and biomagnifies in the polar bear food chain.

  8. Brominated flame retardants as food contaminants

    USDA-ARS?s Scientific Manuscript database

    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...

  9. 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.

  10. 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

  11. Toxicokinetics of sediment-associated polybrominated diphenylethers (flame retardants) in benthic invertebrates (Lumbriculus variegatus, Oligochaeta).

    PubMed

    Leppänen, Matti T; Kukkonen, Jussi V K

    2004-01-01

    Polybrominated diphenylethers (PBDEs) are ubiquitous environmental contaminants showing rapid temporal increase in some sample types. The compounds are known to biomagnify in aquatic food webs and are assumed to archive into sediments and soils. Currently, no direct evidence indicates whether sediment-associated PBDEs are available for biota. The aim of the present study was to explore the uptake and elimination of two common congeners (47 and 99) in sediment-inhabiting invertebrates to shed light on possible bioavailability of sediment-associated PBDEs. Two clean lake sediments were spiked with environmentally relevant concentrations of 14C-labeled tetra- and pentabromo diphenylether, and oligochaetes (Lumbriculus variegatus) were exposed for three or four weeks to allow kinetic accumulation calculations. Subsequent depuration tests were performed after three weeks of exposure to obtain depuration rates. Both congeners were clearly bioavailable, and only slight differences in steady-state tissue concentrations were found between the four sediment-ingesting oligochaete treatments (biota sediment accumulation factors [BSAFs], 3.0-3.7). The tetrabromo diphenylether-exposed oligochaetes that did not ingest sediment had clearly lower influx rates (0.1 vs 1-3 nmol h(-1)) than sediment-ingesting worms. Also, the estimated BSAF (1.8) was statistically different from that of the sediment-ingesting oligochaetes. These findings support the significance of feeding behavior in bioaccumulation of very hydrophobic organic contaminants. Depuration of both congeners was biphasic, indicating two kinetically different compartments in L. variegatus. Compartment A made up 73 to 92% of total radioactivity in tissues and had relatively fast depuration rates (half-lives, 10.5-47.5 h); the smaller compartment B had very slow depuration rates. No significant biotransformation of PBDEs was evident. The present study clearly demonstrates that the sediment-associated PBDEs, like other

  12. 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

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

    PubMed

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

    1999-08-01

    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.

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

    USGS Publications Warehouse

    Henny, C.J.; Kaiser, J.L.; Grove, R.A.; Johnson, B.L.; Letcher, R.J.

    2009-01-01

    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-??-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 ???PBDEs (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 ???PBDE concentrations in osprey eggs exceed 1,000 ng/g ww with negative relationships indicated at both locations between productivity and ???PBDE concentrations in eggs (P = 0.008, P = 0.057). Osprey eggs from

  15. 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

  16. 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.

  17. [Comparative study of the level and distribution of polybrominated diphenyl ethers and new brominated flame retardants in the atmosphere of typical urban].

    PubMed

    Wu, Hui; Jin, Jun; Wang, Ying; Li, Ming-Yuan; He, Song-Jie; Xu, Meng; Sun, Yi-Ming

    2014-04-01

    Brominated flame retardants (BFRs) are widely used in industrial and commercial products and are frequently detected in various environmental media. It might be potential harm to the environment and the human body. This study reported the levels of 8 kinds of polybrominated diphenyl ethers (PBDEs: BDE-28, -47, -100, -99, -154, -153, -183, -209) and 3 kinds of new brominated flame retardants (NBFRs: PBT, PBEB, HBB) in the atmosphere of Binhai Development Zone, Weifang City, Shandong Province, which was taken as a BFR production source area and of Nanning City, Guangxi Province, which was taken as a contrast area. The results showed that the average concentrations of sigma8 PBDEs in the atmosphere of Weifang and Nanning were 1.4 x 10(5) pg x m(-3) and 323.0 pg x m(-3), respectively, and the average concentrations of sigma3 NBFRs were 4.2 x 10(3) pg x m(-3) and 11.9 pg x m(-3), respectively. Compared with other cities, the concentrations of BFRs in the atmosphere of the production area were at a high level in the globe, and the concentrations of BFRs in Nanning were similar with other cities in China. The distribution characteristics of PBDEs and NBFRs in the atmosphere of the production area were different from those of Nanning, and the correlations between PBEB, PBT, HBB and BDE-209 were different between Weifang and Nanning.

  18. 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...

  19. 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...

  20. Removal of pharmaceuticals, polybrominated flame retardants and UV-filters from sludge by the fungus Trametes versicolor in bioslurry reactor.

    PubMed

    Rodríguez-Rodríguez, Carlos E; Barón, Enrique; Gago-Ferrero, Pablo; Jelić, Aleksandra; Llorca, Marta; Farré, Marinella; Díaz-Cruz, M Silvia; Eljarrat, Ethel; Petrović, Mira; Caminal, Glòria; Barceló, Damià; Vicent, Teresa

    2012-09-30

    Conventional wastewater treatments are inefficient in the removal of many organic pollutants. The presence of these contaminants in the final sludge represents a source of environmental pollution due to the increasing use of biosolids in land application. A biotechnological approach which employed the fungus Trametes versicolor in a sludge-bioslurry reactor was assessed in order to remove several groups of emerging pollutants. Biological fungal activity was monitored by means of ergosterol and laccase determinations. Fifteen out of 24 detected pharmaceuticals were removed at efficiencies over 50% after the treatment, including eight completely degraded. Removal ranged between 16-53% and 22-100% for the brominated flame retardants and the UV-filters, respectively. Only two of all the detected compounds remained unchanged after the treatment. Although elimination results are promising, the toxicity of the final sludge increased after the treatment. This finding is contrary to the toxicity results obtained in similar treatments of sludge with T. versicolor in solid-phase.

  1. Determination of novel brominated flame retardants and polybrominated diphenyl ethers in serum using gas chromatography-mass spectrometry with two simplified sample preparation procedures.

    PubMed

    Gao, Le; Li, Jian; Wu, Yandan; Yu, Miaohao; Chen, Tian; Shi, Zhixiong; Zhou, Xianqing; Sun, Zhiwei

    2016-11-01

    Two simple and efficient pretreatment procedures have been developed for the simultaneous extraction and cleanup of six novel brominated flame retardants (NBFRs) and eight common polybrominated diphenyl ethers (PBDEs) in human serum. The first sample pretreatment procedure was a quick, easy, cheap, effective, rugged, and safe (QuEChERS)-based approach. An acetone/hexane mixture was employed to isolate the lipid and analytes from the serum with a combination of MgSO4 and NaCl, followed by a dispersive solid-phase extraction (d-SPE) step using C18 particles as a sorbent. The second sample pretreatment procedure was based on solid-phase extraction. The sample extraction and cleanup were conducted directly on an Oasis HLB SPE column using 5 % aqueous isopropanol, concentrated sulfuric acid, and 10 % aqueous methanol, followed by elution with dichloromethane. The NBFRs and PBDEs were then detected using gas chromatography-negative chemical ionization mass spectrometry (GC-NCI MS). The methods were assessed for repeatability, accuracy, selectivity, limits of detection (LODs), and linearity. The results of spike recovery experiments in fetal bovine serum showed that average recoveries ranged from 77.9 % to 128.8 % with relative standard deviations (RSDs) from 0.73 % to 12.37 % for most of the analytes. The LODs for the analytes in fetal bovine serum ranged from 0.3 to 50.8 pg/mL except for decabromodiphenyl ethane. The proposed method was successfully applied to the determination of the 14 brominated flame retardants in human serum. The two pretreatment procedures described here are simple, accurate, and precise, and are suitable for the routine analysis of human serum. Graphical Abstract Workflow of a QuEChERS-based approach (top) and an SPE-based approach (bottom) for the detection of PBDEs and NBFRs in serum.

  2. 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.

  3. Critical review of soil contamination by polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs); concentrations, sources and congener profiles.

    PubMed

    McGrath, Thomas J; Ball, Andrew S; Clarke, Bradley O

    2017-11-01

    Polybrominated diphenyl ethers (PBDEs) have been used in a broad array of polymeric materials such as plastics, foams, resins and adhesives to inhibit the spread of fires since the 1970s. The widespread environmental contamination and well documented toxic effects of PBDEs have led to bans and voluntary withdrawals in many jurisdictions. Replacement novel brominated flame retardants (NBFRs) have, however, exhibited many of the same toxic characteristics as PBDEs and appear to share similar environmental fate. This paper presents a critical review of the scientific literature regarding PBDE and NBFR contamination of surface soils internationally, with the secondary objective of identifying probable pollution sources. An evaluation of NBFR distribution in soil was also conducted to assess the suitability of the newer compounds as replacements for PBDEs, with respect to their land contamination potential. Principle production of PBDEs and NBFRs and their consequent use in secondary polymer manufacture appear to be processes with strong potential to contaminate surrounding soils. Evidence suggests that PBDEs and NBFRs are also released from flame retarded products during disposal via landfill, dumping, incineration and recycling. While the land application of sewage sludge represents another major pathway of soil contamination it is not considered in this review as it is extensively covered elsewhere. Both PBDEs and NBFRs were commonly detected at background locations including Antarctica and northern polar regions. PBDE congener profiles in soil were broadly representative of the major constituents in Penta-, Octa- and Deca-BDE commercial mixtures and related to predicted market place demand. BDE-209 dominated soil profiles, followed by BDE-99 and BDE-47. Although further research is required to gain baseline data on NBFRs in soil, the current state of scientific literature suggests that NBFRs pose a similar risk to land contamination as PBDEs. Copyright © 2017

  4. Evaluation of DNA damage induced by 2 polybrominated diphenyl ether flame retardants (BDE-47 and BDE-209) in SK-N-MC cells.

    PubMed

    Pellacani, Claudia; Buschini, Annamaria; Galati, Serena; Mussi, Francesca; Franzoni, Susanna; Costa, Lucio G

    2012-01-01

    Polybrominated diphenyl ethers (PBDEs) are a class of flame retardants whose levels have increased in the environment and in human tissues in the past decades. Exposure to PBDEs has been associated with developmental neurotoxicity, endocrine dysfunction, and reproductive disorders. In spite of their widespread distribution and potential adverse health effects, only few studies have addressed the potential neurotoxicity of PBDEs. In the present study, we evaluated the cyto- and genotoxicity of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) and decabrominated diphenyl ether (BDE-209) in human neuroblastoma cells (SK-N-MC). The DNA damage was measured using the alkaline version of the Comet assay, while specific oxidative-generated DNA damage was evaluated by a modified version of the Comet assay with the repair enzyme formamidopyrimidine glycosylase (FPG). The results show that BDE-47 and BDE-209 (5-20 μmol/L) are able to induce DNA damage in human SK-N-MC cells. Pretreatment with the antioxidant melatonin significantly reduced the DNA damage induced by both congeners. The Comet assay carried out in the presence of FPG suggests that both congeners increase purine oxidation. In all cases, BDE-47 was more potent than BDE-209. The results indicate that 2 environmentally relevant PBDEs cause DNA damage which is primarily mediated by the induction of oxidative stress and may contribute to adverse health effects.

  5. 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.

  6. 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

  7. Concentrations of polybrominated diphenyl ethers and alternative flame retardants in surface soils and river sediments from an electronic waste-processing area in northern Vietnam, 2012-2014.

    PubMed

    Matsukami, Hidenori; Suzuki, Go; Someya, Masayuki; Uchida, Natsuyo; Tue, Nguyen Minh; Tuyen, Le Huu; Viet, Pham Hung; Takahashi, Shin; Tanabe, Shinsuke; Takigami, Hidetaka

    2017-01-01

    We investigated the concentrations of polybrominated diphenyl ethers (PBDEs) and alternative flame retardants (FRs) in environmental samples collected in January 2012, 2013, and 2014 from an electronic waste-processing area in northern Vietnam. During the study period, PBDE and alternative FR concentrations in soils around the electronic waste-processing workshops ranged from 37 to 9200 ng g(-1) dry weight (dw) and from 35 to 24,000 ng g(-1) dw; the concentrations in soils around the open-burning sites ranged from 1.6 to 62 ng g(-1) dw and from <4 to 1900 ng g(-1) dw; and the concentrations in river sediments around the workshops ranged from 100 to 3800 ng g(-1) dw and from 23 to 6800 ng g(-1) dw, respectively. Over the course of study period, we observed significant decreases in concentrations of PBDEs and significant increases in concentrations of alternative FRs, particularly Dechlorane Plus isomers and oligomeric organophosphorus FRs (o-PFRs) in both soils and sediments around the workshops. We also report information on concentrations and environmental emissions of o-PFRs and their low-molecular-weight impurities in the same soils and sediments. The detection of o-PFR impurities around the workshops and the open-burning sites highlights an enhanced breakdown of o-PFRs probably due to weathering during open storage and high temperature attained during the burning of electronic wastes. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. 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.

  9. Flame retardant polymeric materials

    SciTech Connect

    Lewin, M.; Atlas, S.M.; Pearce, E.M.

    1982-01-01

    The flame retardation of polyolefins is the focus of this volume. Methods for reduction of smoke and experimental evaluation of flammability parameters for polymeric materials are discussed. The flammability evaluation methods for textiles and the use of mass spectrometry for analysis of polymers and their degradation products are also presented.

  10. 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. Copyright 2009 Elsevier Ltd. All rights reserved.

  11. Modeling human off-site aerosol exposures to polybrominated flame retardants emitted during the land application of sewage sludge.

    PubMed

    Ziemba, Chris; Yang, Wulin; Peccia, Jordan

    2013-10-01

    Elevated sewage sludge concentrations of polybrominated diphenyl ethers (PBDEs) are due to their broad utilization in textiles and polymers, their resistance to biological degradation, and also their hydrophobic nature-which drives partitioning into wastewater solids. This study estimated the total U.S. emissions of PBDE due to sewage sludge land application and then determined the human inhalation exposure to sludge-associated PBDEs as a function meteorological conditions and downwind distances from an application site. These aerosol exposures have also been incorporated into pharmacokinetic models to predict contributions to steady-state body burden. Our results suggest that while the amount of PBDEs aerosolized during the land application process is small compared to aerosol emissions associated with product use, the application of sludges onto U.S. soils constitutes a major source of PBDEs entering the outdoor environment. Regarding aerosol exposure to nearby residents, the maximum daily inhalation dosages from a common land application scenario occur immediately after sewage sludges are applied and were 137, 27, 1.9, and 81pg/day for significant congeners PBDE-47, -99, -153 and 209 respectively. These doses are 1-2 orders of magnitude less than the standard daily inhalation exposure to the same PBDEs associated with home indoor air and are similar to doses from inhalation of urban and rural outdoor air. Under the worst-case atmospheric transport scenario, the dosages are reduced by approximately 1 order of magnitude when the setback distance between the sludge aerosolization source and human receptor is increased to 200m. Though the health implications of low-level exposures are not well-understood, these sludge-derived PBDE dosages contribute less than a tenth of 1% to the estimated total body burden of PBDE produced from inhalation of indoor and outdoor air, exposure to house dust, and exposure to PBDE from food and water intake. Overall, the inhalation of

  12. 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.

  13. Bioaccumulation and toxicity of the flame retardant TBPH or the polychlorinated biphenyl PCB153 during dietary exposure in mummichog (Fundulus heteroclitus)

    EPA Science Inventory

    The use of polybrominated diphenyl ethers as flame retardants in consumer products has been scrutinized increasingly due to their environmental persistence and potential toxicity; however, alternative replacement flame retardants may have similar drawbacks. The alternative bromin...

  14. Bioaccumulation and toxicity of the flame retardant TBPH or the polychlorinated biphenyl PCB153 during dietary exposure in mummichog (Fundulus heteroclitus)

    EPA Science Inventory

    The use of polybrominated diphenyl ethers as flame retardants in consumer products has been scrutinized increasingly due to their environmental persistence and potential toxicity; however, alternative replacement flame retardants may have similar drawbacks. The alternative bromin...

  15. 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

  16. 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.

  17. PBDE FLAME RETARDANTS: TOXICOLOGY, HEALTH EFFECTS, AND RISK ASSESSMENT

    EPA Science Inventory

    Polybrominated diphenyl ether (PBDE) flame retardants have been routinely added to consumer products for several decades in a successful effort to reduce fire-related injury and property damage. Global production of PBDEs has reached 67,000 metric tons per year. Recently concer...

  18. 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...

  19. 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...

  20. 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...

  1. 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) ...

  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. 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) ...

  4. 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...

  5. 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...

  6. 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.

  7. 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

  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

    Dunnick, June K; Nyska, Abraham

    2009-01-01

    Lower molecular weight polybrominated diphenyl ethers (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 500mg/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 50mg/kg and above in rats, and at 100mg/kg and above in mice. Liver Cyp 1A1, 1A2, and 2B levels were increased at exposure levels of 50mg/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 5mg/kg above in rats and 50mg/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.

  9. Firefighters and flame retardant activism.

    PubMed

    Cordner, Alissa; Rodgers, Kathryn M; Brown, Phil; Morello-Frosch, Rachel

    2015-02-01

    In the past decade, exposure to flame retardant chemicals has become a pressing health concern and widely discussed topic of public safety for firefighters in the United States. Working through local, state, and national unions and independent health and advocacy organizations, firefighters have made important contributions to efforts to restrict the use of certain flame retardants. Firefighters are key members in advocacy coalitions dedicated to developing new environmental health regulations and reforming flammability standards to reflect the best available fire science. Their involvement has been motivated by substantiated health concerns and critiques of deceptive lobbying practices by the chemical industry. Drawing on observations and interviews with firefighters, fire safety experts, and other involved stakeholders, this article describes why firefighters are increasingly concerned about their exposure to flame retardant chemicals in consumer products, and analyzes their involvement in state and national environmental health coalitions.

  10. Flame Retardants Used in Flexible Polyurethane Foam

    EPA Pesticide Factsheets

    The partnership project on flame retardants in furniture seeks to update the health and environmental profiles of flame-retardant chemicals that meet fire safety standards for upholstered consumer products with polyurethane foam

  11. 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. Copyright © 2015. Published by Elsevier Ltd.

  12. Brominated flame retardants in US food.

    PubMed

    Schecter, Arnold; Harris, T Robert; Shah, Nirav; Musumba, Alice; Päpke, Olaf

    2008-02-01

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

  13. 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

  14. 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.

  15. Photochemical and microbial transformation of emerging flame retardants: cause for concern?

    PubMed

    Chen, Da; Hale, Robert C; Letcher, Robert J

    2015-04-01

    Among anthropogenic chemicals, flame retardants have attracted mounting environmental concerns. In recent years, an increasing number of studies have been conducted worldwide to investigate flame-retardant sources, environmental distribution, wildlife and human exposure, and toxicity. Data generated have demonstrated that some flame-retardant substances such as polybrominated diphenyl ethers (PBDE) are persistent, bioaccumulative, and toxic to exposed organisms. However, comparatively much less attention has been paid to the mechanisms and products of environmental transformation of flame retardants. This lack of information undermines our understanding of the environmental behavior and fate of flame retardants, as well as the associated risks to environmental and human health. Photochemical and microbial transformation of flame retardants in various matrices and environmental compartments can elevate the toxicological significance of flame retardant exposure, via the formation of, for example, lesser halogenated but more bioaccumulative degradation products and toxic radicals. Such pathways raise concerns related to the environmental safety of some alternative flame retardants that are presumably safe and used to replace PBDEs. To fully assess the environmental risks, more research is needed to investigate the environmental transformation potential of emerging flame retardants including polymeric flame retardants. Enhanced analytical efforts are needed to better characterize transformation products and transient radicals. Additional mesocosm and field studies are needed to elucidate transformation kinetics and consequences under environmentally relevant conditions. © 2015 SETAC.

  16. Halogenated flame retardants in bobcats from the midwestern United States.

    PubMed

    Boyles, Esmarie; Tan, Hongli; Wu, Yan; Nielsen, Clayton K; Shen, Li; Reiner, Eric J; Chen, Da

    2017-02-01

    In response to the restrictions of polybrominated diphenyl ether (PBDE) flame retardants in various consumer products, alternative halogenated flame retardants have been subjected to increased use. Compared to aquatic ecosystems, relatively little information is available on the contamination of alternative flame retardants in terrestrial ecosystems, especially with regards to mammalian wildlife. In this study we used a top terrestrial carnivore, the bobcat (Lynx rufus), as a unique biomonitoring species for assessing flame retardant contamination in the Midwestern United States (U.S.) terrestrial ecosystems. Concentrations of ∑PBDEs (including all detectable PBDE congeners) ranged from 8.3 to 1920 ng/g lipid weight (median: 50.3 ng/g lw) in livers from 44 bobcats collected during 2013-2014 in Illinois. Among a variety of alternative flame retardants screened, Dechloranes (including anti- and syn-Dechlorane Plus and Dechlorane-602, 603, and 604), tetrabromo-o-chlorotoluene (TBCT), and hexabromocyclododecane (HBCD) were also frequently detected, with median concentrations of 28.7, 5.2, and 11.8 ng/g lw, respectively. Dechlorane analogue compositions in bobcats were different from what has been reported in other studies, suggesting species- or analogue-dependent bioaccumulation, biomagnification, or metabolism of Dechlorane chemicals in different food webs. Our findings, along with previously reported food web models, suggest Dechloranes may possess substantial bioaccumulation and biomagnification potencies in terrestrial mammalian food webs. Thus, attention should be given to these highly bioavailable flame retardants in future environmental biomonitoring and risk assessments in a post-PBDE era. Copyright © 2016. Published by Elsevier Ltd.

  17. 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.

  18. 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.

  19. Bioaccumulation and toxicity of the flame retardant TBPH or ...

    EPA Pesticide Factsheets

    The use of polybrominated diphenyl ethers as flame retardants in consumer products has been scrutinized increasingly due to their environmental persistence and potential toxicity; however, alternative replacement flame retardants may have similar drawbacks. The alternative brominated flame retardant bis(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH) is a component of several commercial flame retardants, including Firemaster® 550, Firemaster® BZ-54 and DP-45. Here we investigate the bioaccumulation, bioenergetics and other adverse outcomes pathways (AOPs) predicted for dietary exposure to a carrier control, two levels of TBPH, or 2,2',4,4',5,5'-hexachlorobiphenyl (PCB153, a well-studied compound acting as a positive control for some aspects of the study). The TBPH concentrations chosen were at or well above the environmental concentrations documented in the literature, but similar to those causing toxicity in a previous study. Our experimental model is a small estuarine fish, the mummichog (Fundulus heteroclitus), exposed as individually tagged fish held in small groups (2 male, 2 female) in replicate tanks and fed contaminated food from day 0-28, followed by uncontaminated food from day 29-42. Throughout the experiment, individual growth was measured weekly, and at various time points, fish from replicate tanks were sacrificed, measured and dissected. To support putative AOPs, samples were obtained for analysis of hormone levels and transcriptomic responses

  20. Wastewater dilution index partially explains observed polybrominated diphenyl ether flame retardant concentrations in osprey eggs from Columbia River Basin, 2008-2009.

    PubMed

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

    2011-06-01

    Several polybrominated biphenyl ether (PBDE) congeners were found in all 175 osprey (Pandion haliaetus) eggs collected from the Columbia River Basin between 2002 and 2009. ΣPBDE concentrations in 2008-2009 were highest in osprey eggs from the two lowest flow rivers studied; however, each river flowed through relatively large and populous metropolitan areas (Boise, Idaho and Spokane, Washington). We used the volume of Wastewater Treatment Plant (WWTP) discharge, a known source of PBDEs, as a measure of human activity at a location, and combined with river flow (both converted to millions of gallons/day) created a novel approach (an approximate Dilution Index) to relate waterborne contaminants to levels of these contaminants that reach avian eggs. This approach provided a useful understanding of the spatial osprey egg concentration patterns observed. Individual osprey egg concentrations along the Upper Willamette River co-varied with the Dilution Index, while combined egg data (geometric means) from rivers or segments of rivers showed a strong, significant relationship to the Dilution Index with one exception, the Boise River. There, we believe osprey egg concentrations were lower than expected because Boise River ospreys foraged perhaps 50-75% of the time off the river at ponds and lakes stocked with fish that contained relatively low ΣPBDE concentrations. Our limited temporal data at specific localities (2004-2009) suggests that ΣPBDE concentrations in osprey eggs peaked between 2005 and 2007, and then decreased, perhaps in response to penta- and octa-PBDE technical mixtures no longer being used in the USA after 2004. Empirical estimates of biomagnification factors (BMFs) from fish to osprey eggs were 3.76-7.52 on a wet weight (ww) basis or 4.37-11.0 lipid weight. Our earlier osprey study suggested that ΣPBDE egg concentrations >1,000 ng/g ww may reduce osprey reproductive success. Only two of the study areas sampled in 2008-2009 contained individual eggs with

  1. Wastewater dilution index partially explains observed polybrominated diphenyl ether flame retardant concentrations in osprey eggs from Columbia River Basin, 2008-2009

    USGS Publications Warehouse

    Henry, Charles J.; Grove, Robert A.; Kaiser, James L.; Johnson, Branden L.; Furl, Chad V.; Letcher, Robert J.

    2011-01-01

    Several polybrominated biphenyl ether (PBDE) congeners were found in all 175 osprey (Pandion haliaetus) eggs collected from the Columbia River Basin between 2002 and 2009. ΣPBDE concentrations in 2008–2009 were highest in osprey eggs from the two lowest flow rivers studied; however, each river flowed through relatively large and populous metropolitan areas (Boise, Idaho and Spokane, Washington). We used the volume of Wastewater Treatment Plant (WWTP) discharge, a known source of PBDEs, as a measure of human activity at a location, and combined with river flow (both converted to millions of gallons/day) created a novel approach (an approximate Dilution Index) to relate waterborne contaminants to levels of these contaminants that reach avian eggs. This approach provided a useful understanding of the spatial osprey egg concentration patterns observed. Individual osprey egg concentrations along the Upper Willamette River co-varied with the Dilution Index, while combined egg data (geometric means) from rivers or segments of rivers showed a strong, significant relationship to the Dilution Index with one exception, the Boise River. There, we believe osprey egg concentrations were lower than expected because Boise River ospreys foraged perhaps 50–75% of the time off the river at ponds and lakes stocked with fish that contained relatively low ΣPBDE concentrations. Our limited temporal data at specific localities (2004–2009) suggests that ΣPBDE concentrations in osprey eggs peaked between 2005 and 2007, and then decreased, perhaps in response to penta- and octa-PBDE technical mixtures no longer being used in the USA after 2004. Empirical estimates of biomagnification factors (BMFs) from fish to osprey eggs were 3.76–7.52 on a wet weight (ww) basis or 4.37–11.0 lipid weight. Our earlier osprey study suggested that ΣPBDE egg concentrations >1,000 ng/g ww may reduce osprey reproductive success. Only two of the study areas sampled in 2008–2009 contained

  2. 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. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Some polybrominated diphenyl ether (PBDE) flame retardants with wide environmental distribution inhibit TCDD-induced EROD activity in primary cultured carp (Cyprinus carpio) hepatocytes.

    PubMed

    Kuiper, R V; Bergman, A; Vos, J G; van den Berg, M

    2004-06-10

    Ethoxyresorufin-O-deethylase (EROD) activity, a catalytic function of the cytochrome P450 1A (CYP1A) microsomal oxygenase subfamily, is a popular biomarker for exposure to xenobiotics, polyhalogenated aromatic hydrocarbons (PHAHs) in particular. It has found wide use in aquatic pollution assessment both in vivo and in vitro. In such studies, subjects are often exposed to complex mixtures where various constituents can interfere with EROD-activity, possibly resulting in inadequate estimation of toxic hazard or biological response. The present study investigates the effects of polybrominated diphenyl ethers (PBDEs), a relatively new and increasingly detected group of environmental contaminants, on the validity of EROD activity as exposure marker in carp (Cyprinus carpio) hepatocytes. Freshly isolated hepatocytes of a genetically uniform strain of male carp were co-exposed to 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) at concentrations of 0, 1, 3, 10, 30, and 100 pM, and one of the highly purified PBDE/PCB congeners (at concentrations of 0, 0.25, and 2.5 microM) or cleaned-up and untreated DE-71 samples (0, 0.1, and 1 microM). PBDEs were selected from the 209 possible congeners based on their relative abundance in environmental samples: BDE-47, BDE-99, BDE-100, and BDE-153. A tentative metabolite of BDE-47, 6OH-BDE-47, was also included. In addition, a commercial pentabrominated dipenylether mixture (DE-71) was tested for interference with EROD activity both with and without clean-up by carbon fractionating which removed possible planar contaminants. Polychlorinated biphenyl (PCB)-153, a reported inhibitor of EROD activity in flounder, was included for comparison. Cells were cultured for a total period of 8 days; exposure started at day 3 after cell isolation. After 5 days of exposure, cell pellets were frozen before EROD activity was determined. Upon exposure to TCDD, the cells responded with increased EROD activity as expected. Significant reduction of TCDD

  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) w...

  5. 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...

  6. 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...

  7. 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...

  8. 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

  9. 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...

  10. 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...

  11. 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...

  12. 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...

  13. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Flame retardants and legacy chemicals in Great Lakes' water.

    PubMed

    Venier, Marta; Dove, Alice; Romanak, Kevin; Backus, Sean; Hites, Ronald

    2014-08-19

    The Great Lakes have been the focus of extensive environmental research, but recent data on the aquatic concentrations of emerging compounds, such as flame retardants, are scarce. Water samples from 18 stations on the five Great Lakes were collected in 2011 and 2012 using XAD-2 resin adsorption and analyzed for PCBs, organochlorine pesticides, PAHs, polybrominated diphenyl ethers (PBDEs), and emerging flame retardants, including organophosphate flame retardants (OPEs). Total PCB concentrations ranged from 117 ± 18 pg/L in Lake Superior to 623 ± 113 pg/L in Lake Ontario. Among the organochlorine pesticides, the most abundant was dieldrin, with the highest average concentration of 99 ± 26 pg/L in Lake Erie, followed by p,p'-DDD with an average concentration of 37 ± 8 pg/L in Lake Ontario. Total PAH concentrations were higher in Lakes Erie and Ontario than in Lakes Michigan, Huron, and Superior. Total PBDE concentrations were highest in Lake Ontario (227 ± 75 pg/L), and the most abundant congeners were BDE-47, BDE-99, and BDE-209. Total OPE concentrations ranged between 7.3 ± 4.5 ng/L in Lake Huron to 96 ± 43 ng/L in Lake Erie.

  15. Flame retardant cotton barrier nonwovens for mattresses

    USDA-ARS?s Scientific Manuscript database

    According to regulation CPSC 16 CFR 1633, every new residential mattress sold in the United States since July 2007 must resist ignition by open flame. An environmentally benign “green”, inexpensive way to meet this regulation is to use a low-cost flame retardant (FR) barrier fabric. In this study, a...

  16. 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.

  17. 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

  18. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. [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.

  20. 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

  1. Exposures, mechanisms, and impacts of endocrine-active flame retardants.

    PubMed

    Dishaw, Laura V; Macaulay, Laura J; Roberts, Simon C; Stapleton, Heather M

    2014-12-01

    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 FM 550. 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.

  2. 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…

  3. Preparation and characterizations of flame retardant polyamide 66 fiber

    NASA Astrophysics Data System (ADS)

    Li, Y. Y.; Liu, K.; Xiao, R.

    2017-06-01

    The polyamide 66 (PA66) is one of the most important thermoplastic materials, but it has the drawback of flammability. So the flame retardant PA66 was prepared by condensation polymerization using nylon salt and DOPO-based flame retardant in this paper. Then the flame retardant PA66 fiber was manufactured via melt spinning. The properties of flame retardant PA66 and flame retardant PA66 fiber were investigated by relative viscosity, differential scanning calorimetry (DSC), tensile test, vertical burning test (UL94) and limiting oxygen index (LOI) test. Although the loading of the DOPO-based flame retardant decreased the molecular weight, the melting temperature, the crystallinity and the mechanical properties of flame retardant PA66, the flame retardancy properties improved. The flame retardant PA66 loaded with 5.5 wt% of DOPO-based flame retardant can achieve a UL94 V-0 rating with a LOI value of 32.9%. The tenacity at break decreased from 4.51 cN·dtex-1 for PA66 fiber to 2.82 cN·dtex-1 for flame retardant PA66 fiber which still satisfied the requirements for fabrics. The flame retardant PA66 fiber expanded the application of PA66 materials which had a broad developing prospect.

  4. The role of boron in flame-retardant treatments

    Treesearch

    S. L. LeVan; H. C. Tran

    1990-01-01

    Flame retardants for wood alter the combustion properties of wood to reduce surface flame spread. Flame retardant chemicals cause acid catalyzed dehydration reactions in wood to facilitate the formation of char and reduce the effective heat of combustion, resulting in lower heat release and flame spread. Boron compounds can also form glassy fiis that may inhibit mass...

  5. 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.

  6. Measuring emissions of organophosphate flame retardants using a passive flux sampler

    NASA Astrophysics Data System (ADS)

    Ni, Y.; Kumagai, K.; Yanagisawa, Y.

    Flame retardants are used in polymers to reduce the flammability of building materials, electric appliances, fabric and papers. In recent years, organophosphate flame retardants have been used as substitutes for polybrominated flame retardants (BFRs). In Japan, the amount of organophosphate flame retardants used in 2001 was about five times more than in 2000. Recently, several studies have shown the health concerns for some organophosphate flame retardants. Little research has been performed on the emission of organophosphate flame retardants, especially the relationship between content and emissions. In this study, a new type of passive sampler was developed to measure emissions of organophosphate flame retardants from plastic materials. With this sampler, emissions from polyvinyl chloride wallpaper samples with different content of tris(2-chloroisopropyl)phosphate (TCPP) at different temperatures were examined. The observed maximum emissions of TCPP from 1, 3, 5, 10 and 20 w/w% content wallpaper materials were 262.3, 452.6, 644.8, 1119.1 and 2166.8 μg m -2 h -1, respectively. Emissions from 5% TCPP content materials at 40 and 60 °C were 1135.7 and 2841.2 μg m -2 h -1, respectively. A significantly positive correlation between the flux of TCPP and the TCPP content of the wallpaper samples was observed. A linear relationship was found between the inverse of temperature and the logarithm of TCPP emission. The results imply that the use of materials with a high organophosphate flame retardant content can lead to high emission rates in high-temperature indoor environments.

  7. 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...

  8. 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...

  9. 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...

  10. 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...

  11. 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...

  12. 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...

  13. 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...

  14. Flame retardant exposures in California early childhood education environments.

    PubMed

    Bradman, Asa; Castorina, Rosemary; Gaspar, Fraser; Nishioka, Marcia; Colón, Maribel; Weathers, Walter; Egeghy, Peter P; Maddalena, Randy; Williams, Jeffery; Jenkins, Peggy L; McKone, Thomas E

    2014-12-01

    Infants and young children spend as much as 50h per week in child care and preschool. Although approximately 13 million children, or 65% of all U.S. children, spend some time each day in early childhood education (ECE) facilities, little information is available about environmental exposures in these environments. We measured flame retardants in air and dust collected from 40 California ECE facilities between May 2010 and May 2011. Low levels of six polybrominated diphenyl ether (PBDE) congeners and four non-PBDE flame retardants were present in air, including two constituents of Firemaster 550 and two tris phosphate compounds [tris (2-chloroethyl) phosphate (TCEP) and tris (1,3-dichloroisopropyl) phosphate (TDCIPP)]. Tris phosphate, Firemaster 550 and PBDE compounds were detected in 100% of the dust samples. BDE47, BDE99, and BDE209 comprised the majority of the PBDE mass measured in dust. The median concentrations of TCEP (319 ng g(-1)) and TDCIPP (2265 ng g(-1)) were similar to or higher than any PBDE congener. Levels of TCEP and TDCIPP in dust were significantly higher in facilities with napping equipment made out of foam (Mann-Whitney p-values<0.05). Child BDE99 dose estimates exceeded the RfD in one facility for children<3 years old. In 51% of facilities, TDCIPP dose estimates for children<6 years old exceeded age-specific "No Significant Risk Levels (NSRLs)" based on California Proposition 65 guidelines for carcinogens. Given the overriding interest in providing safe and healthy environments for young children, additional research is needed to identify strategies to reduce indoor sources of flame retardant chemicals.

  15. Recycling of plastic waste: Screening for brominated flame retardants (BFRs).

    PubMed

    Pivnenko, K; Granby, K; Eriksson, E; Astrup, T F

    2017-08-30

    Flame retardants are chemicals vital for reducing risks of fire and preventing human casualties and property losses. Due to the abundance, low cost and high performance of bromine, brominated flame retardants (BFRs) have had a significant share of the market for years. Physical stability on the other hand, has resulted in dispersion and accumulation of selected BFRs in the environment and receiving biota. A wide range of plastic products may contain BFRs. This affects the quality of waste plastics as secondary resource: material recycling may potentially reintroduce the BFRs into new plastic product cycles and lead to increased exposure levels, e.g. through use of plastic packaging materials. To provide quantitative and qualitative data on presence of BFRs in plastics, we analysed bromophenols (tetrabromobisphenol A (TBBPA), dibromophenols (2,4- and 2,6-DBP) and 2,4,6-tribromophenol (2,4,6-TBP)), hexabromocyclododecane stereoisomers (α-, β-, and γ-HBCD), as well as selected polybrominated diphenyl ethers (PBDEs) in samples of household waste plastics, virgin and recycled plastics. A considerable number of samples contained BFRs, with highest concentrations associated with acrylonitrile butadiene styrene (ABS, up to 26,000,000ngTBBPA/g) and polystyrene (PS, up to 330,000ng∑HBCD/g). Abundancy in low concentrations of some BFRs in plastic samples suggested either unintended addition in plastic products or degradation of higher molecular weight BFRs. The presence of currently restricted flame retardants (PBDEs and HBCD) identified in the plastic samples illustrates that circular material flows may be contaminated for extended periods. The screening clearly showed a need for improved documentation and monitoring of the presence of BFRs in plastic waste routed to recycling. Copyright © 2017. Published by Elsevier Ltd.

  16. 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

  17. Analysis of flame retarded polymers and recycling materials.

    PubMed

    Riess, M; Ernst, T; Popp, R; Müller, B; Thoma, H; Vierle, O; Wolf, M; van Eldik, R

    2000-01-01

    Recycling activities on polymeric materials are increasing and becoming more and more important in recent years. For polymers containing no flame retardants, suitable recycling strategies already exist. In order to investigate the recyclability of flame retarded polymers that contain brominated flame retardants, a number of samples were analysed as received from a recycling company. Following the identification and sorting of the samples according to type of polymers and flame retardants, material recycling was tested for the flame retarded polymers identified to occur most frequently. The reactivity of the flame retardants during the recycling procedure was studied by analysing for brominated dioxins and furans. The results demonstrate that flame retarded polymers can be recycled under certain experimental conditions.

  18. 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.

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

    PubMed

    Schreder, Erika D; La Guardia, Mark J

    2014-10-07

    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.

  20. 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

  1. Using silicone wristbands to evaluate preschool children’s exposure to flame retardants

    PubMed Central

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

    2016-01-01

    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

  2. The research of far infrared flame retardant polyester staple fiber

    NASA Astrophysics Data System (ADS)

    Li, Qingshan; Zhang, Kaijun; Luo, Jinqong; Li, Ji’an; Jiang, Jian; Liang, Qianqian; Jin, Yongxia; Liu, Bing

    2017-01-01

    Far infrared flame retardant slices was prepared, fiber with far infrared flame retardant composite function was also prepared by the method of melt spinning. Scanning electron microscopy (SEM) was used to observe the fibrous microscopic structure. In the SEM images, functional ultrafine powder particle size and distribution in the fiber were visible. The results show that the functional ultrafine powder is evenly distributed on the fibrous surface, which is closely combined with fiber, and the far infrared emissivity is F, which is more than (8 to 14 microns) 0.88. Far infrared flame retardant polyester fiber has not only good flame retardant, but also environmental health effect: releasing negative ions and launch far-infrared, which shows wide application prospect. The fiber was processed into far-infrared flame retardant electric blanket, whose functional indicators and flame retardant properties are not reduced.

  3. 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...

  4. 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...

  5. 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...

  6. 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...

  7. Polybrominated Diphenyl Ethers (PBDEs) Action Plan

    EPA Pesticide Factsheets

    Polybrominated diphenyl ethers (PBDEs) have been widely used as flame retardants in a number of applications. EPA is concerned that some of the component congeners are persistent, bioaccumulative and toxic.

  8. [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.

  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. 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.

  11. 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.

  12. 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.

  13. Brominated and organophosphate flame retardants in selected consumer products on the Japanese market in 2008.

    PubMed

    Kajiwara, Natsuko; Noma, Yukio; Takigami, Hidetaka

    2011-09-15

    The concentrations of traditional brominated flame retardants (BFRs) and organophosphate flame retardants (OPFRs) in new consumer products, including electronic equipment, curtains, wallpaper, and building materials, on the Japanese market in 2008 were investigated. Although some components of the electronic equipment contained bromine at concentrations on the order of percent by weight, as indicated by X-ray fluorescence analysis, the bromine content could not be fully accounted for by the BFRs analyzed in this study, which included polybrominated diphenylethers, decabromodiphenyl ethane, tetrabromobisphenol A, polybromophenols, and hexabromocyclododecanes. These results suggest the use of alternative BFRs such as newly developed formulations derived from tribromophenol, tetrabromobisphenol A, or both. Among the 11 OPFRs analyzed, triphenylphosphate was present at the highest concentrations in all the products investigated, which suggests the use of condensed-type OPFRs as alternative flame retardants, because they contain triphenylphosphate as an impurity. Tripropylphosphate was not detected in any samples; and trimethylphosphate, tributyl tris(2-butoxyethyl)phosphate, and tris(1,3-dichloro-2-propyl)phosphate were detected in only some components and at low concentrations. Note that all the consumer products evaluated in this study also contained traditional BFRs in amounts that were inadequate to impart flame retardancy, which implies the incorporation of recycled plastic materials containing BFRs that are of global concern. Copyright © 2011 Elsevier B.V. All rights reserved.

  14. 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.

  15. Are brominated flame retardants endocrine disruptors?

    PubMed

    Legler, Juliette; Brouwer, Abraham

    2003-09-01

    Brominated flame retardants (BFRs) are a group of compounds that have received much attention recently due to their similarity with "old" classes of organohalogenated compounds such as polychlorinated biphenyls (PCBs), in terms of their fate, stability in the environment and accumulation in humans and wildlife. Toxic effects, including teratogenicity, carcinogenicity and neurotoxicity, have been observed for some BFR congeners, in particular the brominated diphenyl ethers (BDEs). This concise review focuses on the potency of BFRs and to disrupt endocrine systems, and attempts to answer the question whether or not BFRs are endocrine disruptors. Evidence is provided on the disruption of the thyroid hormone system by BFRs, with particular emphasis on the BDEs, as most recent data is available on this class of flame retardants. Similar to the hydroxylated PCBs, in vitro mechanistic studies as well as animal experiments have demonstrated the effects of BDEs on thyroid hormone transport and metabolism. An overview of possible effects of BFRs on the estrogen system is also provided. Research gaps are outlined, as well as ongoing and future studies in the European community aimed at contributing to comprehensive risk assessments based on the endocrine-disrupting effects of BFRs.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  17. 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...

  18. Flame retardant antibacterial cotton high-loft nonwoven fabrics

    USDA-ARS?s Scientific Manuscript database

    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...

  19. 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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  1. Halogenated flame retardants: do the fire safety benefits justify the risks?

    PubMed

    Shaw, Susan D; Blum, Arlene; Weber, Roland; Kannan, Kurunthachalam; Rich, David; Lucas, Donald; Koshland, Catherine P; Dobraca, Dina; Hanson, Sarah; Birnbaum, Linda S

    2010-01-01

    Since the 1970s, an increasing number of regulations have expanded the use of brominated and chlorinated flame retardants. Many of these chemicals are now recognized as global contaminants and are associated with adverse health effects in animals and humans, including endocrine and thyroid disruption, immunotoxicity, reproductive toxicity, cancer, and adverse effects on fetal and child development and neurologic function. Some flame retardants such as polybrominated diphenyl ethers (PBDEs) have been banned or voluntarily phased out by manufacturers because of their environmental persistence and toxicity, only to be replaced by other organohalogens of unknown toxicity. Despite restrictions on further production in some countries, consumer products previously treated with banned retardants are still in use and continue to release toxic chemicals into the environment, and the worldwide use of organohalogen retardants continues to increase. This paper examines major uses and known toxic effects of commonly-used organohalogen flame retardants, replacements for those that have been phased out, their combustion by-products, and their effectiveness at reducing fire hazard. Policy and other solutions to maintain fire safety while reducing toxicity are suggested. The major conclusions are: (1) Flammability regulations can cause greater adverse environmental and health impacts than fire safety benefits. (2) The current options for end-of-life disposal of products treated with organohalogens retardants are problematic. (3) Life-cycle analyses evaluating benefits and risks should consider the health and environmental effects of the chemicals, as well as their fire safety impacts. (4) Most fire deaths and most fire injuries result from inhaling carbon monoxide, irritant gases, and soot. The incorporation of organohalogens can increase the yield of these toxic by-products during combustion. (5) Fire-safe cigarettes, fire-safe candles, child-resistant lighters, sprinklers, and

  2. 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...

  3. 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...

  4. Flame retardants in indoor dust and air of a hotel in Japan.

    PubMed

    Takigami, Hidetaka; Suzuki, Go; Hirai, Yasuhiro; Ishikawa, Yukari; Sunami, Masakiyo; Sakai, Shin-ichi

    2009-05-01

    Occurrence of flame retardants (FRs) in the indoor environment of highly flame-retarded public facilities is an important concern from the viewpoint of exposure because it is likely that FRs are used to a greater degree in these facilities than in homes. For this study, brominated flame-retardants (BFRs) and organophosphate flame-retardants and plasticizers (OPs), and brominated dibenzo-p-dioxins/furans (PBDD/DFs) were measured in eight floor dust samples taken from a Japanese commercial hotel that was assumed to have many flame-retardant materials. Concentrations of polybrominated diphenylethers (PBDEs) and hexabromocyclododecanes (HBCDs) varied by about two orders of magnitude, from 9.8-1700 ng/g (median of 1200 ng/g) and from 72-1300 ng/g (median of 740 ng/g), respectively. Concentrations of the two types of BFRs described above were most dominant among the investigated BFRs in the dust samples. It is inferred that BFR and PBDD/DF concentrations are on the same level as those in house and office dust samples reported based on past studies. Regarding concentrations of 11 OPs, 7 OPs were detected on the order of micrograms per gram, which are equivalent to or exceed the BFR concentrations such as PBDEs and HBCDs. Concentrations of the investigated compounds were not uniform among dust samples collected throughout the hotel: concentrations differed among floors, suggesting that localization of source products is associated with FR concentrations in dust. Passive air sampling was also conducted to monitor BFRs in the indoor air of hotel rooms: the performance of an air cleaner placed in the room was evaluated in terms of reducing airborne BFR concentrations. Monitoring results suggest that operation of an appropriate air cleaner can reduce both gaseous and particulate BFRs in indoor air.

  5. Multiparameter toxicity assessment of novel DOPO-derived organophosphorus flame retardants.

    PubMed

    Hirsch, Cordula; Striegl, Britta; Mathes, Stephanie; Adlhart, Christian; Edelmann, Michael; Bono, Epifania; Gaan, Sabyasachi; Salmeia, Khalifah A; Hoelting, Lisa; Krebs, Alice; Nyffeler, Johanna; Pape, Regina; Bürkle, Alexander; Leist, Marcel; Wick, Peter; Schildknecht, Stefan

    2017-01-01

    Halogen-free organophosphorus flame retardants are considered as replacements for the phased-out class of polybrominated diphenyl ethers (PBDEs). However, toxicological information on new flame retardants is still limited. Based on their excellent flame retardation potential, we have selected three novel 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives and assessed their toxicological profile using a battery of in vitro test systems in order to provide toxicological information before their large-scale production and use. PBDE-99, applied as a reference compound, exhibited distinct neuro-selective cytotoxicity at concentrations ≥10 µM. 6-(2-((6-oxido-6H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)amino)ethoxy)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide (ETA-DOPO) and 6,6'-(ethane-1,2-diylbis(oxy))bis(6H-dibenzo[c,e][1,2]oxaphosphinine-6-oxide) (EG-DOPO) displayed adverse effects at concentrations >10 µM in test systems reflecting the properties of human central and peripheral nervous system neurons, as well as in a set of non-neuronal cell types. DOPO and its derivative 6,6'-(ethane-1,2-diylbis(azanediyl))bis(6H-dibenzo[c,e][1,2]oxaphosphinine-6-oxide) (EDA-DOPO) were neither neurotoxic, nor did they exhibit an influence on neural crest cell migration, or on the integrity of human skin equivalents. The two compounds furthermore displayed no inflammatory activation potential, nor did they affect algae growth or daphnia viability at concentrations ≤400 µM. Based on the superior flame retardation properties, biophysical features suited for use in polyurethane foams, and low cytotoxicity of EDA-DOPO, our results suggest that it is a candidate for the replacement of currently applied flame retardants.

  6. Assessing Pediatric Nurses' Knowledge About Chemical Flame Retardants.

    PubMed

    Distelhorst, Laura; Bieda, Amy; DiMarco, Marguerite; Tullai-McGuinness, Susan

    Chemical flame retardants are routinely applied to children's products and are harmful to their health. Pediatric nurses are in a key position to provide education to caregivers on methods to decrease their children's exposure to these harmful chemicals. However, a critical barrier is the absence of any program to educate nurses about chemical flame retardants. In order to overcome this barrier, we must first assess their knowledge. This article provides key highlights every pediatric nurse should know about chemical flame retardants and reports the results of a knowledge assessment study.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  8. 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.

  9. 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.

  10. Sorption of Organophosphorus Flame Retardants (OPFRs) on Settled Dust

    EPA Science Inventory

    Organophosphorus flame retardants (OPFRs) are widely used as additives in industrial and consumer products such as electrical and electronic products, furniture, plastics, textiles, and building/construction materials. Due to human exposure and potential health effects, OPFRs inc...

  11. Sorption of Organophosphorus Flame-Retardants on Settled Dust

    EPA Science Inventory

    Dust is an important sink for indoor air pollutants, such as organophosphorus flame-retardants (OPFRs) that are used as additives in industrial and consumer products including electrical and electronic products, furniture, plastics, textile, and building/construction materials. T...

  12. Aryl Polyphosphonates: Useful Halogen-Free Flame Retardants for Polymers

    PubMed Central

    Chen, Li; Wang, Yu-Zhong

    2010-01-01

    Aryl polyphosphonates (ArPPN) have been demonstrated to function in wide applications as flame retardants for different polymer materials, including thermosets, polycarbonate, polyesters and polyamides, particularly due to their satisfactory thermal stability compared to aliphatic flame retardants, and to their desirable flow behavior observed during the processing of polymeric materials. This paper provides a brief overview of the main developments in ArPPN and their derivatives for flame-retarding polymeric materials, primarily based on the authors’ research work and the literature published over the last two decades. The synthetic chemistry of these compounds is discussed along with their thermal stabilities and flame-retardant properties. The possible mechanisms of ArPPN and their derivatives containing hetero elements, which exhibit a synergistic effect with phosphorus, are also discussed. PMID:28883350

  13. 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)

  14. 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)

  15. Sorption of Organophosphorus Flame-Retardants on Settled Dust

    EPA Science Inventory

    Dust is an important sink for indoor air pollutants, such as organophosphorus flame-retardants (OPFRs) that are used as additives in industrial and consumer products including electrical and electronic products, furniture, plastics, textile, and building/construction materials. T...

  16. Sorption of Organophosphorus Flame Retardants (OPFRs) on Settled Dust

    EPA Science Inventory

    Organophosphorus flame retardants (OPFRs) are widely used as additives in industrial and consumer products such as electrical and electronic products, furniture, plastics, textiles, and building/construction materials. Due to human exposure and potential health effects, OPFRs inc...

  17. 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.

  18. 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...

  19. 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...

  20. 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...

  1. 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...

  2. Bioaccumulation of Dechloranes, organophosphate esters, and other flame retardants in Great Lakes fish.

    PubMed

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

    2017-04-01

    We measured the concentrations of 60 flame retardants (and related compounds) in fish samples collected in the Great Lakes basin. These analytes include dechlorane-related compounds (Decs), organophosphate esters (OPEs), and brominated flame retardants (BFRs). Composite lake trout (Salvelinus namaycush) or walleye (Sander vitreus, from Lake Erie) samples were collected (N=3 for each lake) in 2010 from each of the five Great Lakes (a total of 15 samples). Among the dechlorane-related compounds, Dechlorane, Dechlorane Plus, Dechlorane-602, Dechlorane-603, and Dechlorane-604 (with zero to three bromines and with four chlorines) were detected in >73% of the fish samples. The concentrations of some of these dechlorane-related compounds were 3-10 times higher in Lake Ontario trout than in fish from the other four lakes. Tris(1-chloroisopropyl) phosphate, tri-n-butylphosphate, tris(2-chloroethyl)phosphate, and triphenyl phosphate were found in >50% of the fish samples. Polybrominated diphenyl ethers (PBDEs) were the most abundant of the flame retardants in fish, with a mean concentration of 250ng/g lipid. Our findings suggest that the Decs and BFRs with 3-6 bromines are more bioaccumulative in the fish than the OPEs and high molecular weight BFRs.

  3. 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.

  4. Maternal exposure to brominated flame retardants and infant Apgar scores.

    PubMed

    Terrell, Metrecia L; Hartnett, Kathleen P; Lim, Hyeyeun; Wirth, Julie; Marcus, Michele

    2015-01-01

    Brominated flame retardants (BFRs) and other persistent organic pollutants have been associated with adverse health outcomes in humans and may be particularly toxic to the developing fetus. We investigated the association between in utero polybrominated biphenyl (PBB) and polychlorinated biphenyl (PCB) exposures and infant Apgar scores in a cohort of Michigan residents exposed to PBB through contaminated food after an industrial accident. PBB and PCB concentrations were measured in serum at the time the women were enrolled in the cohort. PBB concentrations were also estimated at the time of conception for each pregnancy using a validated elimination model. Apgar scores, a universal measure of infant health at birth, measured at 1 and 5min, were taken from birth certificates for 613 offspring born to 330 women. Maternal PCB concentrations at enrollment were not associated with below-median Apgar scores in this cohort. However, maternal PBB exposure was associated with a dose-related increase in the odds of a below-median Apgar score at 1min and 5min. Among infants whose mothers had an estimated PBB at conception above the limit of detection of 1 part per billion (ppb) to <2.5ppb, the odds ratio=2.32 (95% CI: 1.22-4.40); for those with PBB⩾2.5ppb the OR=2.62 (95% CI: 1.38-4.96; test for trend p<0.01). Likewise, the odds of a below-median 5min Apgar score increased with higher maternal PBB at conception. It remains critical that future studies examine possible relationships between in utero exposures to brominated compounds and adverse health outcomes.

  5. Maternal exposure to brominated flame retardants and infant Apgar Scores

    PubMed Central

    Terrell, Metrecia L.; Hartnett, Kathleen P.; Lim, Hyeyeun; Wirth, Julie; Marcus, Michele

    2014-01-01

    Brominated flame retardants (BFRs) and other persistent organic pollutants have been associated with adverse health outcomes in humans and may be particularly toxic to the developing fetus. We investigated the association between in utero polybrominated biphenyl (PBB) and polychlorinated biphenyl (PCB) exposures and infant Apgar scores in a cohort of Michigan residents exposed to PBB through contaminated food after an industrial accident. PBB and PCB concentrations were measured in serum at the time the women were enrolled in the cohort. PBB concentrations were also estimated at the time of conception for each pregnancy using a validated elimination model. Apgar scores, a universal measure of infant health at birth, measured at 1 and 5 minutes, were taken from birth certificates for 613 offspring born to 330 women. Maternal PCB concentrations at enrollment were not associated with below–median Apgar scores in this cohort. However, maternal PBB exposure was associated with a dose–related increase in the odds of a below–median Apgar score at 1 minute and 5 minutes. Among infants whose mothers had an estimated PBB at conception above the limit of detection of 1 part per billion, the odds ratio was 2.32 (95 % CI: 1.22– 4.40); for those with PBB ≥ 2.5 ppb the OR=2.62 (95% CI: 1.38-4.96; test for trend p< 0.01). Likewise, the odds of a below–median 5–minute Apgar increased with higher maternal PBB at conception. It remains critical that future studies examine possible relationships between in utero exposures to brominated compounds and adverse health outcomes. PMID:25203650

  6. Ecotoxicity and biodegradability of new brominated flame retardants: a review.

    PubMed

    Ezechiáš, M; Covino, S; Cajthaml, T

    2014-12-01

    Brominated flame retardants (BFRs) have been routinely used as additives in a number of consumer products for several decades in order to reduce the risk of fire accidents. Concerns about the massive use of these substances have increased due to their possible toxicity, endocrine disrupting properties and occurrence in almost all the environmental compartments, including humans and wildlife organisms. Several conventional BFRs (e.g. polybrominated diphenylethers (PBDE)) have been included in the list of Persistent Organic Pollutants and their use has been restricted because of their established toxicity and environmental persistence. Over the past few years, these compounds have been replaced with "new" BFRs (NBFRs). Despite the fact that NBFRs are different chemical molecules than traditional BFRs, most of physical-chemical properties (e.g. aromatic moiety, halogen substitution, lipophilic character) are common to both groups; therefore, their fate in the environment is potentially similar to the banned BFRs. Therefore, this article has been compiled to summarize the published scientific data regarding the biodegradability of the most widely used NBFRs, a key factor in their potential persistency in the environment, and their ecotoxicological effects on humans and test organisms. The data reviewed here document that the mechanisms through NBFRs exibit their ecotoxicity and the processes leading to their biotransformation in the environment are still poorly understood. Thus emphasis is placed on the need for further research in these areas is therefore emphasized, in order to avoid the massive use of further potentially harmful and recalcitrant substances of anthropogenic origin. Copyright © 2014 Elsevier Inc. All rights reserved.

  7. 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

  8. Potential human exposure to halogenated flame-retardants in elevated surface dust and floor dust in an academic environment.

    PubMed

    Allgood, Jaime M; Jimah, Tamara; McClaskey, Carolyn M; La Guardia, Mark J; Hammel, Stephanie C; Zeineddine, Maryam M; Tang, Ian W; Runnerstrom, Miryha G; Ogunseitan, Oladele A

    2017-02-01

    Most households and workplaces all over the world possess furnishings and electronics, all of which contain potentially toxic flame retardant chemicals to prevent fire hazards. Indoor dust is a recognized repository of these types of chemicals including polybrominated diphenyl ethers (PBDEs) and non-polybrominated diphenyl ethers (non-PBDEs). However, no previous U.S. studies have differentiated concentrations from elevated surface dust (ESD) and floor dust (FD) within and across microenvironments. We address this information gap by measuring twenty-two flame-retardant chemicals in dust on elevated surfaces (ESD; n=10) and floors (FD; n=10) from rooms on a California campus that contain various concentrations of electronic products. We hypothesized a difference in chemical concentrations in ESD and FD. Secondarily, we examined whether or not this difference persisted: (a) across the studied microenvironments and (b) in rooms with various concentrations of electronics. A Wilcoxon signed-rank test demonstrated that the ESD was statistically significantly higher than FD for BDE-47 (p=0.01), BDE-99 (p=0.01), BDE-100 (p=0.01), BDE-153 (p=0.02), BDE-154 (p=0.02), and 3 non-PBDEs including EH-TBB (p=0.02), BEH-TEBP (p=0.05), and TDCIPP (p=0.03). These results suggest different levels and kinds of exposures to flame-retardant chemicals for individuals spending time in the sampled locations depending on the position of accumulated dust. Therefore, further research is needed to estimate human exposure to flame retardant chemicals based on how much time and where in the room individuals spend their time. Such sub-location estimates will likely differ from assessments that assume continuous unidimensional exposure, with implications for improved understanding of potential health impacts of flame retardant chemicals. Copyright © 2016 Elsevier Inc. All rights reserved.

  9. Cone calorimeter evaluation of two flame retardant cotton fabrics

    USDA-ARS?s Scientific Manuscript database

    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...

  10. Simultaneous determination of brominated and phosphate flame retardants in flame-retarded polyester curtains by a novel extraction method.

    PubMed

    Miyake, Yuichi; Tokumura, Masahiro; Nakayama, Hayato; Wang, Qi; Amagai, Takashi; Ogo, Sayaka; Kume, Kazunari; Kobayashi, Takeshi; Takasu, Shinji; Ogawa, Kumiko; Kannan, Kurunthachalam

    2017-12-01

    The use of novel brominated flame retardants (BFRs) and phosphate-based flame retardants (PFRs) has increased as substitutes for hexabromocyclododecane (HBCD) in many consumer products. To facilitate collection of data on chemicals used as flame retardants in textiles and fabrics, we developed an analytical method using liquid chromatography interfaced with tandem mass spectrometry (LC-MS/MS). We compared two extraction methods, one involving ultrasonic extraction (traditional method) using dichloromethane, toluene or acetone and the other encompassing complete dissolution of textile with 25% 1,1,1,3,3,3-hexafluoro-2-propanol/chloroform. The dissolution method extracted up to 204 times more BFRs and PFRs than the traditional ultrasonic extraction. Tris(2,3-dibromopropyl) isocyanurate (TDBP-TAZTO), triphenylphosphine oxide (TPhPO), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), tricresyl phosphate (TCsP), and triphenyl phosphate (TPhP) were found in 40 flame-retarded curtain samples purchased from Japanese market in 2014. TDBP-TAZTO was detected in polyester curtains for the first time. Some of the flame-retarded curtain samples did not contain any of the known target analytes, which suggested the presence of other unknown flame retardants in those fabrics. Copyright © 2017. Published by Elsevier B.V.

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

    USDA-ARS?s Scientific Manuscript database

    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 ...

  12. 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.

  13. Photolysis of brominated flame retardants in textiles exposed to natural sunlight.

    PubMed

    Kajiwara, Natsuko; Desborough, Jennifer; Harrad, Stuart; Takigami, Hidetaka

    2013-03-01

    Photolytic transformation profiles of technical hexabromocyclododecane (HBCD) and technical decabromodiphenyl ether (DecaBDE) in flame-retarded textiles exposed to natural sunlight were compared. Textiles that contained approximately 4% HBCDs by weight showed no substantial loss of any of the HBCD diastereomers during the entire exposure period (371 days), indicating that they were resistant to sunlight, that is, that debromination and isomerization of HBCD diastereomers did not occur under the experimental conditions. Exposure of a textile treated with technical DecaBDE resulted in the formation of polybrominated dibenzofurans (PBDFs) as products of photodecomposition of polybrominated diphenyl ethers present in the technical DecaBDE. After 329 days of exposure, the total PBDF concentration reached a maximum of 27 000 ng g(-1), which was approximately 10 times the initial concentration. During the experiment, di- to hexa-BDF congener concentrations increased continuously. Although the concentrations of PBDFs in the textiles were 4–5 orders of magnitude lower than the concentrations of polybrominated diphenyl ethers, it is important to note that PBDFs were formed as a result of sunlight exposure during normal use of products treated with technical DecaBDE.

  14. Detection of Organophosphate Flame Retardants in Furniture Foam and US House Dust

    PubMed Central

    Stapleton, Heather M.; Klosterhaus, Susan; Eagle, Sarah; Fuh, Jennifer; Meeker, John D.; Blum, Arlene; Webster, Thomas F.

    2009-01-01

    Restrictions on the use of polybrominated diphenyl ethers (PBDEs) have resulted in the increased use of alternate flame retardant chemicals to meet flammability standards. However, it has been difficult to determine which chemical formulations are currently being used in high volumes to meet flammability standards since the use of flame retardant formulations in consumer products is not transparent (i.e. not provided to customers). To investigate chemicals being used as replacements for PentaBDE in polyurethane foam, we analyzed foam samples from 26 different pieces of furniture purchased in the United States primarily between 2003 and 2009 using gas chromatography mass spectrometry. Samples included foam from couches, chairs, mattress pads, pillows, and, in one case, foam from a sound proofing system of a laboratory grade dust sieve. Fifteen of the foam samples contained the flame retardant tris(1,3-dichloro-2-propyl) phosphate (TDCPP; 1–5% by weight), four samples contained tris(1-chloro-2-propyl) phosphate (TCPP; 0.5 –2.2 % by weight), one sample contained brominated chemicals found in a new flame retardant mixture called Firemaster 550 (4.2% by weight), and one foam sample collected from a futon likely purchased prior to 2004 contained PentaBDE (0.5% by weight). Due to the high frequency of detection of the chlorinated phosphate compounds in furniture foam, we analyzed extracts from 50 house dust samples collected between 2002 and 2007 in the Boston, MA area for TDCPP, TCPP, and another high volume use organophosphate-based flame retardant used in foam, triphenylphosphate (TPP). Detection frequencies for TDCPP and TPP in the dust samples were >96% and were log normally distributed, similar to observations for PBDEs. TCPP was positively detected in dust in only 24% of the samples, but detection was significantly limited by a co-elution problem. The geometric mean concentrations for TCPP, TDCPP and TPP in house dust were 570, 1890, and 7360 ng/g, respectively

  15. Substance flow analysis of brominated flame retardants and related compounds in waste TV sets in Japan.

    PubMed

    Tasaki, Tomohiro; Takasuga, Takumi; Osako, Masahiro; Sakai, Shin-Ichi

    2004-01-01

    We conducted time-series substance flow analysis of two types of brominated flame retardants (BFRs)--polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA)--and two types of related compounds--Sb (used with BFRs for flame inhibition) and polybrominated dibenzo dioxins and furans (PBDDs/DFs: unintended byproducts)--in five size categories of waste TV sets in Japan. Two scenarios were created with BFR substitutions and compared to a "business as usual" scenario in order to obtain basic information for strategic product management. The results showed that the use of DecaBDE in rear and front covers of TV sets began in fiscal 1987-1990 and 1993-1996, respectively, and that TBBPA was used to some extent as a substitute for DecaBDE in the 90s. The amount of waste Br in the plastic covers is predicted to increase until at least fiscal 2020 due to the increasing size of TV sets. Although substitution of BFRs with non-BFRs in Japan by 2006 will reduce waste Br, the amount in waste TV sets will not peak until fiscal 2009. The results will help inform decisions in Japan regarding the recovery and disposal of waste TV sets. The methods used would benefit waste managers faced with similar issues in other countries.

  16. Exposure to flame retardant chemicals on commercial airplanes.

    PubMed

    Allen, Joseph G; Stapleton, Heather M; Vallarino, Jose; McNeely, Eileen; McClean, Michael D; Harrad, Stuart J; Rauert, Cassandra B; Spengler, John D

    2013-02-16

    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. 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. 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. This study adds to the limited body of knowledge regarding exposure to flame retardants on commercial aircraft, an environment long hypothesized to be at risk for maximum exposures due to strict flame retardant standards for aircraft materials. Our findings indicate that flame retardants are widely used in many airplane components and all airplane types, as

  17. 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

  18. Lightweight and Ultrastrong Polymer Foams with Unusually Superior Flame Retardancy.

    PubMed

    Xu, Linli; Xiao, Linhong; Jia, Pan; Goossens, Karel; Liu, Peng; Li, Hui; Cheng, Chungui; Huang, Yong; Bielawski, Christopher W; Geng, Jianxin

    2017-08-09

    High-performance flame-retardant materials are urgently needed to address outstanding issues that pertain to safety. Traditional flame retardants are toxic to the environment and/or lack the physical properties required for use in many contemporary applications. Here, we show that isocyanate-based polyimide (PI) foam, a flammable material, can exhibit unusually superior flame retardancy as well as other excellent properties, such as being lightweight and displaying high mechanical strength, by incorporating red phosphorus (RP)-hybridized graphene. The covalent bonds formed between the graphene platelets and the PI matrix provide the resultant PI foam with a specific Young's modulus (83 kNm kg(-1)) that is comparable to or even higher than those displayed by state-of-the-art foams, including silica aerogels, polystyrene foams, and polyurethane foams. In addition, even a low content of the RP-hybridized graphene (2.2 wt %) results in an exceptionally higher limiting oxygen index (39.4) than those of traditional flame-retardant polymer-based materials (typically 20-30). The resultant PI foam also exhibits thermal insulation properties that are similar to that of air. Moreover, the RP-hybridized graphene is prepared using a one-step ball milling process in 100% yield, and does not require solvent or produce waste. The preparation of the flame-retardant PI foams can be scaled as the starting materials are commercially available and the techniques employed are industrially compatible.

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

    PubMed

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

    2012-01-15

    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.

  20. Detection and speciation of brominated flame retardants in high-impact polystyrene (HIPS) polymers.

    PubMed

    Holbrook, R D; Davis, J M; Scott, K C K; Szakal, C

    2012-05-01

    Polymeric materials have been suggested as possible environmental sources of persistent organic pollutants such as flame retardants. In situ, micrometre-scale characterization techniques for polymer matrix containing flame retardants may provide some insight into the dominant environmental transfer mechanism(s) of these brominated compounds. In this work, we demonstrate that micro X-ray fluorescence spectroscopy (μXRF), focused ion beam scanning electron microscopy (FIB-SEM) combined with energy dispersive X-ray spectroscopy (EDS), and time-of-flight secondary ion mass spectrometry (ToF-SIMS) are promising techniques for the elemental and chemical identification of brominated fire retardant compounds (such as the deca-congener of polybrominated diphenyl ether, BDE-209) within polymeric materials (e.g. high-impact polystyrene or HIPS). Data from μXRF demonstrated that bromine (Br) inclusions were evenly distributed throughout the HIPS samples, whereas FIB SEM-EDS analysis revealed that small antimony (Sb) and Br inclusions are present, and regionally higher concentrations of Br surround the Sb inclusions (compared to the bulk material). Four prominent mass-to-charge ratio peaks (m/z 485, 487, 489 and 491) that correspond to BDE-209 were identified by ToF-SIMS and can be used to chemically distinguish this molecule on the surface of polymeric materials with respect to other brominated organic molecules. These techniques can be important in any study that investigates the route of entry to the environmental surroundings of BDE-containing materials.

  1. Detection of organophosphate flame retardants in furniture foam and U.S. house dust.

    PubMed

    Stapleton, Heather M; Klosterhaus, Susan; Eagle, Sarah; Fuh, Jennifer; Meeker, John D; Blum, Arlene; Webster, Thomas F

    2009-10-01

    Restrictions on the use of polybrominated diphenyl ethers (PBDEs) have resulted in the increased use of alternate flame retardant chemicals to meet flammability standards. However, it has been difficult to determine which chemical formulations are currently being used in high volumes to meet flammability standards since the use of flame retardant formulations in consumer products is not transparent (i.e., not provided to customers). To investigate chemicals being used as replacements for PentaBDE in polyurethane foam, we analyzed foam samples from 26 different pieces of furniture purchased in the United States primarily between 2003 and 2009. Samples included foam from couches, chairs, mattress pads, pillows, and, in one case, foam from a sound-proofing system of a laboratory-grade dust sieve, and were analyzed using gas chromatography mass spectrometry. Fifteen of the foam samples contained the flame retardanttris(1,3-dichloro-2-propyl) phosphate (TDCPP; 1-5% by weight), four samples contained tris(1-chloro-2-propyl) phosphate (TCPP; 0.5 -22% by weight), one sample contained brominated chemicals found in a new flame retardant mixture called Firemaster 550 (4.2% by weight), and one foam sample collected from a futon likely purchased prior to 2004 contained PentaBDE (0.5% by weight). Due to the high frequency of detection of the chlorinated phosphate compounds in furniture foam,we analyzed extracts from 50 house dust samples collected between 2002 and 2007 in the Boston, MA area for TDCPP, TCPP, and another high volume use organophosphate-based flame retardant used in foam, triphenylphosphate (TPP). Detection frequencies for TDCPP and TPP in the dust samples were > 96% and were log normally distributed, similar to observations for PBDEs. TCPP was positively detected in dust in only 24% of the samples, but detection was significantly limited by a coelution problem. The geometric mean concentrations for TCPP, TDCPP, and TPP in house dust were 570, 1890, and 7360 ng

  2. Brominated flame retardant: environmental and exposed individuals' health impact.

    PubMed

    Dufour, Patrice; Charlier, Corinne

    2017-04-01

    Since Antiquity, men have used chemicals to protect their goods against fire. Effective and easy to use, brominated flame retardants are used since decades massively in plastic industry. Such like other organohalogenated compounds, brominated flame retardants are very persistent in the environment and able to accumulate along the food chain. Many authors highlight their presence in the environment, in many animal species and in the human serum. Worryingly, man is exposed as soon as the pregnancy and then by the breastfeeding. This exposition may have consequence on our health. Many studies (in vitro, in vivo or epidemiologic) highlight brominated flame retardant negative effects on the endocrine system, mainly on the thyroid function but also on the reproduction, the neurodevelopment in the children and on the metabolism with increasing diabetes risk. If authorities and some big enterprises are aware about the problematic, new studies are needed to confirm previous results, elucidate endocrine disrupting mechanisms and highlight hypothetical synergies with other pollutants such like PCBs.

  3. Environmental impact of flame retardants (persistence and biodegradability).

    PubMed

    Segev, Osnat; Kushmaro, Ariel; Brenner, Asher

    2009-02-01

    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.

  4. Polysiloxane-Based Organoclay Nanocomposites as Flame Retardants

    DTIC Science & Technology

    2013-01-01

    2. Kumar, R.; Tyagi, R.; Parmar, V.S.; Samuelson , L.A.; Kumar, J.; Schoemann, A.; Westmoreland, P.R.; Watterson, A.C. Biocatalytic synthesis of...highly flame retardant inorganic-organic hybrid polymers. Adv. Mater. 2004, 16 (17), 1515–1520. 3. Mosurkal, R.; Samuelson , L.A.; Parmar, V.S.; Kumar, J... Samuelson , L.A.; Smith, K.D.; Westmoreland, P.R.; Parmar, V.S.; Kumar, J.; Watterson, A.C. Novel organo-siloxane copolymers for flame retardant applications

  5. Brominated flame retardants in the Australian population: 1993-2009.

    PubMed

    Toms, Leisa-Maree L; Guerra, Paula; Eljarrat, Ethel; Barceló, Damià; Harden, Fiona A; Hobson, Peter; Sjodin, Andreas; Ryan, Elizabeth; Mueller, Jochen F

    2012-10-01

    Brominated flame retardants, including hexabromocyclododecane (HBCD) and polybrominated diphenyl ethers (PBDEs) are used to reduce the flammability of a multitude of electrical and electronic products, textiles and foams. The use of selected PBDEs has ceased, however, use of decaBDE and HBCD continues. While elevated concentrations of PBDEs in humans have been observed in Australia, no data is available on other BFRs such as HBCD. This study aimed to provide background HBCD concentrations from a representative sample of the Australian population and to assess temporal trends of HBCD and compare with PBDE concentrations over a 16 year period. Samples of human milk collected in Australia from 1993 to 2009, primarily from primiparae mothers were combined into 12 pools from 1993 (2 pools); 2001; 2002/2003 (4 pools); 2003/2004; 2006; 2007/2008 (2 pools); and 2009. Concentrations of ∑HBCD ranged from not quantified (nq) to 19 ng g(-1)lipid while α-HBCD and γ-HBCD ranged from nq to 10 ng g(-1)lipid and nq to 9.2 ng g(-1)lipid. β-HBCD was detected in only one sample at 3.6 ng g(-1)lipid while ∑(4)PBDE ranged from 2.5 to 15.8 ng g(-1)lipid. No temporal trend was apparent in HBCD concentrations in human milk collected in Australia from 1993 to 2009. In comparison, PBDE concentrations in human milk show a peak around 2002/03 (mean ∑(4)PBDEs=9.6 ng g(-1)lipid) and 2003/04 (12.4 ng g(-1)lipid) followed by a decrease in 2007/08 (2.7 ng g(-1)lipid) and 2009 (2.6 ng g(-1)lipid). In human blood serum samples collected from the Australian population, PBDE concentrations did not vary greatly (p=0.441) from 2002/03 to 2008/09. Continued monitoring including both human milk and serum for HBCD and PBDEs is required to observe trends in human body burden of HBCD and PBDEs body burden following changes to usage. Copyright © 2012 Elsevier Ltd. All rights reserved.

  6. Flame retardant associations between children's handwipes and house dust.

    PubMed

    Stapleton, Heather M; Misenheimer, John; Hoffman, Kate; Webster, Thomas F

    2014-12-01

    Polybrominated diphenyl ether (PBDE), flame retardants (FRs) have been ubiquitously detected at high concentrations in indoor environments; however, with their recent phase-out, more attention is being focused on measurements of exposure to alternative FRs such as organophosphate FRs (OPFRs). In our previous research, we found that PBDE residues measured on children's handwipes were a strong predictor of serum PBDE levels. Here we build upon this research to examine longitudinal changes in PBDEs in indoor dust and children's handwipes, and explore the associations between handwipes and dust for alternative FRs. Children from our previous study were re-contacted after approximately two years and new samples of indoor dust and handwipes were collected. PBDE dust-levels were significantly correlated between two different sampling rounds separated by two years; however, PBDE levels in handwipes were not correlated, perhaps suggesting that the sources of PBDEs remained relatively constant in the home, but that behavioral differences in children are changing with age and influencing handwipe levels. OPFRs [i.e. tris(1,3-dichloroisopropyl) phosphate (TDCPP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP)], 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB, also known as TBB), di(2-ethylhexyl) tetrabromophthalate (BEH-TEBP, also known as TBPH), and 1,2,5,6,9,10-hexabromocyclododecane (HBCD) were also ubiquitously detected in house dust samples and geometric mean levels were similar to PBDE levels, or higher in the case of the OPFRs. Significant associations between handwipes and house dust were observed for these alternative FRs, particularly for EH-TBB (rs=0.54; p<0.001). Increasing house dust levels and age were associated with higher levels of FRs in handwipes, and high hand washing frequency (>5 times d(-1)) was associated with lower FR levels in handwipes. Overall these data suggest that exposure to these alternative FRs will be similar

  7. Impairment in the mesohippocampal dopamine circuit following exposure to the brominated flame retardant, HBCDD.

    PubMed

    Pham-Lake, Camille; Aronoff, Elizabeth B; Camp, Chad R; Vester, Aimee; Peters, Sam J; Caudle, W Michael

    2017-03-01

    Many chemicals have been used to increase the safety of consumer products by reducing their flammability and risk for ignition. Recent focus on brominated flame retardants, such as polybrominated diphenyl ethers (PBDEs) has shown them to contribute to neurobehavioral deficits in children, including learning and memory. As the manufacture and use of PBDEs have been reduced, replacement chemicals, such as hexabromocyclododecane (HBCDD) have been substituted. Our current study evaluated the neurotoxicity of HBCDD, concentrating on dopaminergic innervation to the hippocampus. Using an in vivo model, we exposed male mice to HBCDD and then assessed alterations to the dopamine synapse 6 weeks later. These exposures elicited significant reductions in presynaptic dopaminergic proteins, including TH, COMT, MAO-B, DAT, VMAT2, and alpha-synuclein. In contrast, postsynaptic dopamine receptors were not impaired. These findings suggest that the mesohippocampal dopamine circuit is vulnerable to HBCDD and the dopamine terminal may be a selective target for alteration.

  8. Brominated flame retardants (BFRs) in eggs from birds of prey from Southern Germany, 2014.

    PubMed

    Vetter, Walter; Gallistl, Christoph; Schlienz, Annika; Preston, Theresa; Müller, Jens; von der Trenck, K Theo

    2017-08-24

    In Southern Germany, peregrine falcons (Falco peregrinus), which almost exclusively prey on other birds, are top predators of the terrestrial food chain. These animals accumulate persistent organic pollutants (POPs) and halogenated flame retardants (HFRs) with mothers transferring these lipophilic contaminants to their eggs. Here we analyzed unhatched eggs of eleven peregrine falcons and six of other species, and report concentrations of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), hexabromobenzene (HBB), 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) and its metabolites, pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), and tribromophenol (TBP). The extract of one purified peregrine falcon egg sample was comprehensively analyzed in a non-target (NT) approach by gas chromatography with mass spectrometry in the electron capture negative ion mode. A total of ∼400 polyhalogenated compounds were detected, among them dechloranes and possibly transformation products, two tetrabrominated metabolites of PBT and several compounds unknown to us which could not be identified. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Reproductive Outcomes Among Women Exposed to a Brominated Flame Retardant In Utero

    PubMed Central

    Small, Chanley M.; Murray, Deanna; Terrell, Metrecia L.; Marcus, Michele

    2014-01-01

    The authors studied 194 women exposed to polybrominated biphenyls (PBB) in utero when their mothers consumed products accidentally contaminated in Michigan in 1973. Generalized estimating equations were used to examine the effect of in utero PBB exposure on adult pregnancy-related outcomes. Compared to those with the lowest exposure (≤1 ppb), those with mid-range (>1–3.16 ppb) and high (≥3.17 ppb) PBB exposure had increased odds of spontaneous abortion with wide confidence intervals (odds ratio [OR] = 2.75, 95% confidence interval [CI] = 0.64–11.79, OR = 4.08, 95% CI = 0.94–17.70; respectively; p for trend = .05). Exposure during infancy to PBB-contaminated breast milk further increased this risk. Time to pregnancy and infertility were not associated with in utero exposure to PBB. Future studies should examine the suggested relationship between spontaneous abortion and other brominated flame retardants. PMID:22014192

  10. 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.

  11. Flame retardants (PBDEs) in marine turtles, dugongs and seafood from Queensland, Australia.

    PubMed

    Hermanussen, S; Matthews, V; Päpke, O; Limpus, C J; Gaus, C

    2008-01-01

    Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in numerous products. These compounds have been found to enter the marine environment where they have the potential to bioaccumulate in biota. Limited information is currently available concerning the levels of PBDEs in Australian marine wildlife. This study presents baseline information on PBDE levels in a variety of marine species from Queensland, Australia and considers the influence of species-specific factors on contaminant levels and tissue distribution in marine turtles. Overall, the PBDE levels measured in this study are relatively low compared to marine biota from the northern hemisphere, indicating low level input into the marine system of Queensland. This is in general agreement with global estimates which suggest low PBDE usage in Australia. Previous studies, however, have found relatively high PBDE levels in Australian human milk and sera. This discrepancy in contamination trends between terrestrial and marine biota suggests that future transport of PBDEs may occur to the marine system in Australia.

  12. 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.

  13. 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

    2016-09-06

    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.

  14. 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

  15. Novel brominated flame retardants and dechloranes in three fish species from the St. Lawrence River, Canada.

    PubMed

    Houde, Magali; Berryman, David; de Lafontaine, Yves; Verreault, Jonathan

    2014-05-01

    Restrictions in the utilization of polybrominated diphenyl ether (PBDE) mixtures have led to the increased usage of alternative flame retardant additives in a wide range of commercial applications. The present study examined the occurrence of established and emerging flame retardants (FRs) in fish from a densely-populated urbanized sector of the St. Lawrence River (Montreal, Quebec, Canada). Thirty-eight PBDE congeners and sixteen emerging FRs were determined in fish belonging to three predatory species (yellow perch, northern pike, and muskellunge). The ∑PBDE in fish were up to 24,115 ng/g lipid weight (l.w.) in the apex predator muskellunge. Twelve emerging FRs including bis(2-ethylhexyl)-tetrabromophthalate (BEHTBP), pentabromoethylbenzene (PBEB), Dechlorane Plus (anti and syn), dechloranes (Dec) 602, Dec 604, Dec 604 Compound B (Dec 604 CB), and Chlordene Plus (CP) were detected (>0.01 ng/gl.w.) in the liver of muskellunge and northern pike but not in yellow perch homogenates. This is the first report of Dec 604 CB in any fish species. The bioavailability of these FRs in human-impacted aquatic ecosystems warrants further environmental assessment and toxicity testing.

  16. 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. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

  17. 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.

  18. Hair and Nails as Noninvasive Biomarkers of Human Exposure to Brominated and Organophosphate Flame Retardants.

    PubMed

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

    2016-03-15

    After the phase-out of polybrominated diphenyl ethers (PBDEs), the use of alternative flame retardants (AFRs), such as FireMaster 550, and of organophosphate esters (OPEs) has increased. However, little is known about human exposure to these chemicals. This lack of biomonitoring studies is partially due to the absence of reliable noninvasive biomarkers of exposure. Human hair and nails can provide integrated exposure measurements, and as such, these matrices can potentially be used as noninvasive biomarkers of exposure to these flame retardants. Paired human hair, fingernail, toenail, and serum samples obtained from 50 adult participants recruited at Indiana University Bloomington campus were analyzed by gas chromatographic mass spectrometry for 36 PBDEs, 9 AFRs, and 12 OPEs. BDE-47, BDE-99, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), di(2-ethylhexyl) tetrabromophthalate (TBPH), tris(1,3-dichloro-2-propyl)phosphate (TDCIPP), and triphenyl phosphate (TPHP) were the most abundant compounds detected in almost all hair, fingernail, and toenail samples. The concentrations followed the order OPEs > TBB+TBPH > Σpenta-BDE. PBDE levels in the hair and nail samples were significantly correlated with their levels in serum (P < 0.05), suggesting that human hair and nails can be used as biomarkers to assess human exposure to PBDEs.

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

    PubMed

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

    2015-01-01

    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. Published by Elsevier Inc.

  20. Organophosphorus flame retardants in house dust from the Philippines: occurrence and assessment of human exposure.

    PubMed

    Kim, Joon-Woo; Isobe, Tomohiko; Sudaryanto, Agus; Malarvannan, Govindan; Chang, Kwang-Hyeon; Muto, Mamoru; Prudente, Maricar; Tanabe, Shinsuke

    2013-02-01

    The use of organophosphorus flame retardants (PFRs) as flame retardants and plasticizers has increased due to the ban on common polybrominated diphenyl ether mixtures. However, only limited information on PFR contamination is available so far from Southeast Asia. In the present study, residual levels of PFRs in house dust and exposure through dust ingestion were investigated in the Philippines. House dust samples (n = 37) were collected from Malate (residential area) and Payatas (municipal dumping area) in the Philippines and analyzed using ultra-high-performance liquid chromatography coupled with tandem mass spectrometry. Among the targeted seven PFRs, triphenyl phosphate (TPP) was the predominant compound. Median levels of ΣPFRs in Malate (530 ng/g) were two times higher (p < 0.05) than in Payatas (240 ng/g). The estimated daily intake of PFRs in the Philippines (of areas studied) via house dust ingestion was below the guideline values. House dust may be an important contributor in the overall exposure of humans to TPP even when considering dietary sources. To our knowledge, this is a first report on PFR contamination in house dust from developing country. PFRs were ubiquitously detected in the home environments in the Philippines. Although estimated exposure levels through dust ingestion were below the guideline, it was suggested that toddlers are at higher risk. Therefore, further investigations to understand the behavior of PFRs in house and other microenvironments and overall exposure pathways for the country's populace to PFRs are necessary.

  1. Innovative green technique for preparing of flame retardant cotton

    USDA-ARS?s Scientific Manuscript database

    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 ...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  3. Phosphorus Containing Flame Retardants and Their Textile Applications

    USDA-ARS?s Scientific Manuscript database

    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)...

  4. Cone calorimeter evaluation of two flame retardant cotton fabrics

    Treesearch

    Robert H. White; Sunghyun Nam; Dharnidhar V. Parikh

    2012-01-01

    Unbleached (gray) cotton needle-punched nonwoven (NW) fabrics with 12.5% polypropylene scrim were treated with two phosphate–nitrogen-based flame retardant (FR) formulations, Southern Regional Research Center (SRRC)-1 and SRRC-2. The SRRC-1 formulation contains diammonium phosphate as the FR chemical along with urea and dimethyloldihydroxyethyleneurea. Because a trace...

  5. 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

  6. Differences in the seasonal variation of brominated and phosphorus flame retardants in office dust.

    PubMed

    Cao, Zhiguo; Xu, Fuchao; Covaci, Adrian; Wu, Min; Yu, Gang; Wang, Bin; Deng, Shubo; Huang, Jun

    2014-04-01

    This study documents the temporal variability in concentrations of flame retardants (FRs) in floor dust from three offices in Beijing, China. Dust from Office A (OAD) was collected weekly from March to August, 2012, and sampling of dust from Office B and C (OBD and OCD) was conducted fortnightly (each two weeks) from March to December 2012. With intensive and continuous sampling, we report for the first time on clear and coherent temporal trends of polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs) and phosphorus flame retardants (PFRs) in indoor dust. The observed mean concentrations of ∑9PBDEs, ∑4NBFRs and ∑9PFRs, were 554, 11,100 and 128,000ngg(-1) in OAD; 7560, 5000 and 17,300ngg(-1) in OBD; and 4750, 3550 and 17,200ngg(-1) in OCD, respectively. With exception of PBDEs, concentrations of FRs were elevated in OAD than in OBD and OCD. Two to ten-fold variations were observed between the minimum and maximum concentrations of FRs in the same office, indicating that the sampling moment exerts a substantial influence on the level of FR contamination. Different seasonality was distinctively found between BFRs and PFRs. Except for a few occasional abnormal values, BFR levels in office dust were generally constant among different seasons. The abundance rank order for PFRs was: winter>autumn>summer, with peak values occurring in late winter and early spring. This pattern may be attributable to the fact that PFRs are more sensitive to temperature changes compared to PBDEs and NBFRs owning to their higher volatilities. The absence of significant seasonal variation for BFR concentrations in indoor dust compared to outdoor air and dust concentrations is also discussed.

  7. Screening for halogenated flame retardants in European consumer products, building materials and wastes.

    PubMed

    Vojta, Šimon; Bečanová, Jitka; Melymuk, Lisa; Komprdová, Klára; Kohoutek, Jiří; Kukučka, Petr; Klánová, Jana

    2017-02-01

    To fulfill national and international fire safety standards, flame retardants (FRs) are being added to a wide range of consumer products and building materials consisting of flammable materials like plastic, wood and textiles. While the FR composition of some products and materials has been identified in recent years, the limited global coverage of the data and the large diversity in consumer products necessitates more information for an overall picture of the FR composition in common products/materials. To address this issue, 137 individual samples of various consumer products, building materials and wastes were collected. To identify and characterize potential sources of FRs in indoor environment, all samples were analyzed for content of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and novel flame retardants (NFRs). The most frequently detected were HBCDDs (85%), with the highest median concentration of Σ4HBCDDs of 300 mg kg(-1) in polystyrenes. The highest median concentration of Σ10PBDEs was found in recycled plastic materials, reaching 4 mg kg(-1). The lowest concentrations were observed for NFRs, where the median of Σ12NFRs reached 0.4 mg kg(-1) in the group of electrical & electronic equipment wastes. This suggests that for consumer products and building materials that are currently in-use, legacy compounds still contribute to the overall burden of FRs. Additionally, contrasting patterns of FR composition in recycled and virgin plastics, revealed using principle component analysis (PCA), suggest that legacy flame retardants are reentering the market through recycled products, perpetuating the potential for emissions to indoor environments and thus for human exposure.

  8. 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...

  9. 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...

  10. 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...

  11. 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...

  12. 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...

  13. 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...

  14. 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...

  15. 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...

  16. Organophosphate flame retardants and plasticisers in wastewater treatment plants.

    PubMed

    Meyer, J; Bester, K

    2004-07-01

    Previous studies have revealed that chlorinated and non-chlorinated organophosphorous flame retardants and plasticisers are important contaminants in German surface waters and it has been demonstrated that wastewater treatment plants contribute to the emission of these substances. In this study temporal development as well as elimination efficiency were determined in two wastewater treatment plants (STP) in the Ruhr/Rhine area at different stages of the wastewater treatment process. The samples were analysed for the non-chlorinated organophosphate esters tri-n-butylphosphate (TnBP), tri-iso-butylphosphate (TiBP), tris-(butoxyethyl)-phosphate (TBEP) and triphenylphosphate (TPP) and the chlorinated organophosphate esters tris-(2-chloro, 1-methylethyl)-phosphate (TCPP), tris-(2-chloro-, 1-chloromethylethyl)-phosphate (TDCP) and tris-(2-chloroethyl)-phosphate (TCEP). The study showed that there were significant differences in the elimination of chlorinated and non-chlorinated organophosphorous flame retardants. The elimination rates ranged from 57-86% for TiBP, TnBP and TBEP at both STP's. No elimination of the chlorinated flame retardants TCPP, TDCP and TCEP was observed in any of the sampled STPs. At both STPs the first treatment steps and the final filtration did not contribute to the elimination of the non-chlorinated organophosphorous flame retardants while the aeration step did. At both STPs the efficiency of the cleaning process concerning the flame retardants was comparable. Thus the type of construction of the STP was not relevant for the elimination of these substances. Additionally a strong day-to-day variation was observed, while in one STP a temporal trend for TCPP during the week was found.

  17. 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

  18. Flame retardants and their metabolites in the homes and urine of pregnant women residing in California (the CHAMACOS cohort).

    PubMed

    Castorina, Rosemary; Butt, Craig; Stapleton, Heather M; Avery, Dylan; Harley, Kim G; Holland, Nina; Eskenazi, Brenda; Bradman, Asa

    2017-03-22

    Organophosphate flame retardants (PFRs), used in consumer products since the 1970s, persist in the environment. Restrictions on penta-polybrominated diphenyl ether (PBDE) flame retardants resulted in increased use of Firemaster(®) 550 (FM(®) 550), and the organophosphate triesters: tris(1,3- dichloro-2-propyl) phosphate (TDCIPP); tris(chloropropyl) phosphate (TCIPP); tris(2-chloroethyl) phosphate (TCEP); and triphenyl phosphate (TPHP). The objectives of this study were to (1) identify determinants of flame retardants (4 PFRs, PentaBDEs and FM(®) 550) in house dust, (2) measure urinary PFR metabolites in pregnant women, and (3) estimate health risks from PFR exposure. We measured flame retardants in house dust (n = 125) and metabolites in urine (n = 310) collected in 2000-2001 from Mexican American women participating in the CHAMACOS birth cohort study in California. We detected FM(®) 550 and PFRs, including two (TCEP and TDCIPP) known to the state of California to cause cancer, in most dust samples. The maximum TCEP and TDCIPP dust levels were among the highest ever reported although the median levels were generally lower compared to other U.S. cohorts. Metabolites of TDCIPP (BDCIPP: bis(1,3-dichloro-2-propyl) phosphate) and TPHP (DPHP: diphenyl phosphate) were detected in 78% and 79% of prenatal urine samples, respectively. We found a weak but positive correlation between TPHP in dust and DPHP in 124 paired prenatal urine samples (Spearman rho = 0.17; p = 0.06). These results provide information on PFR exposure and risk in pregnant women from the early 2000's and are also valuable to assess trends in exposure and risk given changing fire safety regulations and concomitant changes in chemical flame retardant use.

  19. Flame-retardant carbon nanotube films

    NASA Astrophysics Data System (ADS)

    Janas, Dawid; Rdest, Monika; Koziol, Krzysztof K. K.

    2017-07-01

    We have demonstrated fire-retardancy properties of a polymer matrix-free CNT film for the first time. As compared with classical fire-retardant materials such as Kevlar, Twaron or Nomex, the CNT film showed a spectrum of advantages. The material is lightweight, flexible and well-adherent to even the most complicated shapes. The results have showed that by using CNTs for fire-retardancy we can extend the operational time almost two-fold, what makes CNTs a much better protection than the solutions employed nowadays. We believe that among other great properties of CNT, their macroscopic assemblies such as CNT films show significant potential for becoming a fire protective coating, which exhibits high performance in not sustaining fire.

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  2. 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. Copyright © 2014 Elsevier Ltd. All rights reserved.

  3. Report: recycling of flame-retarded plastics from waste electric and electronic equipment (WEEE).

    PubMed

    Schlummer, Martin; Mäurer, Andreas; Leitner, Thomas; Spruzina, Walter

    2006-12-01

    Shredder residues produced in plants processing waste electric and electronic equipment are excluded from material recycling due to a variety of polymeric materials and the presence of brominated flame retardants (BFR), which might contain banned polybrominated diphenyl ethers or toxic polybrominated dioxins and furans (PBDD/F). Herein we present a technological approach to transfer a significant portion of the shredder residue into recycled polymers. The technological approach consists of a density-based enrichment of styrenics, which are subjected to a solvolysis process (CreaSolv process) in a second stage. This stage allows the elimination of non-target polymers and extraction of BFR and PBDD/F. Pilot processing of 11.5 and 50 kg shredder residues indicated a material yield of about 50% in the density stage and 70-80% in the CreaSolv process, and an effective removal of BFR additives. The recycled products were proved to comply with threshold values defined by the European directive on the restriction of hazardous substances (RoHS) and the German Chemikalienverbotsverordnung. Mechanical material properties exhibited high tensile and flexural modules as well as slight impact strength, which qualify the products for applications in new electronic equipment.

  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.

  5. Conferring flame retardancy on cotton using novel halogen-free flame retardant bifunctional monomers: synthesis, characterizations and applications.

    PubMed

    Cheema, Hammad A; El-Shafei, Ahmed; Hauser, Peter J

    2013-01-30

    Two novel halogen-free phosphorous-nitrogen flame retardant bifunctional monomers were synthesized and characterized using attenuated total reflectance/Fourier transform-infrared (ATR/FT-IR) and electrospray ionization mass spectrometry ((+)ESI-MS). The monomers were applied separately and graft polymerized on cotton in the presence of the thermal initiator K(2)S(2)O(8). The performance of each monomer was evaluated using thermal gravimetric analysis (TGA), grafting efficiency, and vertical flame test. It was shown that the performance of N,N-dimethyl di(acryloyloxyethyl)phosphoramide (DMDAEP) (monomer 2) as flame retardant outperformed that of ethyl di(acryloyloxyethyl)phosphorodiamidate (EDAEP) (monomer 1). The superior performance of DMDAEP was attributed to the presence of more nitrogen atoms compared to EDAEP. The increased nitrogen content in DMDAEP increased the synergistic effect of the P-N system. Cotton treated using padding methods showed more promising results than cotton treated by exhaust methods. Published by Elsevier Ltd.

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

    PubMed

    Poon, Chin-Kuen; Kan, Chi-Wai

    2015-05-05

    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.

  7. 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

  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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. Phosphorus-based Flame Retardancy Mechanisms—Old Hat or a Starting Point for Future Development?

    PubMed Central

    Schartel, Bernhard

    2010-01-01

    Different kinds of additive and reactive flame retardants containing phosphorus are increasingly successful as halogen-free alternatives for various polymeric materials and applications. Phosphorus can act in the condensed phase by enhancing charring, yielding intumescence, or through inorganic glass formation; and in the gas phase through flame inhibition. Occurrence and efficiency depend, not only on the flame retardant itself, but also on its interaction with pyrolysing polymeric material and additives. Flame retardancy is sensitive to modification of the flame retardant, the use of synergists/adjuvants, and changes to the polymeric material. A detailed understanding facilitates the launch of tailored and targeted development. PMID:28883349

  16. Graphite oxide flame-retardant polymer nanocomposites.

    PubMed

    Higginbotham, Amanda L; Lomeda, Jay R; Morgan, Alexander B; Tour, James M

    2009-10-01

    Graphite oxide (GO) polymer nanocomposites were developed at 1, 5, and 10 wt % GO with polycarbonate (PC), acrylonitrile butadiene styrene, and high-impact polystyrene for the purpose of evaluating the flammability reduction and material properties of the resulting systems. The overall morphology and dispersion of GO within the polymer nanocomposites were studied by scanning electron microscopy and optical microscopy; GO was found to be well-dispersed throughout the matrix without the formation of large aggregates. Mechanical testing was performed using dynamic mechanical analysis to measure the storage modulus, which increased for all polymer systems with increased GO loading. Microscale oxygen consumption calorimetry revealed that the addition of GO reduced the total heat release and peak heat release rates in all systems, and GO-PC composites demonstrated very fast self-extinguishing times in vertical open flame tests, which are important to some regulatory fire safety applications.

  17. 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.

  18. Interlaboratory study of novel halogenated flame retardants: INTERFLAB.

    PubMed

    Melymuk, Lisa; Goosey, Emma; Riddell, Nicole; Diamond, Miriam L

    2015-09-01

    Flame retardants (FRs) have come under considerable scientific and public scrutiny over the past decade. A lack of reference materials and standardized analytical methods has resulted in questions regarding the variation of measurements from different studies. We evaluated this variation by performing an international interlaboratory study assessing analytical capabilities as well as the accuracy and precision of results for a range of flame retardants (International Flame Retardant Laboratory Study, INTERFLAB). Thirteen international research laboratories participated in a blind interlaboratory comparison of 24 FRs. Results demonstrate good precision within replicates of test mixtures from individual laboratories, but problematic accuracy for several FRs and laboratories. Large ranges in the values reported for decabromodiphenylethane (DBDPE), tris(1,3-dichloropropyl)phosphate (TDCIPP), tetrabromobisphenol-A (TBBPA), and hexabromocyclododecane (HBCD) (>50 % relative standard deviations among measured values) and large deviations from the reference values (>25 % bias in accuracy) suggest potential problems for comparability of results. DBDPE, HBCD, and TBBPA had significantly poorer accuracy and precision, suggesting that current analytical methods are not providing reliable results for these FRs.

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

    PubMed

    Cordner, Alissa; Mulcahy, Margaret; Brown, Phil

    2013-07-02

    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.

  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. 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...

  3. 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...

  4. 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...

  5. 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...

  6. 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.

  7. Priority and emerging flame retardants in rivers: occurrence in water and sediment, Daphnia magna toxicity and risk assessment.

    PubMed

    Cristale, Joyce; García Vázquez, Alejandro; Barata, Carlos; Lacorte, Silvia

    2013-09-01

    The occurrence, partitioning and risk of eight polybrominated diphenyl ethers (PBDEs), nine new brominated (NBFRs) and ten organophosphorus flame retardants (OPFRs) were evaluated in three Spanish rivers suffering different anthropogenic pressures (Nalón, Arga and Besòs). OPFRs were ubiquitous contaminants in water (ΣOPFRs ranging from 0.0076 to 7.2μgL(-1)) and sediments (ΣOPFRs ranging 3.8 to 824μgkg(-1)). Brominated flame retardants were not detected in waters, whereas ΣPBDEs ranged from 88 to 812μgkg(-1) and decabromodiphenyl ethane (DBDPE) reached 435μgkg(-1) in sediments from the River Besòs, the most impacted river. The occurrence of flame retardants in river water and sediment was clearly associated with human activities, since the highest levels occurred near urban and industrial zones and after wastewater treatment plants discharge. Daphnia magna toxicity was carried out for OPFRs, the most ubiquitous flame retardants, considering individual compounds and mixtures. Toxicity of nine tested OPFRs differed largely among compounds, with EC50 values ranging over three magnitude orders (0.31-381mgL(-1)). Results evidenced that these compounds act by non-polar narcosis, since their toxicity was proportional to their lipophilicity (Kow). Furthermore, their joint toxicity was additive, which means that single and joint toxicity can be predicted knowing their concentration levels in water using quantitative structure activity relationships (QSARs) and predictive mixture models. Based on these results, a risk assessment considering joint effect was performed calculating and summing risk quotients (RQs) for the water and sediment samples. No significant risk to D. magna (ΣRQs <1) was observed for any of the monitored rivers.

  8. Air sampling of flame retardants based on the use of mixed-bed sorption tubes--a validation study.

    PubMed

    Lazarov, Borislav; Swinnen, Rudi; Spruyt, Maarten; Maes, Frederick; Van Campenhout, Karen; Goelen, Eddy; Covaci, Adrian; Stranger, Marianne

    2015-11-01

    An analytical methodology using automatic thermal desorption and gas chromatography mass spectrometry analysis was optimized and validated for simultaneous determination of a set of components from three different flame retardant chemical classes: polybrominated diphenyl ethers (PBDEs) (PBDE-28, PBDE-47, PBDE-66, PBDE-85, PBDE-99, PBDE-100), organophosphate flame retardants (PFRs) (tributyl phosphate, tripropyl phosphate, tris(2-chloroethyl)phosphate-, tris(1,3-dichloro-2-propyl) phosphate, tris(2-ethylhexyl) phosphate, triphenyl phosphate, tris(2-chloro-1-methylethyl) phosphate and tricresylphosphate), and "novel" brominated flame retardants (NBFRs) (pentabromotoluene, 2,3,4,5,6-pentabromoethylbenzene, (2,3-dibromopropyl) (2,4,6-tribromophenyl) ether, hexabromobenzene, and 2-ethylhexyl 2,3,4,5-tetrabromobenzoate) in air. The methodology is based on low volume active air sampling of gaseous and particulate air fractions on mixed-bed (polydimethylsiloxane (PDMS)/Tenax TA) sorption tubes. The optimized method provides recoveries >88%; a limit of detection in the range of 6-25 pg m(-3) for PBDEs, 6-171 pg m(-3) for PFRs, and 7-41 pg m(-3) for NBFRs; a linearity greater than 0.996; and a repeatability of less than 10% for all studied compounds. The optimized method was compared with a standard method using active air sampling on XAD-2 sorbent material, followed by liquid extraction. On the one hand, the PDMS/Tenax TA method shows comparable results at longer sampling time conditions (e.g., indoor air sampling, personal air sampling). On the other hand, at shorter sampling time conditions (e.g., sampling from emission test chambers), the optimized method detects up to three times higher concentrations and identifies more flame retardant compounds compared to the standard method based on XAD-2 loading.

  9. Analysis of Ah receptor pathway activation by brominated flame retardants.

    PubMed

    Brown, David J; Van Overmeire, Ilse; Goeyens, Leo; Denison, Michael S; De Vito, Michael J; Clark, George C

    2004-06-01

    Brominated flame-retardants (BFRs) are used as additives in plastics to decrease the rate of combustion of these materials, leading to greater consumer safety. As the use of plastics has increased, the production and use of flame-retardants has also grown. Many BFRs are persistent and have been detected in environmental samples, raising concerns about the biological/toxicological risk associated with their use. Most BFRs appear to be non-toxic, however there is still some concern that these compounds, or possible contaminants in BFRs mixtures could interact with cellular receptors. In this study we have examined the interaction of decabromodiphenyl ether, Firemaster BP4A (tetrabromobisphenol A), Firemaster PHT4 (tetrabromophthalic anhydride), hexabromobenzene, pentabromotoluene, decabromobiphenyl, Firemaster BP-6 (2,2',4,4',5,5'-hexabromobiphenyl) and possible contaminants of BFR mixtures with the Ah receptor. Receptor binding and activation was examined using the Gel Retardation Assay and increased expression of dioxin responsive genes was detected using the reporter gene based CALUX assay. The results demonstrate the ability of BFRs to activate the AhR signal transduction pathway at moderate to high concentrations as assessed using both assays. AhR-dependent activation by BFRs may be due in part to contaminants present in commercial/technical mixtures. This was suggested by our comparative analysis of Firemaster BP-6 versus its primary component 2,2',4,4',5,5'-hexabromobiphenyl. Some technical mixtures of brominated flame-retardants contain brominated biphenyls, dioxins or dibenzofurans as contaminants. When tested in the CALUX assay these compounds were found to be equivalent to, or more active than their chlorinated analogues. Relative effective potency values were determined from dose response curves for these brominated HAHs.

  10. 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...

  11. 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...

  12. 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.

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

    PubMed

    Qiu, Xinghua; Marvin, Chris H; Hites, Ronald A

    2007-09-01

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

  14. Monitoring Indoor Exposure to Organophosphate Flame Retardants: Hand Wipes and House Dust

    PubMed Central

    Hoffman, Kate; Garantziotis, Stavros; Birnbaum, Linda S.

    2014-01-01

    Background: Organophosphate flame retardants (PFRs) are becoming popular replacements for the phased-out polybrominated diphenyl ether (PBDE) mixtures, and they are now commonly detected in indoor environments. However, little is known about human exposure to PFRs because they cannot be easily measured in blood or serum. Objectives: To investigate relationships between the home environment and internal exposure, we assessed associations between two PFRs, tris(1,3-dichloropropyl) phosphate (TDCIPP) and triphenyl phosphate (TPHP), in paired hand wipe and dust samples and concentrations of their metabolites in urine samples (n = 53). We also assessed short-term variation in urinary metabolite concentrations (n = 11 participants; n = 49 samples). Methods: Adult volunteers in North Carolina, USA, completed questionnaires and provided urine, hand wipe, and household dust samples. PFRs and PBDEs were measured in hand wipes and dust, and bis(1,3-dichloropropyl) phosphate (BDCIPP) and diphenyl phosphate (DPHP), metabolites of TDCIPP and TPHP, were measured in urine. Results: TDCIPP and TPHP were detected frequently in hand wipes and dust (> 86.8%), with geometric mean concentrations exceeding those of PBDEs. Unlike PBDEs, dust TDCIPP and TPHP levels were not associated with hand wipes. However, hand wipe levels were associated with urinary metabolites. Participants with the highest hand wipe TPHP mass, for instance, had DPHP levels 2.42 times those of participants with the lowest levels (95% CI: 1.23, 4.77). Women had higher levels of DPHP, but not BDCIPP. BDCIPP and DPHP concentrations were moderately to strongly reliable over 5 consecutive days (intraclass correlation coefficients of 0.81 and 0.51, respectively). Conclusions: PFR exposures are widespread, and hand-to-mouth contact or dermal absorption may be important pathways of exposure. Citation: Hoffman K, Garantziotis S, Birnbaum LS, Stapleton HM. 2015. Monitoring indoor exposure to organophosphate flame retardants

  15. Seasonality and indoor/outdoor relationships of flame retardants and PCBs in residential air.

    PubMed

    Melymuk, Lisa; Bohlin-Nizzetto, Pernilla; Kukučka, Petr; Vojta, Šimon; Kalina, Jiří; Čupr, Pavel; Klánová, Jana

    2016-11-01

    This study is a systematic assessment of different houses and apartments, their ages and renovation status, indoors and outdoors, and in summer vs. winter, with a goal of bringing some insight into the major sources of semivolatile organic compounds (SVOCs) and their variability. Indoor and outdoor air concentrations of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and novel flame retardants (NFRs) were determined at 17-20 homes in Czech Republic in winter and summer. Indoor concentrations were consistently higher than outdoor concentrations for all compounds; indoor/outdoor ratios ranged from 2-20, with larger differences for the current use NFRs than for legacy PCBs. Seasonal trends differed according to the use status of the compounds: the PCBs had higher summer concentrations both indoors and outdoors, suggesting volatilization as a source of PCBs to air. PBDEs had no seasonal trends indoors, but higher summer concentrations outdoors. Several NFRs (TBX, PBT, PBEB) had higher indoor concentrations in winter relative to summer. The seasonal trends in the flame retardants suggest differences in air exchange rates due to lower building ventilation in winter could be driving the concentration differences. Weak relationships were found with building age for PCBs, with higher concentrations indoors in buildings built before 1984, and with the number of electronics for PBDEs, with higher concentrations in rooms with three or more electronic items. Indoor environments are the primary contributor to human inhalation exposure to these SVOCs, due to the high percentage of time spent indoors (>90%) combined with the higher indoors levels for all the studied compounds. Exposure via the indoor environment contributed ∼96% of the total chronic daily intake via inhalation in summer and ∼98% in winter.

  16. Environmental occurrence of emerging and legacy brominated flame retardants near suspected sources in Norway.

    PubMed

    Nyholm, Jenny Rattfelt; Grabic, Roman; Arp, Hans Peter H; Moskeland, Thomas; Andersson, Patrik L

    2013-01-15

    The environmental occurrence of potentially emerging brominated flame retardants (BFRs) was investigated near suspected source zones in Norway, within seepage water, sewage waste water, sewage sludges, and sediments. Analyzed emerging BFRs included 1,2-dibromo-4-(1,2-dibromoethyl) cyclohexane (TBECH), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenylethane (DBDPE), ethylene bis(tetrabromophthalimide) (EBTPI), tetrabromobisphenol A diallyl ether (TBBPA AE), and tetrabromobisphenol A bis(2,3-dipropyl ether) (TBBPA DBPE). In addition selected polybrominated diphenylethers (PBDEs) were analyzed, so that findings could be compared to legacy BFRs. An analytical method based on liquid chromatography atmospheric pressure photoionization tandem mass spectrometry was developed for analysis of EBTPI, TBBPA AE, and TBBPA DBPE. The legacy BFRs were in general found in higher levels and abundances than the studied emerging BFRs. However, BTBPE was detected in most of the studied matrices (sewage sludge, seepage water and sediment). DBDPE was detected in sewage sludge, waste water, seepage water and in sediment taken close to a combined metal recycling and car dismantling site. TBECH was found in seepage water, waste water and sewage sludge. EBTPI was identified in one seepage water sample; TBBPA AE was detected both in seepage water and sediment, and TBPPA DBPE in waste water and seepage water. Of the emerging BFRs, the highest levels in water samples were quantified for TBBPA DBPE (81 ng/L, seepage water from a combined metal recycling and car dismantling site) and in sediment for BTBPE (6.5 ng/g, taken close to landfill). The findings of current-use BFRs in seepage water, sediment and in sewage suggest that further investigations are needed of the environmental fate and effects of these flame retardants. Copyright © 2012 Elsevier B.V. All rights reserved.

  17. Legacy and emerging halogenated flame retardants in the middle and lower stream of the Yellow River.

    PubMed

    Su, Xianfa; Li, Qilu; Feng, Jinglan; Guo, Liya; Sun, Jianhui

    2017-12-01

    Halogenated flame retardants (HFRs), mainly encompassing polybrominated diphenylethers (PBDEs), dechlorane plus (DP) and emerging bromine flame retardants (EBFRs), are widely employed nowadays in daily lives. However, limited knowledge has been gained to date on the concentrations and distributions of HFRs in particular within certain regions. In the present study, legacy and emerging HFRs were systematically measured in suspended particle matter (SPM) and sediments collected in 2014 from the middle and lower reach of the Yellow River in Henan province. The total concentrations of HFRs in SPM among the three seasons were 42.2±91.2ngg(-1), which was far higher than the corresponding values of HFRs in sediments (1.82±2.94ngg(-1)). In this study, PBDEs, DP and EBFRs in sediment almost exhibited relatively lower levels as compared to those found in other studies, where the limited usage of HFRs in the middle and lower stream of the Yellow River was probably the major impact factor. EBFR was the predominate pollutant from SPM and sediments in most of the sampling sites, suggesting that EBFRs were widely used nowadays as substitute materials of 'old' FRs. The mean concentration values of DBDPE/BDE-209 in SPM and sediments were apparently higher than those of previous studies. Furthermore, it is interesting to reveal that herein almost all of the HFR concentrations were unrelated to the population and GDP, which might be attributed to the characteristics of 'elevated stream' of the Yellow River as well as the complex river systems in Henan province. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. 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.

  19. Characterization of brominated flame retardants from e-waste components in China.

    PubMed

    Yu, Danfeng; Duan, Huabo; Song, Qingbin; Liu, Yicheng; Li, Ying; Li, Jinhui; Shen, Weijun; Luo, Jiahui; Wang, Jinben

    2017-10-01

    Many studies show that high levels of many toxic metals and persistent and bio-accumulative chemicals have been found in electronic waste (e-waste) dismantling sites and their surrounding environmental media. Both flame-retardant plastic housing materials and printed circuit boards (PCBs) could be the major contributors. However, relatively little work has focused on the use or content of toxic substances and their changing in scrap housing materials and PCBs from home appliances. This study evaluated the existence of brominated flame retardants (BFRs, including polybrominated diphenyl ethers (PBDEs) and Tetrabromobisphenol-A (TBBPA)) in housing plastics and PCBs from home appliances collected from various e-waste recyclers in China. These were then analyzed for the potential migration of BFRs from the e-waste components into their recycled products. The results show that both PBDEs and TBBPA were found with high level in most of e-waste samples, indicating that the widespread use of BFRs in home appliances are entering into the end-of-life stage. For the plastics samples, CRT TVs and LCD monitors should be given priority for the control of BFRs. Regarding PBDEs, the dominant congeners of BDE-209 in the plastics samples contributed 90.72-93.54% to the total concentrations of PBDEs, yet there are large variations for PCBs samples: BDE-28, -47, -99, and -153 were also important congeners compositions, except for BDE-209. Compared with previous studies, the BFRs concentrations in current Chinese e-waste are trending to decline. This study also found that BFRs in housing plastics and PCBs will be transferred into the recycled products with other purpose use, and the new products could have highly enriched capacities for BFRs. The obtained results could be helpful to manage e-waste and their components properly in order to minimize associated environmental and health risks of BFRs, particularly for their further reuse. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Recent Developments in Halogen Free Flame Retardants for Epoxy Resins for Electrical and Electronic Applications

    PubMed Central

    Rakotomalala, Muriel; Wagner, Sebastian; Döring, Manfred

    2010-01-01

    The recent implementation of new environmental legislations led to a change in the manufacturing of composites that has repercussions on printed wiring boards (PWB). This in turn led to alternate processing methods (e.g., lead-free soldering), which affected the required physical and chemical properties of the additives used to impart flame retardancy. This review will discuss the latest advancements in phosphorus containing flame retardants for electrical and electronic (EE) applications and compare them with commercially available ones. The mechanism of degradation and flame retardancy of phosphorus flame retardants in epoxy resins will also be discussed. PMID:28883331

  1. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. 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. © 2013 Elsevier B.V. All rights reserved.

  3. Critical review of the analysis of brominated flame retardants and their environmental levels in Africa.

    PubMed

    Brits, Martin; de Vos, Jayne; Weiss, Jana M; Rohwer, Egmont R; de Boer, Jacob

    2016-12-01

    World-wide, the prevalence of brominated flame retardants (BFRs) is well documented for routine analysis of environmental and biological matrices. There is, however, limited information on these compounds in the African environment and insufficient information on the analytical approaches used to obtain data. This paper presents a review on BFR levels in the African environment and the various analytical methodologies specifically applied in Africa for polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls and alternative-BFRs. The analyses include liquid sample preparation using liquid-liquid and solid phase extraction and solid sample preparation involving Soxhlet extraction, with ultrasound-assisted extraction increasingly being applied. Instrumental detection techniques were limited to gas chromatography coupled with electron capture detector and electron impact ionisation with single quadrupole mass spectrometers. Information on congener profile prevalence in indoor dust, soil, aquatic environment (water, sediment, and aquatic organisms), eggs, wastewater treatment plant compartments, landfills (leachate and sediment) and breast milk are presented. Although PBDEs were inconsistently detected, contamination was reported for all investigated matrices in the African environment. The manifestation in remote regions indicates the ubiquitous prevalence and long-range transport of these compounds. Levels in sediment, and breast milk from some African countries were higher than reported for Asia and Europe. Due to limited data or non-detection of alternative-BFRs, it is unclear whether banned formulations were replaced in Africa. Most of the data reported for BFR levels in Africa were obtained in non-African laboratories or in South Africa and formed the basis for our discussion of reported contamination levels and related methodologies.

  4. Recent developments in the analysis of brominated flame retardants and brominated natural compounds.

    PubMed

    Covaci, Adrian; Voorspoels, Stefan; Ramos, Lourdes; Neels, Hugo; Blust, Ronny

    2007-06-15

    This article reviews recent literature on the analysis of brominated flame retardants (BFRs) and brominated natural compounds (BNCs). The main literature sources are reviews from the last five years and research articles reporting new analytical developments published between 2003 and 2006. Sample pretreatment, extraction, clean-up and fractionation, injection techniques, chromatographic separation, detection methods, quality control and method validation are discussed. Only few new techniques, such as solid-phase microextraction (SPME) or pressurized liquid extraction (PLE), have been investigated for their ability of combining the extraction and clean-up steps. With respect to the separation of BFRs, the most important developments were the use of comprehensive two-dimensional gas chromatography for polybrominated diphenyl ethers (PBDEs) and the growing tendency for liquid-chromatographic techniques for hexabromocyclododecane (HBCD) stereoisomers and of tetrabromobisphenol-A (TBBP-A). At the detection stage, mass spectrometry (MS) has been developed as well-established and reliable technology in the identification and quantification of BFRs. A growing attention has been paid to quality assurance. Interlaboratory exercises directed towards BFRs have grown in popularity and have enabled laboratories to validate analytical methods and to guarantee the quality of their results. The analytical procedures used for the identification and characterization of several classes of BNCs, such as methoxylated polybrominated diphenyl ethers (MeO-PBDEs) (also metabolites of PBDEs), halogenated methyl or dimethyl bipyrroles (DBPs), are reviewed here for the first time. These compounds were generally identified during the routine analysis of BFRs and have received little attention until recently. For each topic, an overview is presented of its current status.

  5. Brominated flame retardants in children's toys: concentration, composition, and children's exposure and risk assessment.

    PubMed

    Chen, She-Jun; Ma, Yun-Juan; Wang, Jing; Chen, Da; Luo, Xiao-Jun; Mai, Bi-Xian

    2009-06-01

    Brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), and polybrominated biphenyls (PBBs) were found in children's toys purchased from South China. The median BFR concentrations in the hard plastic toys were 53,000, 5540 ng/g, 101.1 ng/g, and 27.9 ng/g, fortotal PBDEs, DBDPE, BTBPE, and PBBs, respectively,which were notably higher than values in other toys. The PBDE concentrations were below the threshold limit (1000 ppm) required bythe European Commission's Restriction of Hazardous Substances (RoHS) and Waste Electrical and Electronic Equipment (WEEE) directives in all of the toys, except for one hard plastic toy with a total PBDE concentration of 5,344,000 ng/g. The BFR profiles in the toys were consistent with the patterns of their current production and consumption in China, where PBDEs, specifically decaBDE product, were the dominant BFR, followed by the emerging DBDPE. The relatively high concentrations of octa- and nonaBDEs in the foam toys and the results of principal component analysis (PCA) may suggest the decomposition of highly brominated BDEs during the manufacturing processes of the toys. Daily total PBDE exposures associated with toys via inhalation, mouthing, dermal contact, and oral ingestion ranged from 82.6 to 8992 pg/kg bw-day for children of 3 months to 14 years of age. Higher exposures, predominantly contributed through the mouthing pathway, were observed for infants and toddlers than for the other subgroups. In most cases, children's BFR exposure via the toys likely accounts for a small proportion of their daily BFR exposure, and the hazard quotients for noncancer risk evaluation were far below 1. To the author's knowledge, this is the first study to examine the concentrations of BFRs in toys, and the potential exposures to children.

  6. 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.

  7. Metabolites of organophosphate flame retardants and 2-ethylhexyl tetrabromobenzoate in urine from paired mothers and toddlers.

    PubMed

    Butt, Craig M; Congleton, Johanna; Hoffman, Kate; Fang, Mingliang; Stapleton, Heather M

    2014-09-02

    As a result of the polybrominated diphenyl ether (PBDE) ban in the mid-2000s, the chemical flame retardant market has moved toward alterative compounds including chlorinated alkyl and nonchlorinated aryl organophosphate flame retardants (OPFRs) as well as aromatic brominated compounds such as Firemaster 550 (FM550). Recent studies have shown that the OPFRs and Firemaster 550 components are frequently detected in polyurethane foams and in indoor dust. Some OPFRs are considered carcinogenic and/or neurodevelopmental toxicants, and children's exposure to these compounds is a concern. OPFRs are readily metabolized and excreted in the urine as their dialkyl and diaryl compounds which function as biomarkers for OPFR exposure. Limited research has shown that adults are broadly exposed to OPFRs, but nothing is known about children's exposure. Similarly, 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), a FM550 component, is metabolized to tetrabromobenzoic acid (TBBA). The current study measured levels of bis(1,3-dichloro-2-propyl) phosphate (BDCIPP), bis(1-chloro-2-propyl) phosphate (BCIPP), diphenyl phosphate (DPHP), 2 alkylated DPHPs, and TBBA in urine collected in 2013 from 21 US mother-toddler pairs. BDCIPP, DPHP, and ip-DPHP were detected in 100%, 98%, and 96% of all individuals, whereas BCIPP and tert-butyl-DPHP (tb-DPHP) were only detected in 8% and 13%. Further, TBBA was detected in 27% of adults but 70% of children. Overall, children had higher urinary levels of BDCIPP, DPHP, ip-DPHP, and TBBA as compared to their mothers, suggesting higher exposure. For example, on average, BDCIPP levels in children were 4.9 times those of mothers. BDCIPP and DPHP levels in mother's urine were also significantly correlated with levels in children's urine, suggesting similar exposure routes, likely in the home environment. Various potential predictors of OPFR exposure were assessed using a questionnaire. In children some predictors of hand-mouth exposure were associated with

  8. Alternate and new brominated flame retardants detected in U.S. house dust.

    PubMed

    Stapleton, Heather M; Allen, Joseph G; Kelly, Shannon M; Konstantinov, Alex; Klosterhaus, Susan; Watkins, Deborah; McClean, Michael D; Webster, Thomas F

    2008-09-15

    Due to the voluntary withdrawals and/or bans on the use of two polybrominated diphenyl ether (PBDE) commercial mixtures, an increasing number of alternate flame retardant chemicals are being introduced in commercial applications. To determine if these alternate BFRs are present in indoor environments, we analyzed dust samples collected from 19 homes in the greater Boston, MA area during 2006. Using pure and commercial standards we quantified the following brominated flame retardant chemicals using GC/ECNI-MS methods: hexabromocyclododecane (sigma HBCD), bis(2,4,6,-tribromphenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), and the brominated components found in Firemaster 550 (FM 550): 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB) and (2-ethylhexyl)tetrabromophthalate (TBPH), the latter compound being a brominated analogue of di(2-ethylhexyl)phthalate (DEHP). The concentrations of all compounds were log-normally distributed and the largest range in concentrations was observed for HBCD (sum of all isomers), with concentrations ranging from <4.5 ng/g to a maximum of 130,200 ng/g with a median value of 230 ng/g. BTBPE ranged from 1.6 to 789 ng/g with a median value of 30 ng/g and DBDPE ranged from <10.0 to 11,070 ng/g with a median value of 201 ng/g. Of the FM 550 components, TBB ranged from <6.6 to 15,030 ng/g with a median value of 133 ng/g; whereas TBPH ranged from 1.5 to 10,630 ng/g with a median value of 142 ng/g. Furthermore, the ratio of TBB/TBPH present in the dust samples ranged from 0.05 to 50 (average 4.4), varying considerably from the ratio observed in the FM 550 commercial mixture (4:1 by mass), suggesting different sources with different chemical compositions, and/or differential fate and transport within the home. Analysis of paired dust samples collected from different rooms in the same home suggests HBCD, TBB, and TBPH are higher in dust from the main living area compared to dust collected in bedrooms; however, BTBPE and DBDPE levels were

  9. Spectroscopic sensing of NH 3 emissions from flame retardants

    NASA Astrophysics Data System (ADS)

    Kantrowitz, Frank T.; Foreman, Dale U.; Gutman, William M.; Winkel, R. J.

    A Fourier transform spectrometer system housed in a four-wheel drive vehicle has been developed by the Army Research Laboratory, and recently was used to observe the smoke plume from a large brush fire in the Organ Mountains of south central New Mexico. The spectrometer was approximately 8 km from the fire during data acquisition. After processing, it was apparent that emission spectra from the plume contained ammonia emission lines. Ammonia is believed to have been released by the thermal decomposition of flame retardant chemicals that were being used to contain the fire.

  10. 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

  11. 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 ...

  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. Determination of flame-retardant hexabromocyclododecane diastereomers in textiles.

    PubMed

    Kajiwara, Natsuko; Sueoka, Minekazu; Ohiwa, Toshio; Takigami, Hidetaka

    2009-03-01

    To establish a concise and rapid procedure to analyze hexabromocyclododecane (HBCD) diastereomers in flame-retarded textiles, three different methods of extraction-Soxhlet, ultrasonic, and soaking extractions with toluene and dichloromethane (DCM)-were compared. During Soxhlet extraction using toluene, the percent contribution of alpha-HBCD to total HBCDs increased slightly and that of gamma-HBCD decreased, indicating that gamma-HBCD was isomerized to some extent at the boiling point of toluene (110.6 degrees C). For ultrasonic extraction, the temperature of the water bath can easily increase over time during the procedure, which might lead to undesirable effects. Therefore, we considered soaking extraction with DCM to be the most facile procedure to analyze HBCD diastereomers in textiles. Using the method established in this study, commercially available textiles in Japan (n=10) were analyzed to understand the actual composition of HBCD contents and its diastereomer profiles. With the exception of one textile sample, HBCDs were detected in all the samples analyzed, with concentrations ranging from 22000 to 43000 mg kg(-1) (i.e. 2.2-4.3%). We found a higher proportion of the alpha-diastereomer in most textile products compared with that of commercial HBCD mixtures, indicating that gamma-HBCD isomerized to alpha-diastereomer by heating processes to incorporate the commercial formulation into treated materials or that the alpha-diastereomer preferentially absorbed onto textile materials during the manufacturing of flame-retarded consumer products.

  14. 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.

  15. Pregnant Women's perceptions of exposure to brominated flame retardants.

    PubMed

    Lane, A; Goodyer, C G; Rab, F; Ashley, J M; Sharma, S; Hodgson, A; Nisker, J

    2016-12-01

    Recent media reports on human studies associating brominated flame retardants (BFRs) in household products in pregnancy with urogenital anomalies in boys and endocrine disruption in both sexes. We sought to explore the perceptions of pregnant women of brominated flame retardant (BFR) exposure, in light of recent media reports on the adverse health effects of BFR exposure prenatally. Pregnant women were recruited for interviews through posters and pamphlets in prenatal clinics, prenatal fairs and community centres. Interviews were audiotaped and transcribed verbatim for Charmaz-based qualitative analysis supported by NVIVO 10™. Theoretical sufficiency was reached after analyzing the interviews of 23 pregnant women. Themes co-constructed were: I-Lack of Awareness of BFRs; II-Factors Influencing BFR Exposure; III-Responsibility; IV-Informed Choice. Almost all participants felt it was difficult to make informed choices to avoid BFRs, and wanted communication from clinicians and regulation from governments regarding decreasing BFR exposure. Pregnant women in Canada may be unaware of the potential risks of exposure to BFRs. Professional organizations and governments should further study risk associated with BFR exposure in pregnancy and provide educational materials for pregnant women and clinicians regarding BFR exposure.

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  18. Phosphorylated lignin as a halogen-free flame retardant additive for epoxy composites

    Treesearch

    Gamini P. Mendis; Sydney G. Weiss; Matthew Korey; Charles R. Boardman; Mark Dietenberger; Jeffrey P. Youngblood; John A. Howarter

    2016-01-01

    Sustainable, non-halogenated flame retardants are desired for a variety of industry applications. Lignin, as an industrially processed wood derivative, has been examined as a potential sustainable flame retardant additive to polymer systems. Here, the lignin is phosphorylated using a pyridine-catalysed esterification reaction with diphenyl phosphoryl chloride to...

  19. Flame Retardancy of Chemically Modified Lignin as Functional Additive to Epoxy Nanocomposites

    Treesearch

    John A. Howarter; Gamini P. Mendis; Alex N. Bruce; Jeffrey P. Youngblood; Mark A. Dietenberger; Laura Hasburgh

    2015-01-01

    Epoxy printed circuit boards are used in a variety of electronics applications as rigid, thermally stable substrates. Due to the propensity of components on the boards, such as batteries and interconnects, to fail and ignite the epoxy, flame retardant additives are required to minimize fire risk. Currently, industry uses brominated flame retardants, such as TBBPA, to...

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. 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.

  6. Measurement and human exposure assessment of brominated flame retardants in household products from South China.

    PubMed

    Chen, She-Jun; Ma, Yun-Juan; Wang, Jing; Tian, Mi; Luo, Xiao-Jun; Chen, Da; Mai, Bi-Xian

    2010-04-15

    Brominated flame retardants (BFRs), polybrominated diphenyl ethers (PBDEs), and decabromodiphenyl ethane (DBDPE) were examined in household products in the Pearl River Delta, South China, including electronic appliances, furniture and upholstery, car interiors, and raw materials for electronics. The concentrations of PBDEs derived from penta-BDE mixture were much lower (<111 ng/g) than those for octa- and deca-BDE commercially derived PBDEs, with maximum values of 15,107 and 1,603,343 ng/g, respectively, in all the household products. Our findings suggest the recycling of old electronic products and their reuse might be also a potential important source of discontinued PBDEs to the environment. DBDPE was found in 20.0% of all the samples, ranging from 311 to 268,230 ng/g. PBDE congener profiles in both the household products and raw materials suggest that some less brominated BDEs in the environment may be derived from the decomposition of higher brominated PBDEs in PBDE-containing products in process of the manufacturing, use and/or recycling. Human exposure to PBDEs from household products via inhalation ranged from 175 to 612 pg/kg bw day, accounting for a small proportion of the total daily exposure via indoor inhalation. Despite the low deleterious risk associated with household products with regard to PBDEs, they are of special concern because of the relatively higher exposures observed for young children and further work is required.

  7. Soil contamination by brominated flame retardants in open waste dumping sites in Asian developing countries.

    PubMed

    Eguchi, Akifimi; Isobe, Tomohiko; Ramu, Karri; Tue, Nguyen Minh; Sudaryanto, Agus; Devanathan, Gnanasekaran; Viet, Pham Hung; Tana, Rouch Seang; Takahashi, Shin; Subramanian, Annamalai; Tanabe, Shinsuke

    2013-03-01

    In Asian developing countries, large amounts of municipal wastes are dumped into open dumping sites each day without adequate management. This practice may cause several adverse environmental consequences and increase health risks to local communities. These dumping sites are contaminated with many chemicals including brominated flame retardants (BFRs) such as polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). BFRs may be released into the environment through production processes and through the disposal of plastics and electronic wastes that contain them. The purpose of this study was to elucidate the status of BFR pollution in municipal waste dumping sites in Asian developing countries. Soil samples were collected from six open waste dumping sites and five reference sites in Cambodia, India, Indonesia, Malaysia, and Vietnam from 1999 to 2007. The results suggest that PBDEs are the dominant contaminants in the dumping sites in Asian developing countries, whereas HBCD contamination remains low. Concentrations of PBDEs and HBCDs ranged from ND to 180 μg/kg dry wt and ND to 1.4 μg/kg dry wt, respectively, in the reference sites and from 0.20 to 430 μg/kg dry wt and ND to 2.5 μg/kg dry wt, respectively, in the dumping sites. Contamination levels of PBDEs in Asian municipal dumping sites were comparable with those reported from electronic waste dismantling areas in Pearl River delta, China. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. 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.

  9. 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. Copyright © 2015. Published by Elsevier Ltd.

  10. Measuring Personal Exposure to Organophosphate Flame Retardants Using Silicone Wristbands and Hand Wipes.

    PubMed

    Hammel, Stephanie C; Hoffman, Kate; Webster, Thomas F; Anderson, Kim A; Stapleton, Heather M

    2016-04-19

    Organophosphate flame retardants (PFRs) are widely used as replacements for polybrominated diphenyl ethers in consumer products. With high detection in indoor environments and increasing toxicological evidence suggesting a potential for adverse health effects, there is a growing need for reliable exposure metrics to examine individual exposures to PFRs. Silicone wristbands have been used as passive air samplers for quantifying exposure in the general population and occupational exposure to polycyclic aromatic hydrocarbons. Here we investigated the utility of silicone wristbands in measuring exposure and internal dose of PFRs through measurement of urinary metabolite concentrations. Wristbands were also compared to hand wipes as metrics of exposure. Participants wore wristbands for 5 consecutive days and collected first morning void urine samples on 3 alternating days. Urine samples were pooled across 3 days and analyzed for metabolites of the following PFRs: tris(1,3-dichloroisopropyl) phosphate (TDCIPP), tris(1-chloro-2-isopropyl) phosphate (TCIPP), triphenyl phosphate (TPHP), and monosubstituted isopropylated triaryl phosphate (mono-ITP). All four PFRs and their urinary metabolites were ubiquitously detected. Correlations between TDCIPP and TCIPP and their corresponding urinary metabolites were highly significant on the wristbands (rs = 0.5-0.65, p < 0.001), which suggest that wristbands can serve as strong predictors of cumulative, 5-day exposure and may be an improved metric compared to hand wipes.

  11. Kinetics of Brominated Flame Retardant (BFR) Releases from Granules of Waste Plastics.

    PubMed

    Sun, Bingbing; Hu, Yuanan; Cheng, Hefa; Tao, Shu

    2016-12-20

    Plastic components of e-waste contain high levels of brominated flame retardants (BFRs), whose releases cause environmental and human health concerns. This study characterized the release kinetics of polybrominated diphenyl ethers (PBDEs) from millimeter-sized granules processed from the plastic exteriors of two scrap computer displays at environmentally relevant temperatures. The release rate of a substitute of PBDEs, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), from the waste plastics, was reported for the first time. Deca-BDE was the most abundant PBDE congeners in both materials (87-89%), while BTBPE was also present at relatively high contents. The release kinetics of BFRs could be modeled as one-dimensional diffusion, while the temperature dependence of diffusion coefficients was well described by the Arrhenius equation. The diffusion coefficients of BFRs (at 30 °C) in the plastic matrices were estimated to be in the range of 10(-27.16) to 10(-19.96) m(2)·s(-1), with apparent activation energies between 88.4 and 154.2 kJ·mol(-1). The half-lives of BFR releases (i.e., 50% depletion) from the plastic granules ranged from thousands to tens of billions of years at ambient temperatures. These findings suggest that BFRs are released very slowly from the matrices of waste plastics through molecular diffusion, while their emissions can be significantly enhanced with wear-and-tear and pulverization.

  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.

  13. Does exposure to flame retardants increase the risk for preterm birth?

    PubMed

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

    2015-02-01

    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 congener 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.

  14. Novel and High Volume Use Flame Retardants in US Couches Reflective of the 2005 PentaBDE Phase Out

    PubMed Central

    2012-01-01

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

  15. Novel and high volume use flame retardants in US couches reflective of the 2005 PentaBDE phase out.

    PubMed

    Stapleton, Heather M; Sharma, Smriti; Getzinger, Gordon; Ferguson, P Lee; Gabriel, Michelle; Webster, Thomas F; Blum, Arlene

    2012-12-18

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

  16. Effects of Several Flame Retardants and Curing Agents on the Fire and Mechanical Properties of Epoxy Resin

    NASA Astrophysics Data System (ADS)

    Li, Pei; Min, Yang; Ban, Da-Ming

    2016-05-01

    Effect of different flame retardant (FR) and curing agent on the epoxy resin was investigated by limiting oxygen index (LOI), mechanical properties and FTIR. The results show that flame retardant effect of PODOPP is better than PSDPP. The curing agent order is: m-phenylenediamine>ethanediamine> polyethylene polyamine. The effect of flame retardant behaviors better when synergist OMMT was added.

  17. Flame Retardant Chemicals in College Dormitories: Flammability Standards Influence Dust Concentrations.

    PubMed

    Dodson, Robin E; Rodgers, Kathryn M; Carey, Gale; Cedeno Laurent, Jose Guillermo; Covaci, Adrian; Poma, Giulia; Malarvannan, Govindan; Spengler, John D; Rudel, Ruthann A; Allen, Joseph G

    2017-05-02

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

  18. Exploring the Modes of Action of Phosphorus-Based Flame Retardants in Polymeric Systems

    PubMed Central

    Rabe, Sebastian; Chuenban, Yuttapong; Schartel, Bernhard

    2017-01-01

    Phosphorus-based flame retardants were incorporated into different, easily preparable matrices, such as polymeric thermoset resins and paraffin as a proposed model for polyolefins and investigated for their flame retardancy performance. The favored mode of action of each flame retardant was identified in each respective system and at each respective concentration. Thermogravimetric analysis was used in combination with infrared spectroscopy of the evolved gas to determine the pyrolysis behavior, residue formation and the release of phosphorus species. Forced flaming tests in the cone calorimeter provided insight into burning behavior and macroscopic residue effects. The results were put into relation to the phosphorus content to reveal correlations between phosphorus concentration in the gas phase and flame inhibition performance, as well as phosphorus concentration in the residue and condensed phase activity. Total heat evolved (fire load) and peak heat release rate were calculated based on changes in the effective heat of combustion and residue, and then compared with the measured values to address the modes of action of the flame retardants quantitatively. The quantification of flame inhibition, charring, and the protective layer effect measure the non-linear flame retardancy effects as functions of the phosphorus concentration. Overall, this screening approach using easily preparable polymer systems provides great insight into the effect of phosphorus in different flame retarded polymers, with regard to polymer structure, phosphorus concentration, and phosphorus species. PMID:28772815

  19. 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.

  20. New halogenated flame retardants in the atmosphere of nine urban areas in China: Pollution characteristics, source analysis and variation trends.

    PubMed

    Li, Qilu; Yang, Kong; Li, Kechang; Liu, Xin; Chen, Duohong; Li, Jun; Zhang, Gan

    2017-05-01

    Since the ban of polybrominated diphenyl ethers (PBDEs) excluding deca-BDE in China, new halogenated flame retardants (NHFRs), such as new brominated flame retardants and Dechlorane Plus, have become widely used. In this study, we assessed the atmospheric gaseous and particulate levels of eight NHFRs in nine urban areas in China. We detected high mean atmospheric (vapour plus particle phases) concentrations of tetrabromophthalate (TBPH) (74.8 pg m(-3)) and decabromodiphenyl ethane (DBDPE) (68.8 pg m(-3)), two major NHFRs. Most of the gaseous and particulate NHFR concentrations presented seasonal variations (from summer to autumn), possibly driven by temperature. Spatially, concentrations and patterns of the NHFRs differed among the nine cities. Significantly higher concentrations were detected in cities with higher gross domestic products. The composition, especially the DBDPE/TBPH ratio (S), were clearly different among the cities, which pattern in each city are likely driven by variations in the type of industries operating in each city. Based on the temporal analysis of other researches and our data, PBDE levels have decreased markedly, while NHFRs levels have increased. Since high NHFR levels had detrimental effects on public health, NHFRs research warrants more attention. Copyright © 2017 Elsevier Ltd. All rights reserved.

  1. 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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. 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.

  3. 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. Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Exposure to an environmentally relevant mixture of brominated flame retardants affects fetal development in Sprague-Dawley rats.

    PubMed

    Berger, Robert G; Lefèvre, Pavine L C; Ernest, Sheila R; Wade, Michael G; Ma, Yi-Qian; Rawn, Dorothea F K; Gaertner, Dean W; Robaire, Bernard; Hales, Barbara F

    2014-06-05

    Brominated flame retardants are incorporated into a wide variety of consumer products and are known to enter into the surrounding environment, leading to human exposure. There is accumulating evidence that these compounds have adverse effects on reproduction and development in humans and animal models. Animal studies have generally characterized the outcome of exposure to a single technical mixture or congener. Here, we determined the impact of exposure of rats prior to mating and during gestation to a mixture representative of congener levels found in North American household dust. Adult female Sprague-Dawley rats were fed a diet containing 0, 0.75, 250 or 750mg/kg of a mixture of flame retardants (polybrominated diphenyl ethers, hexabromocyclododecane) from two weeks prior to mating to gestation day 20. This formulation delivered nominal doses of 0, 0.06, 20 and 60mg/kg body weight/day. The lowest dose approximates high human exposures based on house dust levels and the dust ingestion rates of toddlers. Litter size and resorption sites were counted and fetal development evaluated. No effects on maternal health, litter size, fetal viability, weights, crown rump lengths or sex ratios were detected. The proportion of litters with fetuses with anomalies of the digits (soft tissue syndactyly or malposition of the distal phalanges) was increased significantly in the low (0.06mg/kg/day) dose group. Skeletal analysis revealed a decreased ossification of the sixth sternebra at all exposure levels. Thus, exposure to an environmentally relevant mixture of brominated flame retardants results in developmental abnormalities in the absence of apparent maternal toxicity. The relevance of these findings for predicting human risk is yet to be determined.

  5. Fathead minnow (Pimephales promelas Rafinesque) exposure to three novel brominated flame retardants in outdoor mesocosms: bioaccumulation and biotransformation.

    PubMed

    de Jourdan, Benjamin P; Hanson, Mark L; Muir, Derek C G; Solomon, Keith R

    2014-05-01

    The phaseout of polybrominated diphenyl ethers (PBDEs) has prompted the search for appropriate substitutes. These substitutes, referred to as novel brominated flame retardants (NBFRs), are poorly characterized in terms of their persistence, bioaccumulation, and toxicity. The authors assessed the bioaccumulation potential of 3 non-PBDE brominated flame retardants: 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), tetrabromobisphenol A bis(2,3-dibromopropylether) (TBBPA-BDBPE), and BZ-54, a mixture of bis(2-ethylhexyl)tetrabromophthalate) (BEH-TEBP) and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB). Replicate outdoor aquatic mesocosms were treated individually at concentrations designed to give a maximum load of 500 ng/g of flame retardant in the upper 5 cm of the sediment. Caged fathead minnows (Pimephales promelas, 24 fish per replicate) were introduced to each mesocosm and acclimated for 10 d prior to exposure. The exposure period was 42 d, followed by 28 d of depuration after transfer to a control mesocosm, during which physical, reproductive, and biochemical end points were examined. Tissue samples were taken to measure the accumulation, depuration, and biotransformation of NBFRs. Fathead minnows were observed to accumulate, after growth adjustment, BTBPE (16-4203 ng/g lipid) and TBBPA-BDBPE (>1000 ng/g lipid) but with a lack of consistent accumulation observed for EH-TBB and BEH-TEBP. However, limited biologically meaningful or consistent responses were observed in the monitored physical, reproductive, and biochemical parameters. Fathead minnows from each treatment exhibited several brominated transformation products. The authors conclude that these NBFRs have the potential to be bioaccumulative and persistent in vivo and, therefore, warrant further study of physiological effects linked to chronic, sublethal responses.

  6. 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.

  7. Chemical alternatives assessment: the case of flame retardants.

    PubMed

    Howard, Gregory J

    2014-12-01

    Decisions on chemical substitution are made rapidly and by many stakeholders; these decisions may have a direct impact on consumer exposures, and, when a hazard exists, to consumer risks. Flame retardants (FRs) represent particular challenges, including very high production volumes, designed-in persistence, and often direct consumer exposure. Newer FR products, as with other industrial chemicals, typically lack data on hazard and exposure, and in many cases even basic information on structure and use in products is unknown. Chemical alternatives assessment (CAA) provides a hazard-focused approach to distinguishing between possible substitutions; variations on this process are used by several government and numerous corporate entities. By grouping chemicals according to functional use, some information on exposure potential can be inferred, allowing for decisions based on those hazard properties that are most distinguishing. This approach can help prevent the "regrettable substitution" of one chemical with another of equal, or even higher, risk.

  8. Symptomatology during hypoxic exposure to flame-retardant chamber atmospheres.

    PubMed

    Knight, D R; Cymerman, A; Devine, J A; Burse, R L; Fulco, C S; Rock, P B; Tappan, D V; Messier, A A; Carhart, H

    1990-01-01

    Hypoxia was studied in 12 men during 63-h exposures to 17 and 13% O2, with the subjects serving as their own controls by repeating the measurements in 21% O2. All test atmospheres were contaminated with 0.9% CO2 to simulate the condition of living aboard submarines. The mean SaO2's were 97-98% in all conditions of 21% O2, 96% in 17% O2 (n.s.), and 92% in 13% O2 (P less than 0.05). The blood concentrations of 2,3-diphosphoglycerate were elevated in 13 and 17% O2 (P less than 0.05). Seventeen percent O2 did not cause significant symptoms of environmental stress; however, 13% O2 caused symptoms of acute mountain sickness in 5 of 12 men. In the last 7 h of exposure to 17% O2, reduction of the barometric pressure to 576 Torr reduced the ambient PO2 to 98 Torr (similar to the PO2 of 13% O2 at normobaric pressure). This induced symptoms of acute mountain sickness in 3 of 11 men. All symptomatology and physiologic changes were reversed during recovery in 21% O2. Monitoring devices indicated the presence of volatile organic contaminants at a mean concentration of 6.1 ppm in the chamber atmosphere. Combustion tests in the occupied chamber showed that flame propagation was retarded by lowering the O2 concentration from 21 to 13-17%. We conclude that men can live comfortably in a normobaric, flame-retardant atmosphere consisting of 17% O2-0.9% CO2-6.1 ppm volatile organic compounds-balance N2.

  9. Formation of brominated dibenzofurans from pyrolysis of the polybrominated biphenyl fire retardant, firemaster FF-1.

    PubMed

    O'Keefe, P W

    1978-04-01

    The polybrominated biphenyl (PBB) fire retardant, FireMaster FF-1, was pyrolyzed for 20 min at 380-400 degrees C in open glass tubes and in tubes sealed after nitrogen flushing. The pyrolyzed residue was extracted with benzene, and extracts were cleaned up on columns of graphite (Carbopack A) and alumina. Analysis was carried out by low resolution direct probe mass spectrometry (MS). Spectra from extracts of the open tube pyrolyzed material had a series of ions characteristic of tetra- and pentabrominated dibenzofurans as evidenced by comparison with spectra from 2,3,7,8-tetrabromodibenzofuran (TBDF). Confirmatory evidence for the brominated dibenzofurans was obtained by high resolution MS dual ion analysis of certain fragment and molecular ions. Recovery values of TBDF through the cleanup procedure averaged 50% and, using this recovery value and TBDF as an external standard, dual ion analyses indicated that 40 ppm tetra- and 4 ppm pentabrominanted dibenzofuran were produced based on the PBB level used in the pyrolysis experiments. Additional analysis of the open tube pyrolyzed material by gas chromatography/mass spectrometry provided evidence that there was one tetrabromodibenzofuran compound with a retention time equal to that of TBDF. Trace levels (less than 1 ppm) of the molecular ion of tetrabrominated dibenzofuran were found after analysis by low resolution MS of the PBB pyrolyzed under nitrogen in sealed tubes. The experimental evidence is consistent with a mechanism for brominated dibenzofuran formation involving attack of oxygen on PBB compounds.

  10. Performance of carbon material derived from starch mixed with flame retardant as electrochemical capacitor

    NASA Astrophysics Data System (ADS)

    Tsubota, Toshiki; Morita, Masaki; Murakami, Naoya; Ohno, Teruhisa

    2014-12-01

    Carbon materials derived from starch with an added flame retardant, such as melamine polyphosphate, melamine sulfate, guanylurea phosphate, or guanidine phosphate, were synthesized for investigating the performance as the electrode of an electrochemical capacitor. The yield after the heat treatment of the carbonization reaction increased by the addition of these flame retardants up to 800 °C. Although both the specific surface area and electrical resistivity are almost independent of the addition of the flame retardants, the capacitance values are improved with the addition of the flame retardants. The nitrogen atoms derived from the flame retardants are introduced to some extent into the synthesized carbon material. Moreover, the phosphorous atoms or the sulfur atoms derived from the flame retardants are doped into the synthesized carbon material. The method applied in this study, that is, the addition of flame retardants before the carbonization process can be used for the doping of the hetero atom such as N, P and S into the carbon material.

  11. Developmental neurotoxicity of organophosphate flame retardants in early life stages of Japanese medaka (Oryzias latipes).

    PubMed

    Sun, Liwei; Tan, Hana; Peng, Tao; Wang, Sisi; Xu, Wenbin; Qian, Haifeng; Jin, Yuanxiang; Fu, Zhengwei

    2016-12-01

    Because brominated flame retardants are being banned or phased out worldwide, organophosphate flame retardants have been used as alternatives on a large scale and have thus become ubiquitous environmental contaminants; this raises great concerns about their environmental health risk and toxicity. Considering that previous research has identified the nervous system as a sensitive target, Japanese medaka were used as an aquatic organism model to evaluate the developmental neurotoxicity of 4 organophosphate flame retardants: triphenyl phosphate, tri-n-butyl phosphate, tris(2-butoxyethyl) phosphate, and tris(2-chloroethyl) phosphate (TCEP). The embryo toxicity test showed that organophosphate flame retardant exposure could decrease hatchability, delay time to hatching, increase the occurrence of malformations, reduce body length, and slow heart rate. Regarding locomotor behavior, exposure to the tested organophosphate flame retardants (except TCEP) for 96 h resulted in hypoactivity for medaka larvae in both the free-swimming and the dark-to-light photoperiod stimulation test. Changes of acetylcholinesterase activity and transcriptional responses of genes related to the nervous system likely provide a reasonable explanation for the neurobehavioral disruption. Overall, the present study clearly demonstrates the developmental neurotoxicity of various organophosphate flame retardants with very different potency and contribute to the determination of which organophosphate flame retardants are appropriate substitutes, as well as the consideration of whether regulations are reasonable and required. Environ Toxicol Chem 2016;35:2931-2940. © 2016 SETAC. © 2016 SETAC.

  12. Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods.

    PubMed

    Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

    2017-03-10

    Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate.

  13. Occurrence of PBDEs and alternative halogenated flame retardants in sewage sludge from the industrial city of Guangzhou, China.

    PubMed

    Wu, Qihang; Li, Haiyan; Kuo, Dave T F; Chen, Shejun; Mai, Bixian; Li, Huosheng; Liu, Zhineng; Deng, Mingjun; Zhang, Haozhi; Hu, Xiaodong; Geng, Xinhua; Chen, Yongheng

    2017-01-01

    This study investigated the prevalence and abundance of halogenated flame retardants (HFRs) in sludge samples from 5 sewage treatment plants in Guangzhou, China. Detection of 18 polybrominated diphenyl ethers (PBDEs), 9 alternative HFRs including Dechlorane Plus (DP), brominated alkylbenzenes, and polybrominated biphenyls, and 2 related degradation products was conducted. Decabromodiphenyl ether (BDE 209) and decabromodiphenyl ethane (DBDPE) were the dominant HFRs, with concentrations ranging from 200 to 2150 ng/g and 680-27,400 ng/g, respectively. The DBDPE detected was the highest level reported so far, exceeding those previously reported by 10-100 times. PBDEs were surpassed as the dominant HFRs in sewage sludge, with mean DBDPE/BDE 209 ratio exceeding 2 in all samples. The review of earlier surveys reveals that DBDPE level was surging while BDE 209 was declining. Annual emissions of BDE 209, DP, and DBDPE were estimated to be 227.9, 10.5, and 979.3 kg/yr, respectively. Although ecological risks assessment suggested low risks for the examined sludge, the key environmental properties and transformation pathways of alternative HFRs remain largely unknown. These findings prompt for further investigations on alternative HFR and sustainable management practices for HFR-laden biosolids. The HFR emission pattern revealed in this study is likely representative of other similarly industrialized regions in the post-PBDE era.

  14. Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods

    PubMed Central

    Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

    2017-01-01

    Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate. PMID:28281659

  15. Brominated flame retardants in three terrestrial passerine birds from South China: geographical pattern and implication for potential sources.

    PubMed

    Sun, Yu-xin; Luo, Xiao-jun; Mo, Ling; Zhang, Qiang; Wu, Jiang-ping; Chen, She-jun; Zou, Fa-sheng; Mai, Bi-xian

    2012-03-01

    Polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE), polybrominated biphenyls (PBBs) and pentabromotoluene (PBT) were investigated in light-vented bulbul (LVB), long-tailed shrike (LTS) and oriental magpie-robin (OMR) collected from seven sampling sites in South China. ∑PBDEs, DBDPE, PBB 153, and PBT levels ranged from 35 to 15,000, no detected (nd)-130, nd-6800, and nd-6.8 ng/g lipid weight, respectively. Positive correlations were found between δ(15)N values and brominated flame retardant (BFR) concentrations. The BFR geographic pattern indicated that PBDEs were linked to e-waste recycling and local industry activities as well as urbanization; PBB 153 was derived from e-waste; DBDPE was mainly come from local industry activities; and no specific source was observed for PBT. PBDE congener profiles were found to be depended on bird species and sampling sites with relatively high abundances of lower brominated congeners in e-waste site and significantly higher abundance of BDE153 in LTS and OMR than in LVB. Copyright © 2011 Elsevier Ltd. All rights reserved.

  16. Atmospheric Pressure Chemical Ionization Gas Chromatography Mass Spectrometry for the Analysis of Selected Emerging Brominated Flame Retardants in Foods

    NASA Astrophysics Data System (ADS)

    Lv, Surong; Niu, Yumin; Zhang, Jing; Shao, Bing; Du, Zhenxia

    2017-03-01

    Emerging brominated flame retardants (eBFRs) other than polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs) and their derivatives in foods have been in focus in recent years due to their increasing production volumes, indefinite information on toxicities and the lack of data on occurrence in environments, foods as well as humans. In this study, gas chromatography was coupled to an atmospheric pressure chemical ionization-tandem mass spectrometry (APGC-MS/MS) for the analysis of six eBFRs in pork, chicken, egg, milk and fish. A short section of unpacked capillary column coupled to the end of the analytical column was applied to improve the chromatographic behaviors of high boiling point compounds. The method was comprehensively validated with method limit of quantification (mLOQ) lower than 8 pg/g wet weight (w.w.). Samples from Chinese Total Diet study were quantified following the validated APGC-MS/MS method. 2,3,4,5-pentabromo-6-ethylbenzene (PBEB), hexabromobenzene (HBB), pentabromotoluene (PBT) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) were most frequently detected in samples. The highest concentration was found in fish with 351.9 pg/g w.w. of PBT. This is the first report on the presence of PBT in food samples with non-ignorable concentrations and detection rate.

  17. Organophosphate ester flame retardant-induced acute intoxications in dogs.

    PubMed

    Lehner, Andreas F; Samsing, Francisca; Rumbeiha, Wilson K

    2010-12-01

    Flame retardants have wide industrial applications and are incorporated into articles found in automobiles and home environments, including seat cushions. These compounds differ widely chemically and in their toxic potential. We report here two cases involving dogs following ingestion of car seat cushions impregnated with organophosphate ester fire retardants. Two case reports are presented. Two adult American Pit Bull dogs were presented at an emergency clinic with acute signs of central nervous system excitation including seizures. The most severely affected dog died 15 min after presentation, while the less affected dog fully recovered following treatment. In the second case, both a German Shepherd and a Rottweiler were found dead in the morning after they were left in a car overnight. A comprehensive toxicological analysis of samples from both cases revealed the presence of significant amounts (>2 ppm) of tris(2-chloroethyl)phosphate (TCEP) in stomach contents. This compound is a known inducer of epileptic seizures. Some other structurally related organophosphate ester compounds were found, and their role in the acute intoxications reported here is not known and remains to be determined. This is the first report linking acute deaths in dogs to the ingestion of car seat cushions found to contain large amounts of TCEP, an organophosphate ester compound. It is highly likely that this compound caused death through its known seizure-inducing activity.

  18. Fabrication of Cellulose Nanofiber/AlOOH Aerogel for Flame Retardant and Thermal Insulation.

    PubMed

    Fan, Bitao; Chen, Shujun; Yao, Qiufang; Sun, Qingfeng; Jin, Chunde

    2017-03-17

    Cellulose nanofiber/AlOOH aerogel for flame retardant and thermal insulation was successfully prepared through a hydrothermal method. Their flame retardant and thermal insulation properties were investigated. The morphology image of the cellulose nanofiber/AlOOH exhibited spherical AlOOH with an average diameter of 0.5 μm that was wrapped by cellulose nanofiber or adhered to them. Cellulose nanofiber/AlOOH composite aerogels exhibited excellent flame retardant and thermal insulation properties through the flammability test, which indicated that the as-prepared composite aerogels would have a promising future in the application of some important areas such as protection of lightweight construction materials.

  19. 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%.

  20. Fabrication of Cellulose Nanofiber/AlOOH Aerogel for Flame Retardant and Thermal Insulation

    PubMed Central

    Fan, Bitao; Chen, Shujun; Yao, Qiufang; Sun, Qingfeng; Jin, Chunde

    2017-01-01

    Cellulose nanofiber/AlOOH aerogel for flame retardant and thermal insulation was successfully prepared through a hydrothermal method. Their flame retardant and thermal insulation properties were investigated. The morphology image of the cellulose nanofiber/AlOOH exhibited spherical AlOOH with an average diameter of 0.5 μm that was wrapped by cellulose nanofiber or adhered to them. Cellulose nanofiber/AlOOH composite aerogels exhibited excellent flame retardant and thermal insulation properties through the flammability test, which indicated that the as-prepared composite aerogels would have a promising future in the application of some important areas such as protection of lightweight construction materials. PMID:28772670

  1. Further toxicologic studies with commercial and candidate flame retardant chemicals. Part II.

    PubMed

    Eldefrawi, A T; Mansour, N A; Brattsten, L B; Ahrens, V D; Lisk, D J

    1977-06-01

    A number of commercial and candidate flame retardants were studied with regard to their toxicity to goldfish, inhibition of cholinesterase, inhibition of acetyl choline binding to its receptor and insecticidal properties. Several of the flame retardants were notably toxic to fish. Some of the compounds showed modest inhibition of cholinesterase and/or microsomal oxidases, but none inhibited acetyl choline receptor binding. Whereas several of the flame retardants showed little or no insecticidal properties when added alone to a housefly diet, piperonyl butoxide greatly synergised their toxicity to houseflies.

  2. 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

  3. Assessment of dietary exposure to organohalogen contaminants, legacy and emerging flame retardants in a Norwegian cohort.

    PubMed

    Xu, Fuchao; Tay, Joo-Hui; Covaci, Adrian; Padilla-Sánchez, Juan Antonio; Papadopoulou, Eleni; Haug, Line Småstuen; Neels, Hugo; Sellström, Ulla; de Wit, Cynthia A

    2017-03-20

    Polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), emerging halogenated flame retardants (EHFRs) and organophosphate flame retardants (PFRs) were detected in 24h duplicate diet samples from a Norwegian cohort (n=61), with concentrations ranging from

  4. 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

    2016-08-05

    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.

  5. 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.

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

    PubMed

    Kiciński, Michał; Viaene, Mineke K; Den Hond, Elly; Schoeters, Greet; Covaci, Adrian; Dirtu, Alin C; Nelen, Vera; Bruckers, Liesbeth; Croes, Kim; Sioen, Isabelle; Baeyens, Willy; Van Larebeke, Nicolas; Nawrot, Tim S

    2012-11-14

    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. 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. 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 PBDE's on neurobehavioral domains other than the

  7. 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

  8. 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…

  9. 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…

  10. Alternatives Assessment: Partnership to Evaluate Flame Retardants in Printed Circuit Boards

    EPA Pesticide Factsheets

    The partnership project on flame retardants in printed circuit boards seeks to improve understanding of the environmental and human health impacts of new and current materials that can be used to meet fire safety standards

  11. Migration of Organophosphate Flame Retardants from Closed Cell Foam 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...

  12. 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...

  13. 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...

  14. 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...

  15. 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...

  16. Migration of Organophosphate Flame Retardants from Closed Cell Foam 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...

  17. 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.

  18. Direct probe atmospheric pressure photoionization/atmospheric pressure chemical ionization high-resolution mass spectrometry for fast screening of flame retardants and plasticizers in products and waste.

    PubMed

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

    2014-04-01

    In this study, we develop fast screening methods for flame retardants and plasticizers in products and waste based on direct probe (DP) atmospheric pressure photoionization (APPI) and atmospheric pressure chemical ionization (APCI) coupled to a high-resolution (HR) time-of-flight mass spectrometer. DP-APPI is reported for the first time in this study, and DP-APCI that has been scarcely exploited is optimized for comparison. DP-APPI was more selective than DP-APCI and also more sensitive for the most hydrophobic compounds. No sample treatment was necessary, and only a minimal amount of sample (few milligrams) was used for analysis that was performed within a few minutes. Both methods were applied to the analysis of plastic products, electronic waste, and car interiors. Polybrominated diphenylethers, new brominated flame retardants, and organophosphorus flame retardants were present in most of the samples. The combination of DP with HR mass spectra and data processing based on mass accuracy and isotopic patterns allowed the unambiguous identification of chemicals at low levels of about 0.025 % (w/w). Under untargeted screening, resorcinol bis(biphenylphosphate) and bisphenol A bis(bisphenylphosphate) were identified in many of the consumer products of which literature data are still very limited.

  19. Spatial distribution and implications to sources of halogenated flame retardants in riverine sediments of Taizhou, an intense e-waste recycling area in eastern China.

    PubMed

    Zhou, Shanshan; Fu, Jie; He, Huan; Fu, Jianjie; Tang, Qiaozhi; Dong, Minfeng; Pan, Yongqiang; Li, An; Liu, Weiping; Zhang, Limin

    2017-10-01

    Concentrations and spatial distribution pattern of organohalogen flame retardants were investigated in the riverine surface sediments from Taizhou, an intensive e-waste recycling region in China. The analytes were syn- and anti- Dechlorane Plus (DP), Dechloranes 602, 603, and 604, a DP monoadduct, two dechlorinated DPs and 8 congeners of polybrominated diphenyl ethers (PBDEs). The concentrations of Σ8PBDEs, ΣDP, ΣDec600s, and ΣDP-degradates ranged from <100 to 172,000, 100 to 55,000, not detectable (nd) to 1600, and nd to 2800 pg/g dry weight, respectively. BDE-209 and DP, both have been manufactured in China, had similar spatial distribution patterns in the study area, featured by distinctly recognizable hotspots some of which are in proximity to known e-waste dumping or metal recycling facilities. Such patterns were largely shared by Dec602 and dechlorinated DP, although their concentration levels were much lower. These major flame retardants significantly correlate with each other, and cluster together in the loading plot of principle component analysis. In contrast, most non-deca PBDE congeners do not correlate with DPs. Dec604 stood out having distinctly different spatial distribution pattern, which could be linked to historical use of mirex. Organic matter content of the sediment was not the dominant factor in determining the spatial pattern of pollution by halogenated flame retardants in the rivers of this study. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. 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...

  1. 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...

  2. Applications of the in vitro aryl hydrocarbon hydroxylase induction assay for determining "2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents": pyrolyzed brominated flame retardants.

    PubMed

    Zacharewski, T; Harris, M; Safe, S; Thoma, H; Hutzinger, O

    1988-10-01

    The pyrolysis of brominated flame retardants FR 300 BA (decabromobiphenyl) ether, FireMaster BP-6 (polybrominated biphenyls), Bromkal 70-5-DE (primarily pentabromodiphenylether), Bromkal 70-DE (primarily penta and tetrabromodiphenylether) and Bromkal G1 (pentabromodiphenylether) resulted in the formation of relatively high levels of polybrominated dibenzofurans (PBDFs) and dibenzo-p-dioxins (PBDDs as determined by gas chromatography-mass spectrometric analysis. The dose response EC50 values for the induction of aryl hydrocarbon hydroxylase (AHH) and ethoxyresorufin O-deethylase (EROD) by the flame retardant pyrolysates was determined in rat hepatoma H-4-II E cells and compared to the relative induction activities of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and the concentrations of "2,3,7,8-TCDD equivalents" were calculated. The range of "2,3,7,8-TCDD equivalents" levels (micrograms/g or ppm) derived from values obtained from the AHH and EROD bioassays for each of the pyrolyzed flame retardant samples was: 174-194, 480-1400, 2140-4680, 6740-8780 and 3920-5260 ppm for FR 300 BA, FireMaster BP-6, Bromkal 70 DE, Bromkal 70-5 DE and Bromkal G1, respectively. The in vivo dose-response effects of 2 pyrolyzed flame retardants were determined in immature male Wistar rats and compared to the dose-response activities of 2,3,7,8-TCDD. The in vivo responses which were measured included hepatic microsomal AHH and EROD induction, body weight loss and thymic atrophy. For the pyrolyzed FireMaster BP-6 and Bromkal 70-5 DE samples, the range of calculated in vivo "2,3,7,8-TCDD equivalents" (ppm in sample) for the 4 in vivo bioassays was 520-1780 ppm and 3860-8960 ppm, respectively. The excellent overlap between the in vivo and in vitro 2,3,7,8-TCDD equivalents for the 2 flame retardant pyrolysate extracts supports the utility of the in vitro induction bioassay for quantitatively determining "2,3,7,8-TCDD equivalents" for mixtures containing toxic halogenated aryl hydrocarbons.

  3. Selective damage to dopaminergic transporters following exposure to the brominated flame retardant, HBCDD.

    PubMed

    Genskow, Kelly R; Bradner, Joshua M; Hossain, Muhammad M; Richardson, Jason R; Caudle, W Michael

    2015-01-01

    Over the last several decades, the use of halogenated organic compounds has become the cause of environmental and human health concerns. Of particular notoriety has been the establishment of the neurotoxicity of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). The subsequent banning of PBDEs has led to greatly increased use of 1,2,5,6,9,10-hexabromocyclododecane (HBCDD, also known as HBCD) as a flame retardant in consumer products. The physiochemical similarities between HBCDD and PBDEs suggest that HBCDD may also be neurotoxic to the dopamine system, which is specifically damaged in Parkinson disease (PD). The purpose of this study was to assess the neurotoxicity of HBCDD on the nigrostriatal dopamine system using an in vitro and in vivo approach. We demonstrate that exposure to HBCDD (0-25 μM) for 24 h causes significant cell death in the SK-N-SH catecholaminergic cell line, as well as reductions in the growth and viability of TH+ primary cultured neurons at lower concentrations (0-10 μM) after 72 h of treatment. Assessment of the in vivo neurotoxicity of HBCDD (25 mg/kg for 30 days) resulted in significant reductions in the expression of the striatal dopamine transporter and vesicular monoamine transporter 2, both of which are integral in mediating dopamine homeostasis and neurotransmission in the dopamine circuit. However, no changes were seen in the expression of tyrosine hydroxylase in the dopamine terminal, or striatal levels of dopamine. To date, these are the first data to demonstrate that exposure to HBCDD disrupts the nigrostriatal dopamine system. Given these results and the ubiquitous nature of HBCDD in the environment, its possible role as an environmental risk factor for PD should be further investigated.

  4. 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.

  5. Design and performance evaluation of a medium flow sampler for airborne brominated flame retardants (BFRs).

    PubMed

    Batterman, Stuart; Chen, Tze-Chun; Chernyak, Sergei; Godwin, Christopher

    2009-04-01

    Brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs), have emerged as important and ubiquitous environmental pollutants, and there is a need to accurately measure airborne levels of these chemicals in both indoor and outdoor applications. We review and suggest performance criteria for BFR sampling systems, and then present the design of a new medium flow active sampler. The sampler uses a PTFE filter (47 mm, 1 microm pore size) in front of a polyurethane foam (PUF) adsorbent plug (22 mm dia, 76 mm length) with a nominal flow rate of 15 L min(-1) and a sampling period of one week, giving a sampling volume of 150 m(3). The sampler was evaluated using co-located systems to test precision, backup PUFs to test breakthrough, and distributed volume sampling to test linearity. Field experiments were conducted in five commercial buildings, one residence and outdoors at an urban site. A total of 20 BDE congeners were quantified. After appropriate cleaning of the PUF adsorbent, blank levels were negligible. Method detection limits (MDLs) were sufficiently low to quantify BDE congeners 17, 28, 71, 47, 100 and 99 in ambient air, and more than adequate to quantify these and other congeners in indoor air, where levels are typically much higher. The relative absolute deviation (RAD), based on distributed volume samples, ranged from 21% (BDE-71) to 81% (BDE-75) for indoor samples, and was somewhat higher for ambient samples. Only minimal breakthrough was detected in back-up samples, and over 80% of the samples had very low or negligible breakthrough. Humidity did not influence sampler performance. Overall, the medium-flow sampler can accurately measure PBDEs over a wide range of concentrations and applications.

  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.

  7. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. Maternal Exposure to a Brominated Flame Retardant and Genitourinary Conditions in Male Offspring

    PubMed Central

    Small, Chanley M.; DeCaro, John J.; Terrell, Metrecia L.; Dominguez, Celia; Cameron, Lorraine L.; Wirth, Julie; Marcus, Michele

    2009-01-01

    Background The upward trend in industrial nations in the incidence of male genitourinary (GU) conditions may be attributed to increased exposure to endocrine disruptors. Polybrominated biphenyl (PBB), a brominated flame retardant, is one such suspected endocrine disruptor. Objective We investigated the relationship between maternal serum levels of PBBs and GU conditions among male offspring exposed in utero. Methods In this cohort study of sons born to women accidentally exposed to PBBs during 1973–1974, we examined self-reported data on GU conditions among male offspring in relation to maternal serum PBB levels. We used generalized estimating equations to calculate odds ratios (ORs), controlling for gestational age at birth. Results Of 464 sons, 33 reported any GU condition (13 hernias, 10 hydroceles, 9 cryptorchidism, 5 hypospadias, and 1 varicocele). Four reported both hernia and hydrocele, and one both hernia and cryptorchidism. After adjustment for gestational age at birth, sons of highly exposed women (> 5 ppb) were twice as likely to report any GU condition compared with sons of the least exposed women [≤1 ppb; OR = 2.0; 95% confidence interval (CI), 0.8–5.1]. This risk was increased when we excluded sons born after the exposure but before the mother’s serum PBB measurement (OR = 3.1; 95% CI, 1.0–9.1). We found evidence of a 3-fold increase in reported hernia or hydrocele among sons with higher PBB exposure (test of trend p-value = 0.04). Neither hypospadias nor cryptorchidism was individually associated with PBB exposure. Conclusions Although cryptorchidism and hypospadias were not associated with in utero PBB exposure, this study suggests that other GU conditions may be associated with exposure to endocrine-disrupting chemicals during development. PMID:19654930

  9. PBDE flame retardants, thyroid disease, and menopausal status in U.S. women.

    PubMed

    Allen, Joseph G; Gale, Sara; Zoeller, R Thomas; Spengler, John D; Birnbaum, Linda; McNeely, Eileen

    2016-05-24

    Women have elevated rates of thyroid disease compared to men. Environmental toxicants have been implicated as contributors to this dimorphism, including polybrominated diphenyl ethers (PBDEs), flame retardant chemicals that disrupt thyroid hormone action. PBDEs have also been implicated in the disruption of estrogenic activity, and estrogen levels regulate thyroid hormones. Post-menopausal women may therefore be particularly vulnerable to PBDE induced thyroid effects, given low estrogen reserves. The objective of this study was to test for an association between serum PBDE concentrations and thyroid disease in women from the United States (U.S.), stratified by menopause status. Serum PBDE concentrations (BDEs 47, 99, 100 and 153) from the National Health and Examination Survey (NHANES) and reports on thyroid problems were available in the NHANES 2003-2004 cycle. Odds ratios (ORs) were calculated using multivariate logistic regression models accounting for population-weighted survey techniques and controlling for age, body mass index (BMI), education, smoking, alcohol consumption and thyroid medication. Menopause status was obtained by self-reported absence of menstruation in the previous 12 months and declared menopause. Women in the highest quartile of serum concentrations for BDEs 47, 99, and 100 had increased odds of currently having thyroid disease (ORs: 1.5, 1.8, 1.5, respectively) compared to the reference group (1st and 2nd quartiles combined); stronger associations were observed when the analysis was restricted to postmenopausal women (ORs: 2.2, 3.6, 2.0, respectively). Exposure to BDEs 47, 99, and 100 is associated with thyroid disease in a national sample of U.S. women, with greater effects observed post-menopause, suggesting that the disruption of thyroid signaling by PBDEs may be enhanced by the altered estrogen levels during menopause.

  10. Dietary exposure to brominated flame retardants and abnormal Pap test results.

    PubMed

    Jamieson, Denise J; Terrell, Metrecia L; Aguocha, Nnenna N; Small, Chanley M; Cameron, Lorraine L; Marcus, Michele

    2011-09-01

    This study examined a possible association of dietary exposure to polybrominated biphenyls (PBBs), a brominated flame retardant, and self-reported abnormal Pap test results and cervical dysplasia as a precursor to cervical cancer. Women in Michigan who ingested contaminated poultry, beef, and dairy products in the early 1970s were enrolled in a population-based cohort study in Michigan. Serum PBB and serum polychlorinated biphenyl (PCB) concentrations were measured. Reproductive history and health information, including Pap test results, were self-reported by participants. Of the women, 23% (223 of 956) reported an abnormal Pap test. In unadjusted analyses, self-reporting an abnormal Pap test was associated with younger age, current smoking (hazard ratio [HR] 1.61, 95% confidence interval [CI] 1.19-2.17), and longer duration of lifetime use of oral contraceptives (≥10 years; HR 1.92, 95% CI 1.21-3.06). When adjusting for PCB exposure, age at the interview, and smoking history, there was a slightly elevated risk of self-reporting an abnormal Pap test among the highly exposed women compared to women with nondetectable PBB concentrations (PBB≥13 μg/L, HR 1.23, 95% CI 0.74-2.06); however, the CI was imprecise. When breastfeeding duration after the initial PBB measurement was taken into account, there was a reduced risk of self-reporting an abnormal Pap test among the highly exposed women who breastfed for ≥12 months (HR 0.41, 95% CI 0.06-3.03; referent group: women with nondetectable PBB concentrations who did not breastfeed). It remains important to evaluate the potential reproductive health consequences of this class of chemicals as well as other potential predictors of abnormal Pap tests.

  11. Organophosphorus flame retardants in the European eel in Flanders, Belgium: Occurrence, fate and human health risk.

    PubMed

    Malarvannan, Govindan; Belpaire, Claude; Geeraerts, Caroline; Eulaers, Igor; Neels, Hugo; Covaci, Adrian

    2015-07-01

    The present study investigated the levels, profiles and human health risk of organophosphorus flame retardants and plasticizers (PFRs) in wild European eels (Anguilla anguilla) from freshwater bodies in the highly populated and industrial Flanders region (Belgium). Yellow eels (n=170) were collected at 26 locations between 2000 and 2009 and for each site, muscle samples of 3-10 eels were pooled and analyzed (n=26). Muscle lipid percentages varied widely between 2.4% and 21%, with a median value of 10%. PFRs were detected in all pooled samples in the order of tris-2-chloroisopropyl phosphate (TCIPP)>triphenyl phosphate (TPHP)>2-ethylhexyl diphenyl phosphate (EHDPHP)>tris-2-butoxyethyl phosphate (TBOEP)>tris-2-chloroethyl phosphate (TCEP)>tris-1,3-dichloro-2-propyl phosphate (TDCIPP). The median sum PFR concentration for all 26 sites was 44 ng/g lw (8.4 ng/g ww), and levels ranged between 7.0 and 330 ng/g lw (3.5 and 45 ng/g ww). Levels and profiles of PFRs in eels showed that sampling locations and river basin catchments are possible drivers of spatial variation in the aquatic environment. Median PFR concentrations were lower than those of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs). No correlation was observed between the PFR concentrations and lipid contents, suggesting that the accumulation of PFRs is not primarily associated with lipids. Human exposure to PFRs, due to consumption of wild eels, seems to be of minor importance compared to other potential sources, such as inhalation and ingestion of indoor dust. Nevertheless, considering the very limited data available on PFRs in human dietary items and their expected increasing use after the phase out of PBDEs and HBCDs, further investigations on PFRs in biota and human food items are warranted. Copyright © 2015 Elsevier Inc. All rights reserved.

  12. 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.

  13. Selective damage to dopaminergic transporters following exposure to the brominated flame retardant, HBCDD

    PubMed Central

    Genskow, Kelly R.; Bradner, Joshua M.; Hossain, Muhammad M.; Richardson, Jason R.; Caudle, W. Michael

    2015-01-01

    Over the last several decades, the use of halogenated organic compounds has become the cause of environmental and human health concerns. Of particular notoriety has been the establishment of the neurotoxicity of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). The subsequent banning of PBDEs has led to greatly increased use of 1,2,5,6,9,10-hexabromocyclododecane (HBCDD, also known as HBCD) as a flame retardant in consumer products. The physiochemical similarities between HBCDD and PBDEs suggest that HBCDD may also be neurotoxic to the dopamine system, which is specifically damaged in Parkinson disease (PD). The purpose of this study was to assess the neurotoxicity of HBCDD on the nigrostriatal dopamine system using an in vitro and in vivo approach. We demonstrate that exposure to HBCDD (0–25 μM) for 24 hrs causes significant cell death in the SK-N-SH catecholaminergic cell line, as well as reductions in the growth and viability of TH+ primary cultured neurons at lower concentrations (0–10 μM) after 72 hrs of treatment. Assessment of the in vivo neurotoxicity of HBCDD (25 mg/kg for 30 days) resulted in significant reductions in the expression of the striatal dopamine transporter and vesicular monoamine transporter 2, both of which are integral in mediating dopamine homeostasis and neurotransmission in the dopamine circuit. However, no changes were seen in the expression of tyrosine hydroxylase in the dopamine terminal, or striatal levels of dopamine. To date, these are the first data to demonstrate that exposure to HBCDD disrupts the nigrostriatal dopamine system. Given these results and the ubiquitous nature of HBCDD in the environment, its possible role as an environmental risk factor for PD should be further investigated. PMID:26073293

  14. PBDE, HBCD, and novel brominated flame retardant contamination in sediments from Lake Maggiore (Northern Italy).

    PubMed

    Poma, Giulia; Roscioli, Claudio; Guzzella, Licia

    2014-11-01

    The reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) has opened the way for the introduction of novel brominated flame retardants (NBFRs) in place of the banned formulations. Important representatives of this group are decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB). In this study, the contamination due to NBRFs was investigated for the first time in Italy in the sediments of Lake Maggiore. The aim of the research was to characterize in detail the possible presence of temporal trends and/or to identify potential sources of contamination. The study also considered the PBDE and HBCD lake sediment's current contamination. The analytical results showed that sediments in Lake Maggiore and its tributary rivers had weak concentrations of PBEB, HBB, and BTBPE, but they did not have a negligible/insignificant contamination of HBCD (up to 23.7 ng/g dry weight (d.w.)). The determination of PBDEs in sediments showed that BDE-209 was the predominant congener (up to 217 and 28 ng/g d.w. in river and lake sediments, respectively). DBDPE was detected in the sediments with relevant concentrations (up to 280 ng/g d.w in the River Boesio sediments). The positive correlation of DBDPE with BDE-209 confirmed the wide and important use of this compound in the Lake Maggiore basin and the hypothesis that this compound will soon become one of the most important NBFRs used in Northern Italy. The contamination of Lake Maggiore sediments due to PBDEs, HBCD, and NBFRs were comparable to other worldwide situations.

  15. 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.

  16. Influence of hydrophobic substance on enhancing washing durability of water soluble flame-retardant coating

    NASA Astrophysics Data System (ADS)

    Jindasuwan, Sunisa; Sukmanee, Nattinee; Supanpong, Chanida; Suwan, Mantana; Nimittrakoolchai, On-uma; Supothina, Sitthisuntorn

    2013-06-01

    Flame-retardant textiles are used in many consumer products. Among halogen-free flame retardant substances, inorganic flame retardants are mainly based on phosphorus, antimony, aluminum and boron-containing compounds. These coatings are soluble in water and therefore are not subjected to washing. In this study, washing durability of the inorganic flame retardant has been improved by incorporation of the hydrophobic substance to the coating. Composition of the coating which is the flame-retardant, monoammonium phosphate (MAP), and the hydrophobic substances, poly(methylhydrogen siloxane) (PMHS) and poly(dimethyl siloxane) (PDMS)), were varied to find the optimum coating solution. The results of SEM and TGA analysis, as well as the burning and washing tests, revealed that the coating solution consisting of MAP:PMHS:PDMS = 5:2:1 wt.% was the optimum condition. It showed the increased residue on the TGA profile compared to the uncoated sample, and self-extinguish after removal of the ignition source. The flame-retardant property can be maintained after washing, making it feasible for variety of applications.

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  20. Sorption of Organophosphorus Flame-Retardants on Settled ...

    EPA Pesticide Factsheets

    Dust is an important sink for indoor air pollutants, such as organophosphorus flame-retardants (OPFRs) that are used as additives in industrial and consumer products including electrical and electronic products, furniture, plastics, textile, and building/construction materials. This research investigated the sorption of OPFRs, tris(2-chloroethyl) phosphate (TCEP), tris(1-chlor-2-propyl) phosphate (TCPP), and tris(1,3-dichloro-2-propyl) phosphate (TDCPP) on settled Arizona Test Dust (ATD) using a dual small chamber system. During the test, seven free film release paper dust trays covered with ATD were placed in the sink test chamber. Constant gas phase OPFRs from the source chamber were dosed into the test chamber. The dust evenly spread on each dust tray was removed from the test chamber at different exposure times to determine the amount of OPFRs absorbed by the dust. The ATD has been characterized for a nominal particle size and surface area. The mass of dust on each of seven dust trays was weighed before the dust was placed inside the sink chamber. OPFRs concentrations at the inlet and faceplate of the test chamber were monitored by collecting polyurethane foam (PUF) samples. The OPFR exposed dust and PUF samples were extracted by 1:1 ethyl acetate/methylene chloride and analyzed on GC/MS. The data were used to calculate the OPFR sorption concentration on the dust through dust/air partition. Settled dust can adsorb OPFR from air. The sorption concentration wa

  1. Identification of the flame retardant decabromodiphenyl ethane in the environment.

    PubMed

    Kierkegaard, Amelie; Björklund, Jonas; Fridén, Ulrika

    2004-06-15

    The brominated flame retardant decabromodiphenyl ethane, DeBDethane, is marketed as an alternative to decabromodiphenyl ether, BDE209. There are currently no data available about the presence of DeBDethane in the environment. In this study, DeBDethane was positively identified by high-resolution mass spectrometry and quantified by low-resolution mass spectrometry with electron capture negative ionization in sewage sludge, sediment, and indoor air. It was found in 25 of the 50 Swedish sewage treatment plants investigated, with estimated levels up to about 100 ng/g dry weight. The concentration of DeBDethane in sediment from Western Scheldt in The Netherlands was 24 ng/g dry weight, and in an air sample from a Swedish electronics dismantling facility it was 0.6 ng/m3. DeBDethane was also found together with nonabromodiphenyl ethanes in water piping insulation. All samples contained BDE209 in higher concentrations as compared to DeBDethane (DeBDethane/BDE209 ratios ranging from 0.02 to 0.7), probably reflecting the higher and longer usage of BDE209. There is an ongoing risk assessment within the European Union regarding BDE209. Since DeBDethane has similar applications, it is important to investigate its environmental behavior before using it to replace BDE209.

  2. 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.

  3. 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.

  4. Occurrence of organophosphate flame retardants in drinking water from China.

    PubMed

    Li, Jun; Yu, Nanyang; Zhang, Beibei; Jin, Ling; Li, Meiying; Hu, Mengyang; Zhang, Xiaowei; Wei, Si; Yu, Hongxia

    2014-05-01

    Several organophosphate flame retardants (OPFRs) have been identified as known or suspected carcinogens or neurotoxic substances. Given the potential health risks of these compounds, we conducted a comprehensive survey of nine OPFRs in drinking water in China. We found total concentrations of OPFRs in tap water ranging from 85.1 ng/L to 325 ng/L, and tris(2-butoxyethyl) phosphate (TBEP), triphenyl phosphate (TPP), and tris(2-chloroisopropyl) phosphate (TCPP) were the most common components. Similar OPFR concentrations and profiles were observed in water samples processed through six different waterworks in Nanjing, China. However, boiling affected OPFR levels in drinking water by either increasing (e.g., TBEP) or decreasing (e.g., tributyl phosphate, TBP) concentrations depending on the particular compound and the state of the indoor environment. We also found that bottled water contained many of the same major OPFR compounds with concentrations 10-25% lower than those in tap water, although TBEP contamination in bottled water remained a concern. Finally, we concluded that the risk of ingesting OPFRs through drinking water was not a major health concern for either adults or children in China. Nevertheless, drinking water ingestion represents an important exposure pathway for OPFRs.

  5. Surface nanomodification of cotton fiber for flame retardant application.

    PubMed

    Paosawatyanyong, Boonchoat; Jermsutjarit, Piyarat; Bhanthumnavin, Worawan

    2012-01-01

    This paper presents efficient surface modification methodology to increase fire resistance properties of cotton by radio frequency (RF) plasma-induced graft copolymerization of vinyl phosphate ester as nanometer residue structure onto cotton surface. Methacryloyloxyethyl diphenyl phosphate (MEDP) monomer was synthesized and grafted onto the surface of cotton fabric by argon RF plasma at ambient temperature. Under optimum RF power (30 W), amounts of MEDP and N,N methylenebisacrylamide cross linking agent were varied to obtain optimum graft copolymerization conditions. Untreated and treated cotton were characterized by attenuated total reflectance infrared (ATR-IR) spectroscopy to investigate their functional group characteristics. This showed a strong covalent attachment between the surface of cotton and flame retardant material as the carbonyl functionality of the MEDP was clearly observed in the spectra. Scanning electron microscopic (SEM) analysis also showed grafted material as nanometer residue on cotton surface. Thermogravimetric analysis (TGA) revealed that the decomposition of phosphorus compound which occurs at lower temperature than the cotton itself resulted in the formation of char which covers cotton surface. This protects the fabric surface from further burning, therefore, higher amounts of remaining materials were observed as char in all cases. Furthermore, limiting oxygen index (LOI) had increased from 19 in untreated to 28 in grafted cotton. Detailed analysis on structural and thermal properties as well as surface grafting efficiency are presented.

  6. 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.

  7. A superhydrophobic sponge with excellent absorbency and flame retardancy.

    PubMed

    Ruan, Changping; Ai, Kelong; Li, Xingbo; Lu, Lehui

    2014-05-26

    Frequent oil spillages and the industrial discharge of organic solvents have not only caused severe environmental and ecological damage, but also create a risk of fire and explosion. Therefore, it is imperative, but also challenging, to find high-performance absorbent materials that are both effective and less flammable. Here we present a superior superhydrophobic sponge that exhibits excellent absorption performance through a combination of its superhydrophobicity, high porosity, and robust stability. More importantly, it inherits the intrinsic flame-retardant nature of the raw melamine sponge, and is thus expected to reduce the risk of fire and explosion when being used as an absorbent for flammable oils and organic compounds. Moreover, the fabrication of this sponge is easy to scale up, since it does not use a complicated process or sophisticated equipment. These characteristics make the sponge a much more competitive product than the commercial absorbent, nonwoven polypropylene fabric. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Dechlorane Plus flame retardant in terrestrial raptors from northern China.

    PubMed

    Chen, Da; Wang, Yan; Yu, Lehuan; Luo, Xiaojun; Mai, Bixian; Li, Shaoshan

    2013-05-01

    While a number of studies have addressed the environmental presence and behavior of the Dechlorane Plus (DP) flame retardant, there is still a dearth of information in terrestrial ecosystems. The present study revealed that median ∑DP (including anti- and syn-DP isomers) concentrations ranged from 10 to 810 ng/g lipid weight in muscle and liver tissues of six terrestrial raptor species collected in 2004-2006 from Beijing, China. Some concentrations rival the greatest DP burdens ever reported in global wildlife. Significant, positive correlations were observed between fanti (concentration ratio of anti-isomer to ∑DP) and ∑DP concentrations in the Eurasian sparrowhawk (Accipiter nisus) tissues. These results suggested that the DP burdens could be substantially driven by the accumulation of the anti-isomer in terrestrial birds. The tissue-specific accumulation of DP further suggested that factors (e.g., hepatic binding enzymes) other than lipid solubility could be important in determining tissue deposition of DP. Copyright © 2013 Elsevier Ltd. All rights reserved.

  9. Recent Developments in Organophosphorus Flame Retardants Containing P-C Bond and Their Applications

    PubMed Central

    Wendels, Sophie; Chavez, Thiebault; Bonnet, Martin; Gaan, Sabyasachi

    2017-01-01

    Organophosphorus compounds containing P-C bonds are increasingly developed as flame retardant additives due to their excellent thermal and hydrolytic stability and ease of synthesis. The latest development (since 2010) in organophosphorus flame retardants containing P-C bonds summarized in this review. In this review, we have broadly classified such phosphorus compounds based on the carbon unit linked to the phosphorus atom i.e., could be a part of either an aliphatic or an aromatic unit. We have only considered those published literature where a P-C bond was created as a part of synthetic strategy to make either an intermediate or a final organophosphorus compound with an aim to use it as a flame retardant. General synthetic strategies to create P-C bonds are briefly discussed. Most popular synthetic strategies used for developing P-C containing phosphorus based flame retardants include Michael addition, Michaelis–Arbuzov, Friedels–Crafts and Grignard reactions. In general, most flame retardant derivatives discussed in this review have been prepared via a one- to two-step synthetic strategy with relatively high yields greater than 80%. Specific examples of P-C containing flame retardants synthesized via suitable synthetic strategy and their applications on various polymer systems are described in detail. Aliphatic phosphorus compounds being liquids or low melting solids are generally applied in polymers via coatings (cellulose) or are incorporated in the bulk of the polymers (epoxy, polyurethanes) during their polymerization as reactive or non-reactive additives. Substituents on the P atoms and the chemistry of the polymer matrix greatly influence the flame retardant behavior of these compounds (condensed phase vs. the gas phase). Recently, aromatic DOPO based phosphinate flame retardants have been developed with relatively higher thermal stabilities (>250 °C). Such compounds have potential as flame retardants for high temperature processable polymers such as

  10. Recent Developments in Organophosphorus Flame Retardants Containing P-C Bond and Their Applications.

    PubMed

    Wendels, Sophie; Chavez, Thiebault; Bonnet, Martin; Salmeia, Khalifah A; Gaan, Sabyasachi

    2017-07-11

    Organophosphorus compounds containing P-C bonds are increasingly developed as flame retardant additives due to their excellent thermal and hydrolytic stability and ease of synthesis. The latest development (since 2010) in organophosphorus flame retardants containing P-C bonds summarized in this review. In this review, we have broadly classified such phosphorus compounds based on the carbon unit linked to the phosphorus atom i.e., could be a part of either an aliphatic or an aromatic unit. We have only considered those published literature where a P-C bond was created as a part of synthetic strategy to make either an intermediate or a final organophosphorus compound with an aim to use it as a flame retardant. General synthetic strategies to create P-C bonds are briefly discussed. Most popular synthetic strategies used for developing P-C containing phosphorus based flame retardants include Michael addition, Michaelis-Arbuzov, Friedels-Crafts and Grignard reactions. In general, most flame retardant derivatives discussed in this review have been prepared via a one- to two-step synthetic strategy with relatively high yields greater than 80%. Specific examples of P-C containing flame retardants synthesized via suitable synthetic strategy and their applications on various polymer systems are described in detail. Aliphatic phosphorus compounds being liquids or low melting solids are generally applied in polymers via coatings (cellulose) or are incorporated in the bulk of the polymers (epoxy, polyurethanes) during their polymerization as reactive or non-reactive additives. Substituents on the P atoms and the chemistry of the polymer matrix greatly influence the flame retardant behavior of these compounds (condensed phase vs. the gas phase). Recently, aromatic DOPO based phosphinate flame retardants have been developed with relatively higher thermal stabilities (>250 °C). Such compounds have potential as flame retardants for high temperature processable polymers such as

  11. 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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Flame retardants and organochlorines in indoor dust from several e-waste recycling sites in South China: composition variations and implications for human exposure.

    PubMed

    Zheng, Xiaobo; Xu, Fuchao; Chen, Kehui; Zeng, Yanhong; Luo, Xiaojun; Chen, Shejun; Mai, Bixian; Covaci, Adrian

    2015-05-01

    Several classes of flame retardants, such as polybrominated diphenyl ethers (PBDEs), novel brominated flame retardants (NBFRs), dechlorane plus (DPs), and organophosphate flame retardants (PFRs), together with polychlorinated biphenyls (PCBs) were measured in indoor dust from five villages located in three e-waste recycling regions in Guangdong Province, South China. The medians of PBDEs, NBFRs, and PFRs in dust in five sites ranged from 685-67,500, 1460-50,010, and 2180-29,000ng/g, respectively. These concentrations were much higher than the medians of PCBs (52-2900ng/g). BDE 209 and decabromodiphenyl ethane (DBDPE) were the two major halogen flame retardants in dust, while tris-(1-chloro-2-propyl) phosphate (TCIPP) and triphenyl phosphate (TPHP) were the major PFRs. Principle component analysis revealed the different pollutant patterns among different sites. The estimated median human exposures of PBDEs, NBFRs, PFRs, and PCBs via dust ingestion were 1.1-24.1, 0.73-20.3, 1.36-23.5, and 0.04-0.93ng/kgbw/day for adults, and 16.2-352, 10.7-296, 19.9-343, 0.05-0.61, 0.65-13.6ng/kgbw/day for toddlers, respectively. Residents from Site 5 had the highest exposure (95 percentile levels and high dust ingestion for toddlers) of PBDEs (3920ng/kgbw/day), NBFRs (3200ng/kgbw/day), and PFRs (5280ng/kgbw/day). More attention should be paid to the contamination with NBFRs and PFRs, instead of PCBs, in these e-waste recycling regions, and local public health threat from PBDE alternatives should remain of concern. To the best of our knowledge, this is the first study on human exposure assessment of PFRs at e-waste sites.

  13. Flame-retardant-wrapped polyphosphazene nanotubes: A novel strategy for enhancing the flame retardancy and smoke toxicity suppression of epoxy resins.

    PubMed

    Qiu, Shuilai; Wang, Xin; Yu, Bin; Feng, Xiaming; Mu, Xiaowei; Yuen, Richard K K; Hu, Yuan

    2017-03-05

    The structure of polyphosphazene nanotubes (PZS) is similar to that of carbon nanotubes (CNTs) before modification. For applications of CNTs in polymer composites, surface wrapping is an economically attractive route to achieve functionalized nanotubes. Based on this idea, functionalized polyphosphazene nanotubes (FR@PZS) wrapped with a cross-linked DOPO-based flame retardant (FR) were synthesized via one-step strategy and well characterized. Then, the obtained FR@PZS was introduced into epoxy resin (EP) to investigate flame retardancy and smoke toxicity suppression performance. Thermogravimetric analysis indicated that FR@PZS significantly enhanced the thermal stability of EP composites. Cone calorimeter results revealed that incorporation of FR@PZS obviously improved flame retardant performance of EP, for example, 46.0% decrease in peak heat release rate and 27.1% reduction in total heat release were observed in the case of epoxy composite with 3wt% FR@PZS. The evolution of toxic CO and other volatile products from the EP decomposition was significantly suppressed after the introduction of FR@PZS, Therefore, the smoke toxicity associates with burning EP was reduced. The presence of both PZS and a DOPO-based flame retardant was probably responsible for this substantial diminishment of fire hazard.

  14. 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.

  15. 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.

  16. 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.

  17. Flame Retardant Fibers for Human Space Exploration - Past, Present, and Future

    NASA Technical Reports Server (NTRS)

    Orndoff, Evelyne

    2017-01-01

    The National Aeronautics and Space Administration (NASA) has led in the development of unique flame retardant fibers for human spaceflight since the beginning of the Apollo program. After the Apollo 1 fire which killed Command Pilot Virgil I 'Gus' Grissom, Senior Pilot Edward H. White II, and Pilot Roger B. Chaffee from cardiac arrest on January 27, 1967, the accident investigators found severe third degree burns and melted spacesuits on the astronauts bodies. NASA immediately initiated an extensive research program aimed at developing flame retardant and flame resistant fibers for the enriched oxygen atmosphere of the Apollo crew cabin. Fibers are flame retardant when they have been modified by chemical and thermal treatments. Fibers are flame resistant when they are made of inherently flame resistant materials (i.e. glass, ceramic, highly aromatic polymers). Immediately after this tragic accident, NASA funded extensive research in specifically developing flame retardant fibers and fabrics. The early developmental efforts for human spaceflight were for the outer layer of the Apollo spacesuit. It was imperative that non-flammable fabrics be used in a 100% oxygen environment. Owens-Corning thus developed the Beta fiber that was immediately used in the Apollo program and later in the Space Shuttle program. Aside from the urgent need for protective fabrics for the spacesuit, NASA also needed flame retardant fabrics for both clothing and equipment inside the spacecraft. From the mid-1960s to the early 1980's, NASA contracted with many companies to develop inherently flame retardant fibers and flame retardant finishes for existing fibers. Fluorocarbons and aromatic polyamides were the polymers of great interest for the development of new inherently flame retardant fibers for enriched oxygen environments. These enriched environments varied for different space programs. For example, the Apollo program requirements were for materials that would not support combustion in a

  18. Cross-sectional study of social behaviors in preschool children and exposure to flame retardants.

    PubMed

    Lipscomb, Shannon T; McClelland, Megan M; MacDonald, Megan; Cardenas, Andres; Anderson, Kim A; Kile, Molly L

    2017-03-09

    Children are exposed to flame retardants from the built environment. Brominated diphenyl ethers (BDE) and organophosphate-based flame retardants (OPFRs) are associated with poorer neurocognitive functioning in children. Less is known, however, about the association between these classes of compounds and children's emotional and social behaviors. The objective of this study was to determine if flame retardant exposure was associated with measurable differences in social behaviors among children ages 3-5 years. We examined teacher-rated social behaviors measured using the Social Skills Improvement Rating Scale (SSIS) and personal exposure to flame retardants in children aged 3-5 years who attended preschool (n = 72). Silicone passive samplers worn for 7 days were used to assess personal exposure to 41 compounds using gas chromatography-mass spectrophotometer. These concentrations were then summed into total BDE and total OPFR exposure prior to natural log transformation. Separate generalized additive models were used to evaluate the relationship between seven subscales of the SSIS and lnΣBDE or lnΣOPFR adjusting for other age, sex, adverse social experiences, and family context. All children were exposed to a mixture of flame retardant compounds. We observed a dose dependent relationship between lnΣOPFR and two subscales where children with higher exposures were rated by their preschool teachers as having less responsible behavior (p = 0.07) and more externalizing behavior problems (p = 0.03). Additionally, children with higher lnΣBDE exposure were rated by teachers as less assertive (p = 0.007). We observed a cross-sectional association between children's exposure to flame retardant compounds and teacher-rated social behaviors among preschool-aged children. Children with higher flame retardant exposures exhibited poorer social skills in three domains that play an important role in a child's ability to succeed academically and socially.

  19. Dechlorane plus, a chlorinated flame retardant, in the Great Lakes.

    PubMed

    Hoh, Eunha; Zhu, Lingyan; Hites, Ronald A

    2006-02-15

    A highly chlorinated flame retardant, Dechlorane Plus (DP), was detected and identified in ambient air, fish, and sediment samples from the Great Lakes region. The identity of this compound was confirmed by comparing its gas chromatographic retention times and mass spectra with those of authentic material. This compound exists as two gas chromatographically separable stereoisomers (syn and anti), the structures of which were characterized by one- and two-dimensional proton nuclear magnetic resonance. DP was detected in most air samples, even at remote sites. The atmospheric DP concentrations were higher at the eastern Great Lakes sites (Sturgeon Point, NY, and Cleveland, OH) than those at the western Great Lakes sites (Eagle Harbor, MI, Chicago, IL, and Sleeping Bear Dunes, MI). Atthe Sturgeon Point site, DP concentrations once reached 490 pg/m3. DP atmospheric concentrations were comparable to those of BDE-209 at the eastern Great Lakes sites. DP was also found in sediment cores from Lakes Michigan and Erie. The peak DP concentrations were comparable to BDE-209 concentrations in the sediment core from Lake Erie butwere about 30 times lower than BDE-209 concentrations in the core from Lake Michigan. In the sediment cores, the DP concentrations peaked around 1975-1980, and the surficial concentrations were 10-80% of peak concentrations. Higher DP concentrations in air samples from Sturgeon Point, NY, and in the sediment core from Lake Erie suggest that DP's manufacturing facility in Niagara Falls, NY, may be a source. DP was also detected in archived fish (walleye) from Lake Erie, suggesting that this compound is, at least partially, bioavailable.

  20. 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

  1. Polyhalogenated compounds (chlorinated paraffins, novel and classic flame retardants, POPs) in dishcloths after their regular use in households.

    PubMed

    Gallistl, Christoph; Lok, Bianca; Schlienz, Annika; Vetter, Walter

    2017-04-03

    Dishcloths are routinely used in the clean-up process following daily kitchen activities and are thus subject to contamination commensurate with their frequent use. Here we analyzed dishcloths for the occurrence of polyhalogenated compounds after 14days of use in household kitchens. Analysis of 19 dishcloths revealed the presence of 29 polyhalogenated contaminants with total mean/median concentrations of 6,900/3,600ng/dishcloth, respectively. The spectrum featured classic and novel halogenated flame-retardants (HFRs) like polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), decabromodiphenyl ethane (DBDPE), pentabromoethylbenzene (PBEB), chlordene plus and dechlorane plus, as well as typical chloropesticides and background contaminants (e.g. hexachlorobenzene (HCB), p,p'-dichlorodiphenyldichloroethene (p,p'-DDE), polychlorinated biphenyls (PCBs) and lindane). The individual dishcloths showed highly variable fingerprints of polyhalogenated compounds. If present, medium-chain chlorinated paraffins (MCCPs) were by far the most prominent compound class with up to 55,400ng/dishcloth. Without consideration of chlorinated paraffins, the mean concentration of other polychlorinated compounds (270ng/dishcloth) was generally one order of magnitude lower than the mean concentration of brominated flame retardants (BFRs) (1,700ng/dishcloth). Our study verified that a wide range of polyhalogenated compounds is readily available in the kitchen environment. Furthermore, dishcloths are ordinarily handled without gloves or hand protection, given the observed concentrations of polyhalogenated compounds in dishcloths, such handling may serve as an additional exposure pathway for human users. Evaluation of this thesis was supported by conduction of a dermal uptake assessment.

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

    PubMed Central

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

    2015-01-01

    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 (R2 = 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

  3. Test chamber investigation of the volatilization from source materials of brominated flame retardants and their subsequent deposition to indoor dust.

    PubMed

    Rauert, C; Harrad, S; Stranger, M; Lazarov, B

    2015-08-01

    Numerous studies have reported elevated concentrations of brominated flame retardants (BFRs) in dust from indoor micro-environments. Limited information is available, however, on the pathways via which BFRs in source materials transfer to indoor dust. The most likely hypothesized pathways are (a) volatilization from the source with subsequent partitioning to dust, (b) abrasion of the treated product, transferring microscopic fibers or particles to the dust (c) direct uptake to dust via contact between source and dust. This study reports the development and application of an in-house test chamber for investigating BFR volatilization from source materials and subsequent partitioning to dust. The performance of the chamber was evaluated against that of a commercially available chamber, and inherent issues with such chambers were investigated, such as loss due to sorption of BFRs to chamber surfaces (so-called sink effects). The partitioning of polybrominated diphenyl ethers to dust, post-volatilization from an artificial source was demonstrated, while analysis in the test chamber of a fabric curtain treated with the hexabromocyclododecane formulation, resulted in dust concentrations exceeding substantially those detected in the dust pre-experiment. These results provide the first experimental evidence of BFR volatilization followed by deposition to dust. Brominated flame retardants (BFRs) are ubiquitous in indoor air and dust, leading to human exposure and resultant concerns about their adverse impact on health. Indoor dust has been demonstrated to constitute an important vector of human exposure to BFRs, especially for toddlers. Despite the greater importance of dust contamination in the context of human exposure to BFRs, the mechanisms via which BFRs transfer from source materials to dust have hitherto been subject to only limited research. In this study, a test chamber is utilized to simulate the migration of BFRs to dust via volatilization from source materials

  4. Developmental Exposure to Organophosphate Flame Retardants Elicits Overt Toxicity and Alters Behavior in Early Life Stage Zebrafish (Danio rerio)

    PubMed Central

    Dishaw, Laura V.; Hunter, Deborah L.; Padnos, Beth; Padilla, Stephanie; Stapleton, Heather M.

    2014-01-01

    Organophosphate flame retardants (OPFRs) are common replacements for the phased-out polybrominated diphenyl ethers (PBDEs) and have been detected at high concentrations in environmental samples. OPFRs are structurally similar to organophosphate pesticides and may adversely affect the developing nervous system. This study evaluated the overt toxicity, uptake, and neurobehavioral effects of tris (1,3-dichloro-2-propyl) phosphate (TDCPP), tris (2-chloroethyl) phosphate (TCEP), tris (1-chloro-2-propyl) phosphate (TCPP), and tris (2,3-dibromopropyl) phosphate (TDBPP) in early life stage zebrafish. Chlorpyrifos was used as a positive control. For overt toxicity and neurobehavioral assessments, zebrafish were exposed from 0 to 5 days postfertilization (dpf). Hatching, death, or malformations were evaluated daily. Teratogenic effects were scored by visual examination on 6 dpf. To evaluate uptake and metabolism, zebrafish were exposed to 1 µM of each organophosphate (OP) flame retardant and collected on 1 and 5 dpf to monitor accumulation. Larval swimming activity was measured in 6 dpf larvae to evaluate neurobehavioral effects of exposures below the acute toxicity threshold. TDBPP elicited the greatest toxicity at >1 µM. TDCPP and chlorpyrifos were overtly toxic at concentrations ≥10 µM, TCEP, and TCPP were not overtly toxic at the doses tested. Tissue concentrations increased with increasing hydrophobicity of the parent chemical after 24 h exposures. TDCPP and TDBPP and their respective metabolites were detected in embryos on 5 dpf. For all chemicals tested, developmental exposures that were not overtly toxic significantly altered larval swimming activity. These data indicate that OPFRs adversely affect development of early life stage zebrafish. PMID:25239634

  5. Flame retardants and legacy contaminants in polar bears from Alaska, Canada, East Greenland and Svalbard, 2005-2008.

    PubMed

    McKinney, Melissa A; Letcher, Robert J; Aars, Jon; Born, Erik W; Branigan, Marsha; Dietz, Rune; Evans, Thomas J; Gabrielsen, Geir W; Peacock, Elizabeth; Sonne, Christian

    2011-02-01

    Flame retardants and legacy contaminants were analyzed in adipose tissue from 11 circumpolar polar bear (Ursus maritimus) subpopulations in 2005-2008 spanning Alaska east to Svalbard. Although 37 polybrominated diphenyl ethers (PBDEs), total-(α)-hexabromocyclododecane (HBCD), 2 polybrominated biphenyls (PBBs), pentabromotoluene, pentabromoethylbenzene, hexabromobenzene, 1,2-bis(2,4,6-tribromophenoxy(ethane) and decabromodiphenyl ethane were screened, only 4 PBDEs, total-(α-)HBCD and BB153 were consistently found. Geometric mean ΣPBDE (4.6-78.4 ng/g lipid weight (lw)) and BB153 (2.5-81.1 ng/g lw) levels were highest in East Greenland (43.2 and 39.2 ng/g lipid weight (lw), respectively), Svalbard (44.4 and 20.9 ng/g lw) and western (38.6 and 30.1 ng/g lw) and southern Hudson Bay (78.4 and 81.1 ng/g lw). Total-(α)-HBCD levels (<0.3-41.1 ng/g lw) were lower than ΣPBDE levels in all subpopulations except in Svalbard, consistent with greater European HBCD use versus North American pentaBDE product use. ΣPCB levels were high relative to flame retardants as well as other legacy contaminants and increased from west to east (1797-10,537 ng/g lw). ΣCHL levels were highest among legacy organochlorine pesticides and relatively spatially uniform (765-3477 ng/g lw). ΣDDT levels were relatively low and spatially variable (31.5-206 ng/g lw). However, elevated proportions of p,p'-DDT to ΣDDT in Alaska and Beaufort Sea relative to other subpopulations suggested fresh inputs from vector control use in Asia and/or Africa. Comparing earlier circumpolar polar bear studies, ΣPBDE, total-(α)-HBCD, p,p'-DDE and ΣCHL levels consistently declined, whereas levels of other legacy contaminants did not. International regulations have clearly been effective in reducing levels of several legacy contaminants in polar bears relative to historical levels. However, slow or stalling declines of certain historic pollutants like PCBs and a complex mixture of "new" chemicals continue to be of

  6. 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.

  7. Influence of Flame Retardants on the Melt Dripping Behaviour of Thermoplastic Polymers.

    PubMed

    Matzen, Melissa; Kandola, Baljinder; Huth, Christian; Schartel, Bernhard

    2015-08-27

    Melt flow and dripping of the pyrolysing polymer melt can be both a benefit and a detriment during a fire. In several small-scale fire tests addressing the ignition of a defined specimen with a small ignition source, well-adjusted melt flow and dripping are usually beneficial to pass the test. The presence of flame retardants often changes the melt viscosity crucially. The influence of certain flame retardants on the dripping behaviour of four commercial polymers, poly(butylene terephthalate) (PBT), polypropylene (PP), polypropylene modified with ethylene-propylene rubber (PP-EP) and polyamide 6 (PA 6), is analysed based on an experimental monitoring of the mass loss due to melt dripping, drop size and drop temperature as a function of the furnace temperature applied to a rod-shaped specimen. Investigating the thermal transition (DSC), thermal and thermo-oxidative decomposition, as well as the viscosity of the polymer and collected drops completes the investigation. Different mechanisms of the flame retardants are associated with their influence on the dripping behaviour in the UL 94 test. Reduction in decomposition temperature and changed viscosity play a major role. A flow limit in flame-retarded PBT, enhanced decomposition of flame-retarded PP and PP-EP and the promotion of dripping in PA 6 are the salient features discussed.

  8. 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.

  9. Biobased polyelectrolyte multilayer-coated hollow mesoporous silica as a green flame retardant for epoxy resin.

    PubMed

    Jiang, Shu-Dong; Tang, Gang; Chen, Junmin; Huang, Zheng-Qi; Hu, Yuan

    2017-09-04

    Here, we describe a multifunctional biobased polyelectrolyte multilayer-coated hollow mesoporous silica (HM-SiO2@CS@PCL) as a green flame retardant through layer-by-layer assembly using hollow mesoporous silica (HM-SiO2), chitosan (CS) and phosphorylated cellulose (PCL). The electrostatic interactions deposited the CS/PCL coating on the surface of HM-SiO2. Subsequently, this multifunctional flame retardant was used to enhance thermal properties and flame retardancy of epoxy resin. The addition of HM-SiO2@CS@PCL to the epoxy resin thermally destabilized the epoxy resin composite, but generated a higher char yield. Furthermore, HM-SiO2 played a critical role and generated synergies with CS and PCL to improve fire safety of the epoxy resin due to the multiple flame retardancy elements (P, N and Si). This multi-element, synergistic, flame-retardant system resulted in a remarkable reduction (51%) of peak heat release rate and a considerable removal of flammable decomposed products. Additionally, the incorporation of HM-SiO2@CS@PCL can sustainably recycle the epoxy resin into high value-added hollow carbon spheres during combustion. Therefore, the HM-SiO2@CS@PCL system provides a practical possibility for preparing recyclable polymer materials with multi-functions and high performances. Copyright © 2017 Elsevier B.V. All rights reserved.

  10. Influence of Flame Retardants on the Melt Dripping Behaviour of Thermoplastic Polymers

    PubMed Central

    Matzen, Melissa; Kandola, Baljinder; Huth, Christian; Schartel, Bernhard

    2015-01-01

    Melt flow and dripping of the pyrolysing polymer melt can be both a benefit and a detriment during a fire. In several small-scale fire tests addressing the ignition of a defined specimen with a small ignition source, well-adjusted melt flow and dripping are usually beneficial to pass the test. The presence of flame retardants often changes the melt viscosity crucially. The influence of certain flame retardants on the dripping behaviour of four commercial polymers, poly(butylene terephthalate) (PBT), polypropylene (PP), polypropylene modified with ethylene-propylene rubber (PP-EP) and polyamide 6 (PA 6), is analysed based on an experimental monitoring of the mass loss due to melt dripping, drop size and drop temperature as a function of the furnace temperature applied to a rod-shaped specimen. Investigating the thermal transition (DSC), thermal and thermo-oxidative decomposition, as well as the viscosity of the polymer and collected drops completes the investigation. Different mechanisms of the flame retardants are associated with their influence on the dripping behaviour in the UL 94 test. Reduction in decomposition temperature and changed viscosity play a major role. A flow limit in flame-retarded PBT, enhanced decomposition of flame-retarded PP and PP-EP and the promotion of dripping in PA 6 are the salient features discussed. PMID:28793527

  11. Intrinsic Flame-Retardant and Thermally Stable Epoxy Endowed by a Highly Efficient, Multifunctional Curing Agent

    PubMed Central

    Dong, Chunlei; Wirasaputra, Alvianto; Luo, Qinqin; Liu, Shumei; Yuan, Yanchao; Zhao, Jianqing; Fu, Yi

    2016-01-01

    It is difficult to realize flame retardancy of epoxy without suffering much detriment in thermal stability. To solve the problem, a super-efficient phosphorus-nitrogen-containing reactive-type flame retardant, 10-(hydroxy(4-hydroxyphenyl)methyl)-5,10-dihydrophenophosphazinine-10-oxide (HB-DPPA) is synthesized and characterized. When it is used as a co-curing agent of 4,4′-methylenedianiline (DDM) for curing diglycidyl ether of bisphenol A (DGEBA), the cured epoxy achieves UL-94 V-0 rating with the limiting oxygen index of 29.3%. In this case, the phosphorus content in the system is exceptionally low (0.18 wt %). To the best of our knowledge, it currently has the highest efficiency among similar epoxy systems. Such excellent flame retardancy originates from the exclusive chemical structure of the phenophosphazine moiety, in which the phosphorus element is stabilized by the two adjacent aromatic rings. The action in the condensed phase is enhanced and followed by pressurization of the pyrolytic gases that induces the blowing-out effect during combustion. The cone calorimeter result reveals the formation of a unique intumescent char structure with five discernible layers. Owing to the super-efficient flame retardancy and the rigid molecular structure of HB-DPPA, the flame-retardant epoxy acquires high thermal stability and its initial decomposition temperature only decreases by 4.6 °C as compared with the unmodified one. PMID:28774127

  12. 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.

  13. 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.

  14. Association of Brominated Flame Retardants With Diabetes and Metabolic Syndrome in the U.S. Population, 2003–2004

    PubMed Central

    Lim, Ji-Sun; Lee, Duk-Hee; Jacobs, David R.

    2008-01-01

    OBJECTIVE—Chlorinated persistent organic pollutants (POPs), endocrine disruptors accumulated in adipose tissue, were associated with diabetes and metabolic syndrome. Brominated flame retardants (BFRs), such as polybrominated diphenyl ethers (PBDEs) or polybrominated biphenyls (PBBs), are another class of POPs for which body burden is increasing. Cross-sectional associations of serum concentrations of BFRs with diabetes and metabolic syndrome were studied. RESEARCH DESIGN AND METHODS—In the National Health and Nutrition Examination Survey 2003–2004, 1,367 adults were examined with respect to diabetes status. Five PBDEs and one PBB were selected, detectable in ≥60% of participants. For the outcome metabolic syndrome, we restricted the analysis to 637 participants with a morning fasting sample. RESULTS—Compared with subjects with serum concentrations below the limit of detection, prevalent diabetes had differing dose-response associations with serum concentrations of PBB-153 and PBDE-153. Adjusted odds ratios across quartiles of serum concentrations for PBB-153 or PBDE-153 were 1.0, 0.7, 1.4, 1.6, and 1.9 (P for trend <0.01) and 1.0, 1.6, 2.6, 2.7, and 1.8 (P for quadratic term <0.01), respectively. PBB-153 was also positively associated with the prevalence of metabolic syndrome with adjusted odds ratios of 1.0, 1.5, 3.1, 3.1, and 3.1 (P for trend<0.01). As in its association with diabetes, PBDE-153 showed an inverted U-shaped association with metabolic syndrome. CONCLUSIONS—Pending confirmation in prospective studies, lipophilic xenobiotics, including brominated POPs stored in adipose tissue, may be involved in the pathogenesis of diabetes and metabolic syndrome. PMID:18559655

  15. 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

    2013-05-07

    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

  16. 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

  17. Effect of biochar on mechanical and flame retardant properties of wood - Plastic composites

    NASA Astrophysics Data System (ADS)

    Zhang, Qingfa; Cai, Hongzhen; Yang, Keyan; Yi, Weiming

    Biochar/wood/plastic composites were prepared with different biochar content by the extrusion method, and the mechanical properties and flame retardant properties were tested. The study indicated that: with the increase of biochar content, the mechanical properties of the composites tended to rise at first and then fell. This suggested that the appropriate amount of biochar can promote the mechanical properties of the biochar/wood/plastic composites. Though both Mg(OH)2 and Al(OH)3 could improve the Flame retardant properties of the material evidently, Mg(OH)2 obtained a better effect than Al(OH)3. In particular, when the adding amount of Mg(OH)2 is 40 wt%, the flame retardant effect is the best. Al(OH)3 can reduce the mechanical properties of the material, while Mg(OH)2 could evidently promote the tensile strength and impact resistance strength of the material.

  18. 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.

  19. 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.

  20. 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.

  1. ACCUMULATION AND DNA DAMAGE IN FATHEAD MINNOWS (PIMEPHALES PROMELAS) EXPOSED TO 2 BROMINATED FLAME-RETARDANT MIXTURES, FIREMASTER® 550 AND FIREMASTER® BZ-54

    PubMed Central

    BEARR, JONATHAN S.; STAPLETON, HEATHER M.; MITCHELMORE, CARYS L.

    2015-01-01

    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

  2. Unsaturated polyester/expanded polystyrene composite : thermal characteristics and flame retardancy effects

    NASA Astrophysics Data System (ADS)

    Mohamed, R.; Syed Mustafa, S. A.; Norizan, Mohd N.; Amerudin, L. S.

    2017-07-01

    Panels for energy efficient buildings has to meet certain requirements such as low thermal conductivity and inherent flame retardancy characteristics, before being eligible for buildings and construction applications. Expanded Polystyrene (EPS) as waste material had been incorporated as filler in Unsaturated Polyester Resin (UPR) composites. The composite are fabricated as flat panel window or glazing to replace glass. In this study, different EPS content incorporated was found to affect flammability and thermal characteristics. Core additives such as Flame Retardant (FR) and Antioxidant (AO) were added to the composite for imparting flame retardancy and prevent aging of the composite. The result obtained via the comparison of the various composite systems studied had revealed that organic and metal oxide flame retardant (FR) additives imparts higher flame retardancy levels than others, but each type of additives had interacted with the polymeric matrixes differently. The thermal conductivity, k value, as measured from a handheld thermal probe had showed a minimum of ~0.124 W/m.K for the 1%wt zinc oxide sample, while the highest k value of ~0.280 W/m.K was exhibited by the 2%wt tin oxide sample. The first 1%wt of either metal oxide FR initially decreases both the thermal conductivity, k value; and volumetric specific heat, Cp,v of the samples. At 2%wt, increases in k value were obtained. The flammability was reduced with the use of organic Phosphate Ester FR, which had reduced the flame speed to about 37.1% of the original flame speed. With the equivalent mixture of all three organic FR system, the flammability reduced less than 30%, while the metal oxide FR additive doesn't reduces the flammability.

  3. 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.

  4. Unique synergism in flame retardancy in ABS based composites through blending PVDF and halloysite nanotubes

    NASA Astrophysics Data System (ADS)

    Remanan, Sanjay; Sharma, Maya; Jayashree, Priyadarshini; Parameswaranpillai, Jyotishkumar; Fabian, Thomas; Shih, Julie; Shankarappa, Prasad; Nuggehalli, Bharath; Bose, Suryasarathi

    2017-06-01

    This study demonstrates flame retardant materials designed using bi-phasic polymer blends of acrylonitrile butadiene styrene (ABS) and polyvinylidene fluoride (PVDF) containing halloysite nanotubes (HNTs) and Cloisite 30B nanoclay. The prepared blends with and without nanoparticles were extensively characterized. The nanoparticles were added in different weight concentrations to improve the flame retardancy. It was observed that prepared ABS/PVDF blends showed better flame retardancy than ABS based composites. The flame resistance was further improved by the addition of nanoparticles in the blends. The microscale combustion calorimetry (MCC) test showed better flame resistance in ABS/PVDF blends filled with 5 wt% HNTs than other composites. The total heat release of ABS/PVDF blend filled with 5 wt% HNTs decreased by 31% and also the heat of combustion decreased by 26% as compared to neat ABS. When compared with nanoparticles, the addition of PVDF reduced the peak heat release rate (PHRR) and increased the char residue more effectively. A synergistic improvement was observed from both PVDF and HNTs on the flame resistance properties.

  5. The first exposure assessment of legacy and unrestricted brominated flame retardants in predatory birds of Pakistan.

    PubMed

    Abbasi, Naeem Akhtar; Eulaers, Igor; Jaspers, Veerle Leontina Bernard; Chaudhry, Muhammad Jamshed Iqbal; Frantz, Adrien; Ambus, Per Lennart; Covaci, Adrian; Malik, Riffat Naseem

    2017-01-01

    The exposure to legacy polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDDs) and unrestricted 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE), bis (2-ethylhexyl)-2,3,4,5-tetrabromophthalate (BEH-TEBP) and 2-ethylhexyl-2,3,4,5-tetrabromo-benzoate (EH-TBB) was examined in tail feathers of 76 birds belonging to ten predatory species inhabiting Pakistan. In addition, different feather types of six individuals of Black kite (Milvus migrans) were compared for their brominated flame retardant (BFR) levels. Black kite was found to be the most contaminated species with a median (minimum-maximum) tail feather concentration of 2.4 (0.70-7.5) ng g(-1) dw for ∑PBDEs, 1.5 (0.5-8.1) ng g(-1) dw for ∑HBCDDs and 0.10 ( 0.05 for both). Similarly, no significant concentration differences were observed among different feather types (all P > 0.05) suggesting their similar exposure. While variables such as species, trophic guild and δ(15)N values were evaluated as major predictors for BFR accumulation in the studied species, we predict that combined effects of just mentioned factors may govern the intra- and interspecific differences in BFR contamination profiles. We urge for further investigation of BFR exposure and potential toxicological effects in

  6. Flame Retardant Associations Between Children’s Handwipes and House Dust

    PubMed Central

    Stapleton, Heather M.; Misenheimer, John; Hoffman, Kate; Webster, Thomas F.

    2014-01-01

    Polybrominated diphenyl ether (PBDE) flame retardants (FRs) have been ubiquitously detected at high concentrations in indoor environments; however, with their recent phase-out, more attention is being focused on measurements of exposure to alternative FRs such as organophosphate FRs (OPFRs). In our previous research, we found that PBDE residues measured on children’s handwipes were a strong predictor of serum PBDE levels. Here we build upon this research to examine longitudinal changes in PBDEs in indoor dust and children’s handwipes, and explore the associations between handwipes and dust for alternative FRs. Children from our previous study were re-contacted after approximately two years and new samples of indoor dust and handwipes were collected. PBDE dust-levels were significantly correlated between two different sampling rounds separated by two years; however, PBDE levels in handwipes were not correlated, perhaps suggesting that the sources of PBDEs remained relatively constant in the home, but that behavioral differences in children are changing with age and influencing handwipe levels. OPFRs [i.e. tris (1,3-dichloroisopropyl) phosphate (TDCPP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP)], 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB, also known as TBB), di(2-ethylhexyl) tetrabromophthalate (BEH-TEBP, also known as TBPH), and 1,2,5,6,9,10-hexabromocyclododecane (HBCD) were also ubiquitously detected in house dust samples and geometric mean levels were similar to PBDE levels, or higher in the case of the OPFRs. Significant associations between handwipes and house dust were observed for these alternative FRs, particularly for EH-TBB (rs= 0.54; p<0.001). Increasing house dust levels and age were associated with higher levels of FRs in handwipes, and high hand washing frequency (>5 times/day) was associated with lower FR levels in handwipes. Overall these data suggest that exposure to these alternative FRs will be

  7. 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

  8. Fate of brominated flame retardants and organochlorine pesticides in urban soil: volatility and degradation.

    PubMed

    Wong, Fiona; Kurt-Karakus, Perihan; Bidleman, Terry F

    2012-03-06

    As the uses of polybrominated diphenyl ethers (BDEs) are being phased out in many countries, soils could become a secondary emission source to the atmosphere. It is also anticipated that the demand for alternative brominated flame retardants (BFRs) will grow, but little is known about their environmental fate in soils. In this study, the volatility and degradation of BFRs and organochlorine pesticides (OCPs) in soil was investigated. A low organic carbon (5.6%) urban soil was spiked with a suite of BFRs and OCPs, followed by incubation under laboratory condition for 360 days. These included BDE- 17, -28, -47, -99; α- and β-1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), β-1,2,5,6-tetrabromocyclooctane (TBCO), and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), OCPs: α-hexachlorocyclohexane (α-HCH) and (13)C(6)-α-HCH, trans-chlordane (TC), and (13)C(10)-TC. The volatility of spiked chemicals was investigated using a fugacity meter to measure the soil-air partition coefficient (K(SA)). K(SA) of some spiked BFRs and OCPs increased from Day 10 to 60 or 90 and leveled off afterward. This suggests that the volatility of BFRs and OCPs decreases over time as the chemicals become more strongly bound to the soil. Degradation of alternative BFRs (α- and β-TBECH, β-TBCO, DPTE), BDE-17, and α-HCH ((13)C-labeled and nonlabeled) was evident in soils over 360 days, but no degradation was observed for the BDE-28, -47, -99, and TC ((13)C-labeled and nonlabeled). A method to separate the enantiomers of α-TBECH and β-TBCO was developed and their degradation, along with α-HCH ((13)C-labeled and nonlabeled) was enantioselective. This is the first study which reports the enantioselective degradation of chiral BFRs in soils. Discrepancies between the enantiomer fraction (EF) of chemicals extracted from the soil by dichloromethane (DCM) and air were found. It is suggested that DCM removes both the sequestered and loosely bound fractions of chemicals in soil, whereas

  9. Brominated flame retardants in waste electrical and electronic equipment: substance flows in a recycling plant.

    PubMed

    Morf, Leo S; Tremp, Josef; Gloor, Rolf; Huber, Yvonne; Stengele, Markus; Zennegg, Markus

    2005-11-15

    Brominated flame retardants (BFRs) are synthetic additives mainly used in electrical and electronic appliances and in construction materials. The properties of some BFRs are typical for persistent organic pollutants, and certain BFRs, in particular some polybrominated diphenyl ether (PBDE) congeners and hexabromocyclododecane (HBCD), are suspected to cause adverse health effects. Global consumption of the most demanded BFRs, i.e., penta-, octa-, and decaBDE, tetrabromobisphenol A (TBBPA), and HBCD, has doubled in the 1990s. Only limited and rather uncertain data are available regarding the occurrence of BFRs in consumer goods and waste fractions as well as regarding emissions during use and disposal. The knowledge of anthropogenic substance flows and stocks is essential for early recognition of environmental impacts and effective chemicals management. In this paper, actual levels of penta-, octa-, and decaBDE, TBBPA, and HBCD in waste electrical and electronic equipment (WEEE) as a major carrier of BFRs are presented. These BFRs have been determined in products of a modern Swiss recycling plant applying gas chromatography/electron capture detection and gas chromatography/mass spectrometry analysis. A substance flow analysis (SFA) technique has been used to characterize the flows of target substances in the recycling process from the bulk WEEE input into the output products. Average concentrations in small size WEEE, representing the relevant electric and electronic appliances in WEEE, sampled in 2003 amounted to 34 mg/kg for pentaBDE, 530 mg/kg for octaBDE, 510 mg/kg for decaBDE, 1420 mg/kg for TBBPA (as an additive), 17 mg/kg for HBCD, 5500 mg/kg for bromine, and 1700 mg/kg for antimony. In comparison to data that have been calculated by SFA for Switzerland from literature for the 1990s, these measured concentrations in small size WEEE were 7 times higher for pentaBDE, unexpectedly about 50% lower for decaBDE, and agreed fairly well for TBBPA (as an additive) and

  10. Birds and flame retardants: A review of the toxic effects on birds of historical and novel flame retardants.

    PubMed

    Guigueno, Mélanie F; Fernie, Kim J

    2017-04-01

    Flame retardants (FRs) are a diverse group of chemicals, many of which persist in the environment and bioaccumulate in biota. Although some FRs have been withdrawn from manufacturing and commerce (e.g., legacy FRs), many continue to be detected in the environment; moreover, their replacements and/or other novel FRs are also detected in biota. Here, we review and summarize the literature on the toxic effects of various FRs on birds. Birds integrate chemical information (exposure, effects) across space and time, making them ideal sentinels of environmental contamination. Following an adverse outcome pathway (AOP) approach, we synthesized information on 8 of the most commonly reported endpoints in avian FR toxicity research: molecular measures, thyroid-related measures, steroids, retinol, brain anatomy, behaviour, growth and development, and reproduction. We then identified which of these endpoints appear more/most sensitive to FR exposure, as determined by the frequency of significant effects across avian studies. The avian thyroid system, largely characterized by inconsistent changes in circulating thyroid hormones that were the only measure in many such studies, appears to be moderately sensitive to FR exposure relative to the other endpoints; circulating thyroid hormones, after reproductive measures, being the most frequently examined endpoint. A more comprehensive examination with concurrent measurements of multiple thyroid endpoints (e.g., thyroid gland, deiodinase enzymes) is recommended for future studies to more fully understand potential avian thyroid toxicity of FRs. More research is required to determine the effects of various FRs on avian retinol concentrations, inconsistently sensitive across species, and to concurrently assess multiple steroid hormones. Behaviour related to courtship and reproduction was the most sensitive of all selected endpoints, with significant effects recorded in every study. Among domesticated species (Galliformes), raptors

  11. Determination of polyparameter linear free energy relationship (pp-LFER) substance descriptors for established and alternative flame retardants.

    PubMed

    Stenzel, Angelika; Goss, Kai-Uwe; Endo, Satoshi

    2013-02-05

    Polyparameter linear free energy relationships (pp-LFERs) can predict partition coefficients for a multitude of environmental and biological phases with high accuracy. In this work, the pp-LFER substance descriptors of 40 established and alternative flame retardants (e.g., polybrominated diphenyl ethers, hexabromocyclododecane, bromobenzenes, trialkyl phosphates) were determined experimentally. In total, 251 data for gas-chromatographic (GC) retention times and liquid/liquid partition coefficients (K) were measured and used to calibrate the pp-LFER substance descriptors. Substance descriptors were validated through a comparison between predicted and experimental log K for the systems octanol/water (K(ow)), water/air (K(wa)), organic carbon/water (K(oc)) and liposome/water (K(lipw)), revealing a high reliability of pp-LFER predictions based on our descriptors. For instance, the difference between predicted and experimental log K(ow) was <0.3 log units for 17 out of 21 compounds for which experimental values were available. Moreover, we found an indication that the H-bond acceptor value (B) depends on the solvent for some compounds. Thus, for predicting environmentally relevant partition coefficients it is important to determine B values using measurements in aqueous systems. The pp-LFER descriptors calibrated in this study can be used to predict partition coefficients for which experimental data are unavailable, and the predicted values can serve as references for further experimental measurements.

  12. Occurrence, removal and release characteristics of dissolved brominated flame retardants and their potential metabolites in various kinds of wastewater.

    PubMed

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

    2016-11-01

    The dissolved phase compound and congener specific distribution characteristics of three widely used brominated flame retardants (BFRs) comprising 27 polybrominated diphenyl ethers (PBDEs), 12 hydroxylated and methoxylated metabolites (OH- and MeO-BDEs), 3 hexabromocyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA) were investigated in influents and effluents of various kinds of wastewater treatment plants (WWTPs), with varying source of wastewater and type of treatment, and nearby rivers in Korea. The concentration of total BFRs were the highest in industrial WWTPs nearby large industrial complexes specialized in heavy chemicals. The distribution of BFRs was differed according to composition of wastewater, with predominance of TBBPA in WWTPs with higher portion of inflowing industrial wastewater. Among HBCD diastereomers, γ-HBCD was dominant in industrial wastewater as consistent to the previous reports, however, similar contribution of α- and γ-HBCD was found in sewage and human wastewater. Through treatment process, PBDEs were the most effectively removed with a mean removal efficiency of 68.3%. HBCDs and TBBPA had removal efficiencies of 41.3% and 48.7%, respectively. The lowest removal efficiency (10.3%) was observed for PBDE metabolites and their concentration in effluent of human wastewater was even increased at maximum 1.9 fold compared with influent, implying the possibility of transformation during treatment. The estimated dissolved phase daily load of PBDEs was highest in sewage while that of TBBPA was highest in industrial wastewater.

  13. 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.

  14. 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.

  15. Brominated flame retardants in the urban atmosphere of Northeast China: concentrations, temperature dependence and gas-particle partitioning.

    PubMed

    Qi, Hong; Li, Wen-Long; Liu, Li-Yan; Song, Wei-Wei; Ma, Wan-Li; Li, Yi-Fan

    2014-09-01

    57 pairs of air samples (gas and particle phases) were collected using a high volume air sampler in a typical city of Northeast China. Brominated flame retardants (BFRs) including 13 polybrominated diphenyl ethers (PBDEs, including BDEs 17, 28, 47, 49, 66, 85, 99, 100, 138, 153, 154, 183, and 209) and 9 alternative BFRs (p-TBX, PBBZ, PBT, PBEB, DPTE, HBBZ, γ-HBCD, BTBPE, and DBDPE) were analyzed. The annual average total concentrations of the 13 PBDEs and the 9 alternative BFRs were 69 pg/m(3) and 180 pg/m(3), respectively. BDE 209 and γ-HBCD were the dominant congeners, according to the one-year study. The partial pressure of BFRs in the gas phase was significantly correlated with the ambient temperature, except for BDE 85, γ-HBCD and DBDPE, indicating the important influence of ambient temperature on the behavior of BFRs in the atmosphere. It was found that the gas-particle partitioning coefficients (logKp) for most low molecular weight BFRs were highly temperature dependent as well. Gas-particle partitioning coefficients (logKp) also correlated with the sub-cooled liquid vapor pressure (logPL(o)). Our results indicated that absorption into organic matter is the main control mechanism for the gas-particle partitioning of atmospheric PBDEs. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. 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 (

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

    PubMed

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

    2013-09-03

    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 nonlinear relationships between BDE-209 exposures and thyroid dysfunction.

  18. 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.

  19. 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. Copyright © 2012 Elsevier Ltd. All rights reserved.

  20. Organophosphorus Flame Retardants and Plasticizers in Building and Decoration Materials and Their Potential Burdens in Newly Decorated Houses in China.

    PubMed

    Wang, Yan; Hou, Minmin; Zhang, Qiaonan; Wu, Xiaowei; Zhao, Hongxia; Xie, Qing; Chen, Jingwen

    2017-10-03

    Organophosphorus flame retardants (OPFRs) have been increasingly used in various building and decoration materials to fulfill fire safety standards since the phasing out of polybrominated diphenyl ethers. We determined OPFR concentrations in the most commonly used building and decoration materials available in local markets and online in China. The OPFR concentrations varied significantly, from 14.78 ng/g (putty powder) to 9649000 ng/g (expanded polystyrene panel (EPS)). Relatively high concentrations of OPFRs were found in foam samples, followed by nonwoven and polyvinyl chloride (PVC) wallpaper, PVC pipes, sealing materials, boards, and paints. Low concentrations were found mostly in wall decoration powders, suggesting that no OPFRs had been added to these powders. Tris(1-chloro-2-propyl) phosphate and tris(1,3-dichloro-2-propyl) phosphate were the most detected halogenated OPFRs, while tri-n-butyl phosphate and tris(2-butoxyethyl) phosphate were the dominant nonhalogenated OPFRs, implying that they are commonly used in building and decoration materials. The estimated OPFR burden in interior decoration using nonwoven wallpaper was 330- and 2110-fold higher than that using latex paint and diatomite, respectively. The emission periods of OPFRs from nonwoven and PVC wallpaper may be greater than 13 years. We estimated that the total burden of OPFRs for decoration using wallpaper in newly decorated houses in China is ∼63 t/y. Significantly higher concentrations of OPFRs in interior decoration materials, especially nonwoven wallpaper, pose potential health risks to the people using the buildings.

  1. 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.

  2. Do temporal and geographical patterns of HBCD and PBDE flame retardants in U.S. fish reflect evolving industrial usage?

    PubMed

    Chen, Da; La Guardia, Mark J; Luellen, Drew R; Harvey, Ellen; Mainor, T Matteson; Hale, Robert C

    2011-10-01

    Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) are common flame retardants in polymers and textiles. Recognition of the persistent, bioaccumulative, and toxic properties of PBDEs has prompted reductions in their use. In contrast, HBCD has received less scrutiny. The U.S has historically been a dominant BFR consumer. However, the few publications on HBCD in wildlife here suggest modest levels compared to Asian and European studies. In contrast, the HBCD concentrations we detected in U.S. fish are among the highest reported in the world. The temporal trends observed suggest that HBCD use may have risen, and that of Penta-BDE declined, following the 2004 termination of its U.S. manufacture. For example, Hyco River carp collected in 1999-2002 exhibited a mean ∑HBCD (sum of α-, β- and γ-HBCD) concentration of only 13 ng/g (lipid weight basis), but was 4640 ng/g in fish collected in 2006-2007. In contrast, the mean ∑PBDE level in these same fish decreased from 40,700 ng/g in 1999-2002 to 9140 ng/g in 2006-2007. Concentrations of HBCD and PBDEs in several Hyco River fish species exceeded those from rivers less influenced by manufacturing outfalls. Results support the contention that textile-related production, relative to its BFR market share, may release disproportionately large amounts of HBCD to the environment.

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

    PubMed

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

    2015-05-01

    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 (10mg/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.

  4. Levels and sources of brominated flame retardants in human hair from urban, e-waste, and rural areas in South China.

    PubMed

    Zheng, Jing; Luo, Xiao-Jun; Yuan, Jian-Gang; Wang, Jing; Wang, Yu-Tao; Chen, Shen-Jun; Mai, Bi-Xian; Yang, Zhong-Yi

    2011-12-01

    Human hair and indoor dust from urban, e-waste, and rural areas in south China were collected and analyzed for brominated flame retardants (BFRs). BFRs concentrations in hair from occupational e-waste recycling workers were higher than those from non-occupational exposed residents in other sampling areas. Polybrominated diphenyl ethers (PBDEs) and decabromodiphenyl ethane (DBDPE) are two major BFRs in hair samples. The PBDE congener profiles in hair from the e-waste area are different from those from urban and rural areas with relatively higher contribution of lower brominated congeners. DBDPE, instead of BDE209, has become the major BFR in non-e-waste recycling areas. Significant correlations were found between hair level and dust level for DBDPE and BTBPE but not for PBDEs. The different PBDE congener profiles between dust and hair may suggest that exogenous exposure to the PBDE adsorbed on dust is not a major source of hair PBDEs.

  5. Microwave-assisted extraction for qualitative and quantitative determination of brominated flame retardants in styrenic plastic fractions from waste electrical and electronic equipment (WEEE).

    PubMed

    Vilaplana, Francisco; Ribes-Greus, Amparo; Karlsson, Sigbritt

    2009-04-15

    A fast method for the determination of brominated flame retardants (BFRs) in styrenic polymers using microwave-assisted extraction (MAE) and liquid chromatography with UV detection (HPLC-UV) was developed. Different extraction parameters (extraction temperature and time, type of solvent, particle size) were first optimised for standard high-impact polystyrene (HIPS) samples containing known amounts of tetrabromobisphenol A (TBBPA) and decabromodiphenyl ether (Deca-BDE). Complete extraction of TBBPA was achieved using a combination of polar/non-polar solvent system (isopropanol/n-hexane) and high extraction temperatures (130 degrees C). Lower extraction yields were, however, obtained for Deca-BDE, due to its high molecular weight and its non-polar nature. The developed method was successfully applied to the screening of BFRs in standard plastic samples from waste electrical and electronic equipment (WEEE); TBBPA could be fully recovered, and Deca-BDE could be identified, together with minor order polybrominated diphenyl ether (PBDE) congeners.

  6. Determinants of plasma PCB, brominated flame retardants, and organochlorine pesticides in pregnant women and 3 year old children in The Norwegian Mother and Child Cohort Study.

    PubMed

    Caspersen, Ida Henriette; Kvalem, Helen Engelstad; Haugen, Margaretha; Brantsæter, Anne Lise; Meltzer, Helle Margrete; Alexander, Jan; Thomsen, Cathrine; Frøshaug, May; Bremnes, Nanna Margrethe Bruun; Broadwell, Sharon Lynn; Granum, Berit; Kogevinas, Manolis; Knutsen, Helle Katrine

    2016-04-01

    Exposure to persistent organic pollutants (POPs) during prenatal and postnatal life has been extensively studied in relation to adverse health effects in children. The aim was to identify determinants of the concentrations of polychlorinated biphenyls (PCBs), brominated flame retardants (polybrominated diphenyl ethers, PBDEs; polybrominated biphenyl, PBB), and organochlorine pesticides (OCPs) in blood samples from pregnant women and children in The Norwegian Mother and Child Cohort Study (MoBa). Blood samples were collected from two independent subsamples within MoBa; a group of women (n=96) enrolled in mid-pregnancy during the years 2002-2008 and a group of 3 year old children (n=99) participating during 2010-2011. PCB congeners (74, 99, 138, 153, 180, 170, 194, 209, 105, 114, 118, 156, 157, 167, and 189), brominated flame retardants (PBDE-28, 47, 99, 100, 153, 154, and PBB-153), as well as the OCPs hexachlorobenzene (HCB), oxychlordane, 4,4'dichlorodiphenyltrichloroethane (DDT), and 4,4'dichlorodiphenyldichloroethylene (DDE) were measured in both pregnant women and children. Age, low parity, and low pre-pregnant BMI were the most important determinants of increased plasma concentrations of POPs in pregnant women. In 3 year old children, prolonged breastfeeding duration was a major determinant of increased POP concentrations. Estimated dietary exposure to PCBs during pregnancy was positively associated with plasma concentrations in 3 year old children, but not in pregnant women. Plasma concentrations were approximately 40% higher in children compared to pregnant women. Several factors associated with exposure and toxicokinetics, i.e. accumulation, excretion and transfer via breastmilk of POPs were the main predictors of POP levels in pregnant women and children. Diet, which is the main exposure source for these compounds in the general population, was found to predict PCB levels only among children. For the PBDEs, for which non-dietary sources are more important

  7. Brominated and chlorinated flame retardants in Lake Ontario, Canada, lake trout (Salvelinus namaycush) between 1979 and 2004 and possible influences of food-web changes.

    PubMed

    Ismail, Nargis; Gewurtz, Sarah B; Pleskach, Kerri; Whittle, D Michael; Helm, Paul A; Marvin, Chris H; Tomy, Gregg T

    2009-05-01

    Concentrations of non-polybrominated diphenyl ether (PBDE) brominated (hexabromocyclododecane [HBCD], 1,2-bis[2,4,6-tribromophenoxy]ethane [BTBPE], and pentabromoethylbenzene [PEB]) and chlorinated (Dechlorane Plus [DP] as well as short- and medium-chain chlorinated paraffins [SCCP and MCCP, respectively]) flame retardants were evaluated in archived Lake Ontario, Canada, lake trout (Salvelinus namaycush) samples collected between 1979 and 2004. Polybrominated diphenyl ethers also were analyzed to provide a point of reference for comparison to previous studies. Concentrations of the dominant PBDE congeners (BDEs 28, 47, 99, 100, 153, and 154) increased significantly from 1979 until the mid-1990s, then either leveled off or decreased significantly between 1998 and 2004, a result that corresponds to those of previous studies. In contrast, BDE 209 increased approximately fourfold between 1998 and 2004. The temporal trends of the non-PBDE flame retardants varied, with sum (sigma) HBCD and DP showing significant overall decreases; BTBPE, sigmaSCCP, and sigmaMCCP showing parabolic trends; and PEB showing no overall change during the study period. Because many of the non-PBDE chemicals may be used as replacements for penta- and octa-BDE mixtures, these results will provide a baseline to evaluate future usage patterns. Possible changes in food-web structure, evaluated through stable nitrogen isotopes (delta15N), may be influencing our interpretations of contaminant trends in lake trout and are hypothesized to be partially responsible for the observed decrease in concentrations of BDEs 28, 47, 99, 100, 153, and 154 between 1998 and 2004. Retrospective analyses evaluating temporal trends in stable isotope values at the base of the food web, however, are recommended to test this hypothesis further.

  8. 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.

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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, ...

  11. 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.

  12. 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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  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. Using the parallelogram approach to estimate human percutaneous bioavailability for novel & legacy brominated flame retardants

    EPA Science Inventory

    (This is an extended abstract. The following text was taken from the Discussion and Conclusion section.) Humans are frequently exposed to brominated flame retardants (BFRs), especially via dermal contact with contaminated dust. Human and rat skin data were integrated using a pa...

  16. Titanate Nanotubes Decorated Graphene Oxide Nanocomposites: Preparation, Flame Retardancy, and Photodegradation

    NASA Astrophysics Data System (ADS)

    Sang, Bin; Li, Zhi-wei; Li, Xiao-hong; Yu, Lai-gui; Zhang, Zhi-jun

    2017-07-01

    Most polymers exhibit high flammability and poor degradability, which restrict their applications and causes serious environmental problem like "white pollution." Thus, titanate nanotubes (TNTs) were adopted to decorate graphene oxide (GO) by a facile solution method to afford TNTs/GO nanocomposites with potential in improving the flame retardancy and photodegradability of flexible polyvinyl chloride (PVC). Results show that the as-prepared TNTs/GO can effectively improve the thermal stability and flame retardancy than TNTs and GO, especially, the peak heat release rate and total heat release were reduced by 20 and 29% with only 2.5 wt.% loading. And more, the TNTs/GO also improve the photodegradability of PVC compared with the neat PVC. The reasons can be attributed to synergistic flame-retardant and photocatalytic effects between TNTs and GO. The present research could contribute to paving a feasible pathway to constructing polymer-matrix composites with desired flame retardancy and photodegradability, thereby adding to the elimination of white pollution caused by polymers.

  17. Flame-retardant EPDM compounds containing phenanthrene to enhance radiation resistance

    NASA Astrophysics Data System (ADS)

    Chen, Jian; Huang, Wei; Jiang, Shu-Bin; Li, Xiao-Yan; An, You; Li, Chuang; Gao, Xiao-Ling; Chen, Hong-Bing

    2017-01-01

    Ethylene propylene diene monomer (EPDM) compounds with good flame-retardant and γ-ray radiation resistant properties were prepared by adding complex flame retardants and phenathrene. The resultant EPDM formulations have a long time to ignition (TTI >46 s), a low peak heat release rate (PHRR 341 kW/m2) and a high limited oxygen index (LOI >30). Effects of γ-ray radiation on the resultant flame-retardant EPDM was investigated. The formulated EPDM is a crosslinking dominated polymer under γ-ray radiation. The γ-ray radiation resistant property of EPDM was enhanced by adding phenanthrene. Elongation at break of EPDM formulated with phenanthrene could retain 91% after being irradiated to 0.3 MGy and still retains 40% elongation even after being irradiated to 0.9 MGy, which is much better the control. It is expected that the formulated flame-retardant and radiation resistant EPDM materials could meet the requirements for use in radiation environments.

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

    USDA-ARS?s Scientific Manuscript database

    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 ...

  19. Intumescent flame-retardant cotton produced by tannic acid and sodium hydroxide

    USDA-ARS?s Scientific Manuscript database

    This study showed that tannic acid can form intumescent flame-retardant coating on cotton nonwoven fabric with an aid of NaOH. Tannic acid alone altered the thermal patterns of the pyrolysis and combustion of cotton and increased the char yield, but its improvement in limiting oxygen index (LOI) wa...

  20. 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.

  1. Structural effect of phosphoramidate derivatives on the thermal and flame retardant behaviors of treated cotton cellulose

    USDA-ARS?s Scientific Manuscript database

    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...

  2. Structural effect of phosphorous-nitrogen containing flame retardant derivatives on thermal behaviors of treated cotton

    USDA-ARS?s Scientific Manuscript database

    The present research is aimed at studying the structural effect of two phosphoramidate derivatives such as Diethyl 3-hydroxypropylphosphoramidate and Dimethyl 3-hydroxypropylphosphoramidate as flame retardants (FRs) for cotton. These FRs were obtained in very high yield and purity by one step proced...

  3. 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...

  4. Flame retardants in the serum of pet dogs and in their food.

    PubMed

    Venier, Marta; Hites, Ronald A

    2011-05-15

    A previous study from our laboratory showed that pet cats had much higher serum levels of flame retardants compared to humans, despite sharing the same household environment. Dogs, on the other hand, are expected to have lower serum levels of flame retardants because they are metabolically better equipped to degrade these compounds. Thus, we hypothesized that dogs might be more similar to humans in their response to these environmental stressors and be better indicators of human exposures to these contaminants. Serum samples and their food were collected from 18 dogs and analyzed for PBDEs and other emerging flame retardants. The concentrations of PBDEs in dog serum and dog food averaged 1.8 ± 0.4 ng/g wet weight (ww) and 1.1 ± 0.2 ng/g ww, respectively. While the dog serum samples were dominated by the tetra to hepta BDE congeners, BDE-209 was the most abundant congener in the dog food. This difference in congener pattern was analyzed in terms of half-lives. Assuming food as the main exposure source, the average half-life in dog serum was 450 ± 170 days for the less brominated congeners and 2.3 ± 0.5 days for BDE-209. Dust was also considered as an additional exposure source, giving unreasonable residence times. In addition to PBDEs, other flame retardants, including Dechlorane Plus, decabromodiphenylethane, and hexabromocyclododecane, were identified in these samples.

  5. 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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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. ...

  8. 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...

  9. 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...

  10. Levels of Urinary Metabolites of Organophosphate Flame Retardants, TDCIPP, and TPHP, in Pregnant Women in Shanghai

    PubMed Central

    Ouyang, Fengxiu; Liu, Liangpo; Wang, Xu; Wang, Xia; Li, Yi-Ju; Murtha, Amy; Shen, Heqing; Zhang, Junfeng; Zhang, Jun Jim

    2016-01-01

    Flame retardants are widely used in consumer products to reduce their flammability. Previously used flame retardants have been sequentially banned due to their environmental and human toxicity. Currently, tris(1,3-dichloropropyl) phosphate (TDCIPP) and triphenyl phosphate (TPHP) are among the most commonly used flame retardants. TDCIPP and TPHP are reproductive toxins and have carcinogenic, neurotoxic, and endocrine-disrupting properties. Although high levels of TDCIPP and TPHP have been found in drinking water, seawater, and office air in China, data regarding human exposure are lacking. In this study, we assessed the level of urinary TPHP and TDCIPP metabolites (DPHP and BDCIPP, resp.) in a cohort of pregnant women (N = 23) from Shanghai, China, using liquid chromatography-tandem mass spectrometry. DPHP were detected in 100% urine samples, while only four urine samples had detectable level of BDCIPP in this cohort (17% detected). Geometric means of DPHP and BDCIPP concentrations were 1.1 ng/mL (interquartile range [IQR]: 0.6, 1.5 ng/mL) and 1.2 ng/mL (IQR: 0.6, 2.2 ng/mL), respectively. In this small cohort, urinary DPHP and BDCIPP levels were not significantly correlated with miscarriages, neonatal birthweight, gestational diabetes, or maternal age. These data suggest that exposure to TPHP is widespread, and they demonstrate the feasibility of using urinary biomarkers to measure exposures to modern flame-retardant chemicals. PMID:28115951

  11. 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...

  12. Mineralisation and primary biodegradation of aromatic organophosphorus flame retardants in activated sludge.

    PubMed

    Jurgens, Sharona S; Helmus, Rick; Waaijers, Susanne L; Uittenbogaard, Dirk; Dunnebier, Dorien; Vleugel, Melissa; Kraak, Michiel H S; de Voogt, Pim; Parsons, John R

    2014-09-01

    Halogen-free flame retardants (HFFRs), such as the aromatic organophosphorus flame retardants (OPFRs) triphenyl phosphate (TPHP), resorcinol bis(diphenylphosphate) (PBDPP) and bisphenol A bis(diphenylphosphate) (BPA-BDPP) have been proposed as potential replacements for brominated flame retardants in polymers and textiles. Although these OPFRs are already marketed, their environmental fate and effects are poorly characterised. The aim of this study was therefore to determine the mineralisation and primary biodegradation of these OPFRs by activated sludge. Mineralisation was monitored by measuring CO2 production by means of GC analysis, whereas primary biodegradation was monitored by LC-MS/MS analysis of the OPFRs and their potential metabolites. TPHP was biodegraded and mineralised most rapidly and achieved the requirement for ready biodegradability (60% of theoretical maximum mineralisation). Primary biodegradation was also rapid for PBDPP, but 60% mineralisation was not achieved within the time of the test, suggesting that transformation products of PBDPP may accumulate. Primary degradation of BPA-BDPP was very slow and very low CO2 production was also observed. Based on these results, TPHP and to a lesser extent PBDPP appear to be suitable replacements for the more environmentally persistent brominated flame retardants. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. 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...

  14. 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...

  15. Titanate Nanotubes Decorated Graphene Oxide Nanocomposites: Preparation, Flame Retardancy, and Photodegradation.

    PubMed

    Sang, Bin; Li, Zhi-Wei; Li, Xiao-Hong; Yu, Lai-Gui; Zhang, Zhi-Jun

    2017-12-01

    Most polymers exhibit high flammability and poor degradability, which restrict their applications and causes serious environmental problem like "white pollution." Thus, titanate nanotubes (TNTs) were adopted to decorate graphene oxide (GO) by a facile solution method to afford TNTs/GO nanocomposites with potential in improving the flame retardancy and photodegradability of flexible polyvinyl chloride (PVC). Results show that the as-prepared TNTs/GO can effectively improve the thermal stability and flame retardancy than TNTs and GO, especially, the peak heat release rate and total heat release were reduced by 20 and 29% with only 2.5 wt.% loading. And more, the TNTs/GO also improve the photodegradability of PVC compared with the neat PVC. The reasons can be attributed to synergistic flame-retardant and photocatalytic effects between TNTs and GO. The present research could contribute to paving a feasible pathway to constructing polymer-matrix composites with desired flame retardancy and photodegradability, thereby adding to the elimination of white pollution caused by polymers.

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

    Treesearch

    Sunghyun Nam; Brian D. Condon; Robert H. White; Qi Zhao; Fei Yao; Michael Santiago Cintrón

    2012-01-01

    Urea is well known to have a synergistic action with phosphorus-based flame retardants (FRs) in enhancing the FR performance of cellulosic materials, but the effect of urea on the thermal decomposition kinetics has not been thoroughly studied. In this study, the activation energy (Ea) for the thermal decomposition of greige...

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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 ...

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

    USDA-ARS?s Scientific Manuscript database

    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...

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

    USDA-ARS?s Scientific Manuscript database

    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...

  3. Using the parallelogram approach to estimate human percutaneous bioavailability for novel & legacy brominated flame retardants

    EPA Science Inventory

    (This is an extended abstract. The following text was taken from the Discussion and Conclusion section.) Humans are frequently exposed to brominated flame retardants (BFRs), especially via dermal contact with contaminated dust. Human and rat skin data were integrated using a pa...

  4. Brominated and phosphate flame retardants (FRs) in indoor dust from different microenvironments: Implications for human exposure via dust ingestion and dermal contact.

    PubMed

    Zheng, Xiaobo; Qiao, Lin; Covaci, Adrian; Sun, Runxia; Guo, Huiying; Zheng, Jing; Luo, Xiaojun; Xie, Qilai; Mai, Bixian

    2017-10-01

    Indoor dust has been widely used to monitor flame retardants (FRs) in indoor environment, but most studies only focused on floor dust. In the present study, FRs were examined in indoor dust from different locations. Dust from air conditioner (AC) filters, beddings, floor, and windows in bedrooms, and dust from AC filters, printer table surface, computer table surface, floor, and windows in offices were collected, respectively. Polybrominated diphenyl ether congener 209 (BDE 209) and decabromodiphenyl ethane (DBDPE) were the most abundant brominated flame retardants (BFRs), and tris(chloroisopropyl) phosphate (TCIPP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP), and triphenyl phosphate (TPHP) were the most abundant phosphate flame retardants (PFRs). In bedrooms, the AC filter dust had the highest median levels of BDE 209 (536 ng/g) and DBDPE (2720 ng/g), while bed dust had the highest median levels of ΣPFRs (2750 ng/g) among dust samples. In offices, printer table dust had higher median levels of BDE 209 (1330 ng/g), DBDPE (8470 ng/g), and ΣPFRs (11,000 ng/g) than those in other dust samples. The high dust ingestion values of BDE 209, DBDPE, and individual PFR were 0.28, 1.20, and <0.01-0.32 ng/kg bw/day and 7.37, 31.2, and <0.01-4.54 ng/kg bw/day for BDE 209, DBDPE, and individual PFR for adults and toddlers, respectively. The high dermal exposure values of individual PFR during sleeping were <0.01-0.23 and <0.01-0.36 ng/kg bw/day for adults and toddlers, respectively. More human exposure pathways other than dust ingestion should be considered, such as the dermal contact with beddings and furniture. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. 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...

  6. 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...

  7. 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...

  8. 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 ...

  9. 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...

  10. 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...

  11. 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 ...

  12. 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...

  13. 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...

  14. 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...

  15. Encapsulation of flame retardants for application in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Huang, Pei-Hsuan; Chang, Shinn-Jen; Li, Chia-Chen

    2017-01-01

    In this investigation, improvements in the fire-extinguishing behavior of the cathode/electrolyte mixture are achieved using the lithium iron phosphate cathode with a pre-embedded flame retardant. To minimize the possible negative effects of the embedded retardant on the electrochemical properties of the cathode, two commercially available flame retardants, triphenyl phosphate (TPP) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (DOPO), are encapsulated by chemically stable poly(urea-formaldehyde) and denoted as en-TPP and en-DOPO, respectively. The additions of en-TPP and en-DOPO improve the dispersion of the cathode slurry, while the additions of bare TPP and DOPO cause severe powder aggregation and poor electrochemical conductivity. The self-extinguishing efficiency of the cathode/electrolyte mixture is greatly increased by 30%-40% without sacrificing the electrochemical performance of the cathodes when 15 wt% of en-TPP is added.

  16. 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

    2016-09-05

    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.

  17. Characterization of heavy metals and brominated flame retardants in the indoor and outdoor dust of e-waste workshops: implication for on-site human exposure.

    PubMed

    Xu, Feng; Liu, Yangcheng; Wang, Junxia; Zhang, Gang; Zhang, Wei; Liu, Lili; Wang, Jinfu; Pan, Bishu; Lin, Kuangfei

    2015-04-01

    Forty-four indoor and outdoor dust samples were collected from e-waste workshops and were analyzed to characterize the heavy metals and brominated flame retardants (BFRs) as well as on-site human exposure. The results showed that the most abundant Polybrominated diphenyl ethers (PBDE) congener from three sites was deca-BDE, and it was penta-BDE for the other site. A significant and positive association was found between BDE-209 and decabromodiphenyl ethane (DBDPE). The high percentage of nona-BDE indicated the debromination of deca-BDE during e-waste recycling. The ratio comparison of BDE-47 to (BDE-100 + BDE-99) indicated that the outdoor dust went through more physiochemical processes. The enrichment factors for Cu and Pb were high in both the indoor and outdoor samples. Cd significantly exceeded the Chinese soil guideline grade III. The PCA results combined with the enrichment factor (EF) values suggested common sources and behaviours of Cu, Pb and Sb in the indoor dust. Co, Cr, Ni, Zn and Mn in the outdoor samples were more likely affected by crust. Strong correlations were found only for Pb and Sb with polybrominated diphenyl ethers (PBDEs). The hazard index for on-site human exposure to Pb was at a chronic risk. Despite the low deleterious risk of BFRs, concern should be given to DBDPE; the chronic toxicity of which is not known.

  18. Improved derivatization protocol for simultaneous determination of alkylphenol ethoxylates and brominated flame retardants followed by gas chromatography-mass spectrometry analyses.

    PubMed

    Chokwe, T B; Okonkwo, J O; Sibali, L L; Ncube, E J

    2014-01-01

    An improved derivatization protocol for the simultaneous determination of alkylphenol ethoxylates and brominated flame retardants with heptafluorobutyric anhydride under triethylamine amine base was investigated. The derivatization reaction was completed in 30 min at 50 °C using hexane as solvent. Under these conditions, it was observed that alkylphenol ethoxylates and tetrabromobisphenol A were derivatized successfully in the presence of hexabromocyclododecane, lower congeners of polybrominated biphenyls and polybrominated diphenyl ethers. The improved protocol was applied to the recover of the analytes of interest from a simulated water sample after solid phase extraction. The recoveries achieved were above 60%. The limit of detection and limit of quantification ranged from 0.01-0.20 and 0.05-0.66 μg L(-1), respectively. The improved derivatization procedure was also successfully applied to determine trace amounts of these compounds in environmental water samples. The concentrations of the targeted analytes from the environmental samples were determined from limit of quantification. The levels of the targeted compounds in the environmental samples ranged from nd-7.63 ±2.83 μg L(-1).

  19. 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.

  20. 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

  1. 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 toxic