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Sample records for additive brominated flame

  1. Polyfunctional epoxies - Different molecular weights of brominated polymeric additives as flame retardants in graphite composites

    NASA Technical Reports Server (NTRS)

    Nir, Z.; Gilwee, W. J.; Kourtides, D. A.; Parker, J. A.

    1983-01-01

    The imparting of flame retardancy to graphite-reinforced composites without incurring mechanical property deterioration is investigated for the case of an experimental, trifunctional epoxy resin incorporating brominated polymeric additives (BPAs) of the diglycidyl type. Such mechanical properties as flexural strength and modulus, and short beam shear strength, were measured in dry and in hot/wet conditions, and the glass transition temperature, flammability, and water absorption were measured and compared with nonbromilated systems. Another comparison was made with a tetrafunctional epoxy system. The results obtained are explained in terms of differences in the polymeric backbone length of the bromine carrier polymer. BPAs are found to be a reliable bromine source for fire inhibition in carbon-reinforced composites without compromise of mechanical properties.

  2. 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...

  3. A new brominated polymeric additive for flame retardant glass-filled polybutylene terephthalate

    NASA Technical Reports Server (NTRS)

    Nir, Z.; Kourtides, D. A.; Parker, J. A.; Bar-Yaacov, Y.; Minke, R.; Touval, I.

    1982-01-01

    Attention is called to the undesirable effects (poor ultraviolet light stability and blooming) sometimes introduced by brominated flame retarders. A brominated polymeric additive (BPA) with little or none of these undesirable side effects is compared with decabromobiphenyl oxide (DBBPO). The additive bears the product name F-2300. It is found to be more easily dispersed than DBBPO. The F-2300 is as effective as the DBBPO in the oxygen index test. The improved efficiency of the F-2300 may be explained by its better dispersion in polybutylene terephthalate (PBT). Glass-filled PBT containing F-2300 is found to be more resistant to UV degradation than DBBPO-containing formulas. Formulations with F-2300 therefore have a longer useful outdoor life. F-2300 is a diglycidyl-type polymer containing 50 percent aromatically bound bromine. Its melting point is 112 C, and it is stable up to 372 C. It is pointed out that since its melts at a relatively low temperature, it can be introduced into the formulation as a large agglomerate and still be dispersed evenly throughout the polymer.

  4. 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...

  5. 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...

  6. 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...

  7. 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...

  8. 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...

  9. 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...

  10. 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...

  11. Brominated flame retardants as food contaminants

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  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. 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

  14. Rubberized, Brominated Epoxies

    NASA Technical Reports Server (NTRS)

    Gilwee, W.; Kourtides, D.; Parker, J.; Nir, Z.

    1985-01-01

    Graphite/epoxy composite materials made with resins containing bromine and rubber additives. New composites tougher and more resistant to fire. Flame resistance increased by introducing bromine via commercial brominated flame-retartant polymeric additives.

  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. 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.

  17. 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.

  18. 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.

  19. 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.

  20. Discrimination of hexabromocyclododecane from new polymeric brominated flame retardant in polystyrene foam by nuclear magnetic resonance.

    PubMed

    Jeannerat, Damien; Pupier, Marion; Schweizer, Sébastien; Mitrev, Yavor Nikolaev; Favreau, Philippe; Kohler, Marcel

    2016-02-01

    Hexabromocyclododecane (HBCDD) is a brominated flame retardant (BFR) and major additive to polystyrene foam thermal insulation that has recently been listed as a persistent organic pollutant by the Stockholm Convention. During a 2013/2014 field analytical survey, we measured HBCDD content ranging from 0.2 to 2.4% by weight in 98 polystyrene samples. Liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) analyses indicated that expandable (EPS) and extruded (XPS) polystyrene foams significantly differed in the α/γ HBCDD isomer ratio, with a majority of α and γ isomers in XPS and EPS, respectively. Interestingly, this technique indicated that some recent materials did not contain HBCDD, but demonstrated bromine content when analysed with X-ray fluorescence (XRF). Further investigation by Nuclear Magnetic Resonance (NMR) was able to discriminate between the BFRs present. In addition to confirming the absence or presence of HBCDD in polystyrene samples, high-field NMR spectroscopy provided evidence of the use of brominated butadiene styrene (BBS) as copolymer in the production of polystyrene. Use of this alternative flame retardant is expected to cause fewer health and environmental concerns. Our results highlight a trend towards the use of copolymerized BFRs as an alternative to HBCDD in polystyrene foam boards. In addition to providing a rapid NMR method to identify polymeric BFR, our analytical approach is a simple method to discriminate between flame-retardants in polystyrene foam insulating materials.

  1. Analysis and occurrence of emerging brominated flame retardants in the Llobregat River basin

    NASA Astrophysics Data System (ADS)

    Guerra, Paula; Eljarrat, Ethel; Barceló, Damià

    2010-03-01

    SummaryIn response to increasing international regulations on brominated flame retardants (BFR) formulations, alternative additive flame retardants for achieving commercial product fire safety standards are being developed and used. Some of these non-BDE (brominated diphenyl ethers) BFRs are pentabromoethylbenzene (PBEB), hexabromobenzene (hexaBBz), and decabromodiphenylethane (deBDethane). The present study investigated the occurrence of these emerging BFRs, together with 38 BDE congeners (from di- to deca-BDE) in sediments sampled from different points along Llobregat basin (Spain) in three different sampling campaigns between 2005 and 2006. Emerging BFRs were detected in all sediment samples analyzed, at concentrations ranging from 3.1 to 9.6 ng/g for PBEB, from 0.4 to 2.4 ng/g for hexaBBz and from 4.8 to 23 ng/g for deBDethane. These levels are lower than concentrations obtained for PBDEs (from nd to 82 ng/g).

  2. 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.

  3. 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

  4. 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.

  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) ...

  6. 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.

  7. 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.

  8. 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

  9. 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.

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

    PubMed

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

    2009-03-01

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

  11. 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.

  12. Thermal Recycling of Brominated Flame Retardants with Fe2O3.

    PubMed

    Altarawneh, Mohammednoor; Ahmed, Oday H; Jiang, Zhong-Tao; Dlugogorski, Bogdan Z

    2016-08-04

    Plastics containing brominated flame retardants (BFRs) constitute the major fraction of nonmetallic content in e-waste. Co-pyrolysis of BFRs with hematite (Fe2O3) represents a viable option for the thermal recycling of BFRs. Consensus of experimental findings confirms the excellent bromine fixation ability of Fe2O3 and the subsequent formation of iron bromides. This contribution provides a comprehensive mechanistic account of the primary reactions between a cluster model of Fe2O3 and major bromine-bearing products from the decomposition of tetrabromobisphenol A (TBBA), the most commonly deployed BFR. We estimate the thermo-kinetic parameters for interactions of Fe2O3 with HBr, brominated alkanes and alkenes, bromobenzene, and bromophenol. Dissociative addition of HBr at a Fe-O bond proceeds through a trivial barrier of 8.2 kcal/mol with fitted parameters in the Arrhenius equation of k(T) = 7.96 × 10(11) exp(-6400/RT) s(-1). The facile and irreversible nature for HBr addition to Fe2O3 accords with the experimentally reported 90% reduction in HBr emission when Fe2O3 interacts with TBBA pyrolysates. A detailed kinetic analysis indicates that, transformation of Fe2O3 into iron bromides and oxybromides occurs via successive addition of HBr to Fe(Br)-O(H) entities. Elimination of a water molecule proceeds through an intramolecular H transfer. A direct elimination one-step mechanism operates in the dehydrohalogenation of bromoethane into ethene over Fe2O3. Dissociative decomposition and direct elimination channels assume comparable reaction rates in formation of acetylene from vinyl bromide. Results from this study provide an atomic-based insight into a promising thermal recycling route of e-waste.

  13. New brominated flame retardants and their metabolites as activators of the pregnane X receptor.

    PubMed

    Gramec Skledar, Darja; Tomašič, Tihomir; Carino, Adriana; Distrutti, Eleonora; Fiorucci, Stefano; Peterlin Mašič, Lucija

    2016-09-30

    The present study investigated the activities on different nuclear receptors of the new brominated flame retardants 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB) and bis(2-ethylhexyl) 2,3,4,5-tetrabromophthalate (TBPH), and their main carboxylic acid metabolites 2,3,4,5-tetrabromobenzoic acid (TBBA) and mono(2-ethylhexyl) tetrabromophthalate (TBMEPH). None of selected chemicals exhibited marked activity towards PPARα and PPARγ by the use of transactivation assays in HepG2 cells transfected with peroxisome proliferator-activated receptors. In contrast, selected flame retardants all exhibited potent agonist activity on pregnane X receptor (PXR), with EC50 values of 5.5μM for TBPH and 2.0μM for its metabolite TBMEPH. Molecular docking of TBPH and TBMEPH to the PXR ligand binding site revealed similar interactions, with differences only for conformation and orientation of the alkyl chains. Additionally, TBPH showed antagonist activity on PXR (IC50, 13.9μM). Moreover, there was significant up-regulation of CYP3A4 expression via PXR activation for TBB and TBPH and their metabolites. Induction of CYP3A4 might cause undesired drug-drug interactions, lower bioavailability of pharmaceutical drugs, higher formation of reactive toxic metabolites, or enhanced elimination of endogenous hormones, such as T3/T4, to lead to endocrine disruption. These data provide new and important insights into the toxicity of these new polybrominated flame retardants, TBB and TBPH, and their metabolites.

  14. Photochemical degradation of a brominated flame retardant (tetrabromobisphenol A) in ice under field and laboratory conditions

    NASA Astrophysics Data System (ADS)

    Waligroski, G.; Grannas, A. M.

    2013-12-01

    Studies of brominated flame retardants have raised awareness of their potential environmental impact as toxic compounds. Because these compounds are now globally distributed, including in the Polar Regions, it is important to assess their potential fate in the environment. It has been shown that active photochemistry occurs in sunlit snow and ice, but there is little information regarding potential photochemical degradation of brominated flame retardants in snow and ice. The purpose of this research is to investigate the direct and indirect photochemical transformation pathways of a widely used brominated flame retardant, tetrabromobisphenol A (TBBPA). We have conducted field-based experiments in Barrow, Alaska to investigate the potential photochemical degradation of TBBPA in snow and ice under environmentally-relevant conditions. Field-based results show that TBBPA is efficiently degraded under direct photolysis conditions in frozen aqueous samples under natural Barrow sunlight. In aqueous solution the light absorption properties of TBBPA are pH dependent. Therefore, the photodegradation of TBBPA in snow and ice will be highly pH dependent. Reactions that are pH dependent may be affected by the nature of the liquid-like layers in snow/ice as well as the presence of other solutes that may indirectly affect the local pH experienced by TBBPA in snow and ice samples. In order to establish how the effective pH of liquid-like regions in ice might impact the degradation of TBBPA, various salts (sodium chloride, sodium fluoride, sodium bromide, ammonium chloride, ammonium acetate and ammonium sulfate) were added to aqueous solutions of TBBPA. Upon freezing, these different salts will induce pH differences in the liquid-like regions of the sample due to a phenomenon known as the freezing potential. Observed reactivity differences upon addition of these salts will be evaluated and discussed. Additionally, the presence of natural dissolved organic matter (DOM), an effective

  15. 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...

  16. 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...

  17. 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

  18. 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.

  19. Bromine

    USGS Publications Warehouse

    Ober, Joyce A.

    2011-01-01

    All U.S. production of bromine in 2010 came from underground brines in Arkansas. It was the leading mineral commodity produced in the state in terms of value. Albemarle Corp. and Chemtura Corp. recovered bromine.

  20. 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.

  1. Bromine

    USGS Publications Warehouse

    Ober, J.A.

    2013-01-01

    The element bromine is found principally as a dissolved species in seawater, evaporitic (salt) lakes and underground brines associated with petroleum deposits. Seawater contains about 65 parts per million of bromine or an estimated 907 Gt (100 trillion st). In the Middle East, the highly saline waters of the Dead Sea are estimated to contain 907 Mt (1 billion st) of bromine. Bromine also may be recovered from seawater as a coproduct during evaporation to produce salt.

  2. Bromine

    USGS Publications Warehouse

    Ober, Joyce A.

    2012-01-01

    The element bromine is found principally as a dissolved species in seawater, evaporitic (salt) lakes and underground brines associated with petroleum deposits. Seawater contains about 65 parts per million of bromine or an estimated 100 Tt (110 trillion st). In the Middle East, the highly saline waters of the Dead Sea are estimated to contain 1 Gt (1.1billion st) of bromine. Bromine is also recovered from seawater as a coproduct during evaporation to produce salt.

  3. 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.

  4. Bromine

    USGS Publications Warehouse

    Apodaca, Lori E.

    2010-01-01

    The entire U.S. production of bromine in 2009 came from underground brines in Arkansas, where it was the leading mineral commodity produced in terms of value. Two companies, Albermarle Corp. and Chemtura Corp., were responsible for bromine recovery. Worldwide, the United States is still the leading producer. However, U.S. dominance has decreased, as countries like China, Israel, Japan and Jordan have strengthened their positions as world producers of elemental bromine.

  5. 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

  6. Distribution of copper, silver and gold during thermal treatment with brominated flame retardants

    SciTech Connect

    Oleszek, Sylwia; Grabda, Mariusz; Shibata, Etsuro; Nakamura, Takashi

    2013-09-15

    Highlights: • Copper, silver and gold during thermal treatment with brominated flame retardants. • Distribution of copper, silver and gold during thermal processing. • Thermodynamic considerations of the bromination reactions. - Abstract: The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition. In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000 °C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is

  7. 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.

  8. Characterization of brominated flame retardants in construction and demolition waste components: HBCD and PBDEs.

    PubMed

    Duan, Huabo; Yu, Danfeng; Zuo, Jian; Yang, Bo; Zhang, Yukui; Niu, Yongning

    2016-12-01

    The vast majority of construction material is inert and can be managed as nonhazardous. However, structures may have either been built with some environmentally unfriendly substances such as brominated flame retardants (BFRs), or have absorbed harmful elements such as heavy metals. This study focuses on end-of-life construction materials, i.e. construction and demolition (C&D) waste components. The aim was to characterize the concentration of extremely harmful substances, primarily BFRs, including hexabromocyclododecane (HBCD) and polybrominateddiphenyl ethers (PBDEs). Results revealed extremely high contents of HBCD and PBDEs in typical C&D waste components, particularly polyurethane foam materials. Policies should therefore be developed for the proper management of C&D waste, with priority for POP-containing debris. The first priority is to develop a classification system and procedures to separate out the harmful materials for more extensive processing. Additionally, identification and quantification of the environmental implications associated with dumping-dominated disposal of these wastes are required. Finally, more sustainable materials should be selected for use in the construction industry.

  9. Vapor pressure of three brominated flame retardants determined by using the Knudsen effusion method.

    PubMed

    Fu, Jinxia; Suuberg, Eric M

    2012-03-01

    Brominated flame retardants (BFRs) have been used in a variety of consumer products in the past four decades. The vapor pressures for three widely used BFRs, that is, tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), and octabromodiphenyl ethers (octaBDEs) mixtures, were determined using the Knudsen effusion method and compared with those of decabromodiphenyl ether (BDE209). The values measured extrapolated to 298.15 K are 8.47 × 10⁻⁹, 7.47 × 10⁻¹⁰, and 2.33 × 10⁻⁹  Pa, respectively. The enthalpies of sublimation for these BFRs were estimated using the Clausius-Clapeyron equation and are 143.6 ± 0.4, 153.7 ± 3.1, and 150.8 ± 3.2 kJ/mole, respectively. In addition, the enthalpies of fusion and melting temperatures for these BFRs were also measured in the present study.

  10. 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.

  11. Microbial degradation of the brominated flame retardant TBNPA by groundwater bacteria: laboratory and field study.

    PubMed

    Balaban, Noa; Bernstein, Anat; Gelman, Faina; Ronen, Zeev

    2016-08-01

    In the present study, the biodegradation of the brominated flame retardant tribromoneopentylalcohol (TBNPA) by a groundwater enrichment culture was investigated using a dual carbon ((13)C/(12)C)- bromine ((81)Br/(79)Br) stable isotope analysis. An indigenous aerobic bacterial consortium was enriched from the polluted groundwater underlying an industrial site in the northern Negev Desert, Israel, where TBNPA is an abundant pollutant. Aerobic biodegradation was shown to be rapid, with complete debromination within a few days, whereas anaerobic biodegradation was not observed. Biodegradation under aerobic conditions was accompanied by a significant carbon isotope effect with an isotopic enrichment factor of ɛCbulk = -8.8‰ ± 1.5‰, without any detectable bromine isotope fractionation. It was found that molecular oxygen is necessary for biodegradation to occur, suggesting an initial oxidative step. Based on these results, it was proposed that H abstraction from the C-H bond is the first step of TBNPA biodegradation under aerobic conditions, and that the C-H bond cleavage results in the formation of unstable intermediates, which are rapidly debrominated. A preliminary isotopic analysis of TBNPA in the groundwater underlying the industrial area revealed that there are no changes in the carbon and bromine isotope ratio values downstream of the contamination source. Considering that anoxic conditions prevail in the groundwater of the contaminated site, the lack of isotope shifts in TBNPA indicates the lack of TBNPA biodegradation in the groundwater, in accordance with our findings.

  12. Influence of Antimony-Halogen Additives on Flame Propagation.

    PubMed

    Babushok, Valeri I; Deglmann, Peter; Krämer, Roland; Linteris, Gregory T

    2017-01-01

    A kinetic model for flame inhibition by antimony-halogen compounds in hydrocarbon flames is developed. Thermodynamic data for the relevant species are assembled from the literature, and calculations are performed for a large set of additional species of Sb-Br-C-H-O system. The main Sb- and Br-containing species in the combustion products and reaction zone are determined using flame equilibrium calculations with a set of possible Sb-Br-C-H-O species, and these are used to develop the species and reactions in a detailed kinetic model for antimony flame inhibition. The complete thermodynamic data set and kinetic mechanism are presented. Laminar burning velocity simulations are used to validate the mechanism against available data in the literature, as well as to explore the relative performance of the antimony-halogen compounds. Further analysis of the premixed flame simulations has unraveled the catalytic radical recombination cycle of antimony. It includes (primarily) the species Sb, SbO, SbO2, and HOSbO, and the reactions: Sb+O+M=SbO+M; Sb+O2+M=SbO2+M; SbO+H=Sb+OH; SbO+O=Sb+O2; SbO+OH+M=HOSbO+M; SbO2+H2O=HOSbO+OH; HOSbO+H=SbO+H2O; SbO+O+M=SbO2+M. The inhibition cycles of antimony are shown to be more effective than those of bromine, and intermediate between the highly effective agents CF3Br and trimethylphosphate. Preliminary examination of a Sb/Br gas-phase system did not show synergism in the gas-phase catalytic cycles (i.e., they acted essentially independently).

  13. Advances in Instrumental Analysis of Brominated Flame Retardants: Current Status and Future Perspectives

    PubMed Central

    2014-01-01

    This review aims to highlight the recent advances and methodological improvements in instrumental techniques applied for the analysis of different brominated flame retardants (BFRs). The literature search strategy was based on the recent analytical reviews published on BFRs. The main selection criteria involved the successful development and application of analytical methods for determination of the target compounds in various environmental matrices. Different factors affecting chromatographic separation and mass spectrometric detection of brominated analytes were evaluated and discussed. Techniques using advanced instrumentation to achieve outstanding results in quantification of different BFRs and their metabolites/degradation products were highlighted. Finally, research gaps in the field of BFR analysis were identified and recommendations for future research were proposed. PMID:27433482

  14. 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.

  15. Flame retardant brominated styrene-based polymers. VI. Synthesis and characterization of dibromostyrene graft latices

    SciTech Connect

    Favstritsky, N.A.; Wang, J.L.

    1995-12-01

    Nine dibromostyrene-grafted commercial lattices were prepared in 8 oz bottles by an emulsion polymerization technique. Proper selection of lattices used in conjunction with the dibromostyrene monomer enables production of flame retardant latex products useful in a wide range of coating applications. The prime factor to be considered in the choice of a latex or a latex mixture to be grafted is the glass transition temperature(s) of the polymer(s) in the final latex desired. Lattices chosen for grafting are commercial lattices, such as Rhoplex HA-24 and HA-8, Hystretch V-29, Airflex 465, 4500, 4514 and 4530, Pliolite SBR latex and polybutadiene latex. The graft latex was characterized in terms of glass transition temperature, solids content, bromine content, grafted dibromostyrene and flame retardancy.

  16. Fabric phase sorptive extraction: Two practical sample pretreatment techniques for brominated flame retardants in water.

    PubMed

    Huang, Guiqi; Dong, Sheying; Zhang, Mengfei; Zhang, Haihan; Huang, Tinglin

    2016-09-15

    Sample pretreatment is the critical section for residue monitoring of hazardous pollutants. In this paper, using the cellulose fabric as host matrix, three extraction sorbents such as poly (tetrahydrofuran) (PTHF), poly (ethylene glycol) (PEG) and poly (dimethyldiphenylsiloxane) (PDMDPS), were prepared on the surface of the cellulose fabric. Two practical extraction techniques including stir bar fabric phase sorptive extraction (stir bar-FPSE) and magnetic stir fabric phase sorptive extraction (magnetic stir-FPSE) have been designed, which allow stirring of fabric phase sorbent during the whole extraction process. In the meantime, three brominated flame retardants (BFRs) [tetrabromobisphenol A (TBBPA), tetrabromobisphenol A bisallylether (TBBPA-BAE), tetrabromobisphenol A bis(2,3-dibromopropyl)ether (TBBPA-BDBPE)] in the water sample were selected as model analytes for the practical evaluation of the proposed two techniques using high-performance liquid chromatography (HPLC). Moreover, various experimental conditions affecting extraction process such as the type of fabric phase, extraction time, the amount of salt and elution conditions were also investigated. Due to the large sorbent loading capacity and unique stirring performance, both techniques possessed high extraction capability and fast extraction equilibrium. Under the optimized conditions, high recoveries (90-99%) and low limits of detection (LODs) (0.01-0.05 μg L(-1)) were achieved. In addition, the reproducibility was obtained by evaluating the intraday and interday precisions with relative standard deviations (RSDs) less than 5.1% and 6.8%, respectively. The results indicated that two pretreatment techniques were promising and practical for monitoring of hazardous pollutants in the water sample. Due to low solvent consumption and high repeated use performance, proposed techniques also could meet green analytical criteria.

  17. 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.

  18. 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.

  19. Removal of brominated flame retardant from electrical and electronic waste plastic by solvothermal technique.

    PubMed

    Zhang, Cong-Cong; Zhang, Fu-Shen

    2012-06-30

    Brominated flame retardants (BFRs) in electrical and electronic (E&E) waste plastic are toxic, bioaccumulative and recalcitrant. In the present study, tetrabromobisphenol A (TBBPA) contained in this type of plastic was tentatively subjected to solvothermal treatment so as to obtain bromine-free plastic. Methanol, ethanol and isopropanol were examined as solvents for solvothermal treatment and it was found that methanol was the optimal solvent for TBBPA removal. The optimum temperature, time and liquid to solid ratio for solvothermal treatment to remove TBBPA were 90°C, 2h and 15:1, respectively. After the treatment with various alcohol solvents, it was found that TBBPA was finally transferred into the solvents and bromine in the extract was debrominated catalyzed by metallic copper. Bisphenol A and cuprous bromide were the main products after debromination. The morphology and FTIR properties of the plastic were generally unchanged after the solvothermal treatment indicating that the structure of the plastic maintained after the process. This work provides a clean and applicable process for BFRs-containing plastic disposal.

  20. 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

  1. Oxidation of flame retardant tetrabromobisphenol a by aqueous permanganate: reaction kinetics, brominated products, and pathways.

    PubMed

    Pang, Su-Yan; Jiang, Jin; Gao, Yuan; Zhou, Yang; Huangfu, Xiaoliu; Liu, Yongze; Ma, Jun

    2014-01-01

    In this work, the most widely used brominated flame retardant tetrabromobisphenol A (TBrBPA) was shown to exhibit appreciable reactivity toward potassium permanganate [Mn(VII)] in water over a wide pH range of 5-10 with the maxima of second-order rate constants (kMn(VII) = 15-700 M(-1) s(-1)) at pH near its pKa values (7.5/8.5). A novel precursor ion scan (PIS) approach using negative electrospray ionization-triple quadrupole mass spectrometry (ESI-QqQMS) was adopted and further optimized for fast selective detection of brominated oxidation products of TBrBPA by Mn(VII). By setting PIS of m/z 79 and 81, two major products (i.e., 4-(2-hydroxyisopropyl)-2,6-dibromophenol and 4-isopropylene-2,6-dibromophenol) and five minor ones (including 2,6-dibromophenol, 2,6-dibromo-1,4-benzoquinone, and three dimers) were detected and suggested with chemical structures from their product ion spectra and bromine isotope patterns. Reaction pathways mainly involving the initial one-electron oxidation of TBrBPA and subsequent release and further reactions of 2,6-dibromo-4-isopropylphenol carbocation intermediate were proposed. The effectiveness of Mn(VII) for treatment of TBrBPA in real waters was confirmed. It is important to better understand the reactivity and toxicity of primary brominated products before Mn(VII) can be applied for treatment of TBrBPA-contaminated wastewater and source water.

  2. Assessing the persistence, bioaccumulation potential and toxicity of brominated flame retardants: data availability and quality for 36 alternative brominated flame retardants.

    PubMed

    Stieger, Greta; Scheringer, Martin; Ng, Carla A; Hungerbühler, Konrad

    2014-12-01

    Polybrominated diphenylethers (PBDEs) and hexabromocyclododecane (HBCDD) are major brominated flame retardants (BFRs) that are now banned or under restrictions in many countries because of their persistence, bioaccumulation potential and toxicity (PBT properties). However, there is a wide range of alternative BFRs, such as decabromodiphenyl ethane and tribromophenol, that are increasingly used as replacements, but which may possess similar hazardous properties. This necessitates hazard and risk assessments of these compounds. For a set of 36 alternative BFRs, we searched 25 databases for chemical property data that are needed as input for a PBT assessment. These properties are degradation half-life, bioconcentration factor (BCF), octanol-water partition coefficient (Kow), and toxic effect concentrations in aquatic organisms. For 17 of the 36 substances, no data at all were found for these properties. Too few persistence data were available to even assess the quality of these data in a systematic way. The available data for Kow and toxicity show surprisingly high variability, which makes it difficult to identify the most reliable values. We propose methods for systematic evaluations of PBT-related chemical property data that should be performed before data are included in publicly available databases. Using these methods, we evaluated the data for Kow and toxicity in more detail and identified several inaccurate values. For most of the 36 alternative BFRs, the amount and the quality of the PBT-related property data need to be improved before reliable hazard and risk assessments of these substances can be performed.

  3. The Addition of Bromine to 1,2-Diphenylethene

    ERIC Educational Resources Information Center

    Amburgey-Peters, Judith C.; Haynes, Leroy W.

    2005-01-01

    The bromination of 1,2-diphenylethene, using a variety of solvents and brominating agents, can be used in both introductory and advanced organic chemistry courses. The reactions can be used to illustrate the effects of changing solvents and reagents, as well as to reveal interesting aspects of organic reaction mechanisms.

  4. 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.

  5. 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.

  6. 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

  7. Distribution of copper, silver and gold during thermal treatment with brominated flame retardants.

    PubMed

    Oleszek, Sylwia; Grabda, Mariusz; Shibata, Etsuro; Nakamura, Takashi

    2013-09-01

    The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition. In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000°C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is resistant to HBr and remains unchanged in the residue.

  8. Exposure of Female Rats to an Environmentally Relevant Mixture of Brominated Flame Retardants Targets the Ovary, Affecting Folliculogenesis and Steroidogenesis.

    PubMed

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

    2016-01-01

    Brominated flame retardants (BFRs) are incorporated into various consumer products to prevent flame propagation. These compounds leach into the domestic environment, resulting in chronic exposure and contamination. Pregnancy failure is associated with high levels of BFRs in human follicular fluid, raising serious questions regarding their impact on female reproductive health. The goal of this study is to elucidate the effects of an environmentally relevant BFR mixture on female rat ovarian functions (i.e., folliculogenesis and steroidogenesis). A BFR dietary mixture formulated to mimic the relative BFR congener levels in North American house dust was administered to adult female Sprague-Dawley rats from 2 to 3 wk before mating until Gestational Day 20; these diets were designed to deliver nominal doses of 0, 0.06, 20, or 60 mg/kg/day of the BFR mixture. Exposure to BFRs triggered an approximately 50% increase in the numbers of preantral and antral follicles and an enlargement of the antral follicles in the ovaries of the dams. A significant reduction in the expression of catalase, an antioxidant enzyme, and downregulation of the expression of insulin-like factor 3 (Insl3) and 17alpha-hydroxylase (Cyp17a1) were observed in the ovary. In addition, BFR exposure affected steroidogenesis; we observed a significant decrease in circulating 17-hydroxypregnenolone and an increase in testosterone concentrations in BFR-exposed dams. Thus, BFRs target ovarian function in the rat, adversely affecting both folliculogenesis and steroidogenesis.

  9. Deposition of brominated flame retardants to the Devon Ice Cap, Nunavut, Canada.

    PubMed

    Meyer, Torsten; Muir, Derek C G; Teixeira, Camilla; Wang, Xiaowa; Young, Teresa; Wania, Frank

    2012-01-17

    Brominated flame retardants (BFRs) can be transported to Arctic regions via atmospheric long-range transport, however, relatively little is known about their deposition to terrestrial environments. Snow cores from the Devon Ice Cap in Nunavut, Canada served to determine the recent depositional trends of BFRs. Snow pits were dug in 2005, 2006, and 2008. Dating using annual snow accumulation data, ion chemistry, and density measurements established that the pits covered the period from approximately 1993 to spring 2008. Samples were extracted under clean room conditions, and analyzed using GC-negative ion MS for 26 tri- to decabromodiphenyl ethers (BDEs), as well as other BFRs, nonbrominated flame retardants, and industrial chemicals. Decabromodiphenyl ether (BDE-209) was the major congener present in all samples followed by nona-BDEs (BDE-207, BDE-206, and BDE-208), both accounting for 89% and 7% of total BDE, respectively. BDE-209 concentrations were in most cases significantly correlated (P < 0.05) to tri- to nona-BDE homologues, and the strength of the correlations increased with increasing degree of bromination. Prior to or after deposition BDE-209 may be subject to debromination to lighter congeners. Deposition fluxes of BDE-209 show no clear temporal trend and range between 90 and 2000 pg·cm(-2)·year(-1). Back trajectory origin in densely populated areas of northeastern North America is significantly correlated (P < 0.005) with the BDE-209 deposition flux. Several other high production volume and/or alternative BFRs such as hexabromocyclododecane (HBCD), 1,2-bis(2,4,6-dibromophenoxy)ethane (BTBPE), pentabromo ethyl benzene (PBEBz), and pentabromobenzene (PBBz), as well as the industrial chemical 1,3,5-tribromobenzene (135-TBBz) were found consistently in the snow pits.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Flame retardant brominated styrene-based polymers. II. Synthesis, characterization and application of dibromostyrene, styrene and butadiene terpolymers

    SciTech Connect

    Wang, J.L.; Favstritsky, N.A.

    1993-12-31

    Brominated styrene-based polymers having surprisingly good physical properties in combination with flame retardancy are prepared from terpolymers of dibromostyrene, styrene and butadiene. Polymerization compositions were determined by bromine contents (% Br) of the polymers by Schoeninger Combustion Method and {sup 1}H NMR integration. Weight losses (% loss) were measured at 20{degrees}C/min by Thermogravimetric Analysis (TGA). Molecular weights were measured by GPC based on a standard molecular weight (MW) of polystyrene (PS)> Flammability of the latex products when used in textile backcoatings was testing by Motor Vehicle Safety Standard 302 (MVSS-302) flammability test. As latexes were used as non-woven binders, flammability was tested by exposure to a 4 in high, 1950{degrees}F propane flame from a Fisher Burner. When latexes were employed for carpet backing, flammability was tested by DOC. FF-1-70 (pill test) flammability tests.

  18. Levels of brominated flame retardants (BFRs) in honey samples from different geographic regions.

    PubMed

    Mohr, Susana; García-Bermejo, Angel; Herrero, Laura; Gómara, Belén; Costabeber, Ijoni Hilda; González, María José

    2014-02-15

    Concentrations of 17 brominated flame retardants (BFRs), including two "novel" BFRs (1,2-bis(2,4,6-tribromophenoxy)ethane, BTBPE and decabromodiphenylethane, DBDPE), have been determined to be in 35 commercial honey samples from Brazil, Spain, Portugal, Slovenia and Morocco. The results revealed the presence of low amounts (betweenbrominated PBDEs, principally BDE-47, found in honey samples from Slovenia, Spain and Portugal. Meanwhile the most abundant BFRs found in Brazilian and Moroccan honeys were the two novel BFRs (BTBPE and DBDPE). The detection of BFRs in honeys from different countries highlights the risk that their presence poses to the health of humans and wildlife since honey is a non-fatty natural product that is highly consumed all over the world.

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

    SciTech Connect

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

    2006-10-15

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

  20. Degradation of Polymeric Brominated Flame Retardants: Development of an Analytical Approach Using PolyFR and UV Irradiation.

    PubMed

    Koch, Christoph; Dundua, Alexander; Aragon-Gomez, Jackelyn; Nachev, Milen; Stephan, Susanne; Willach, Sarah; Ulbricht, Mathias; Schmitz, Oliver J; Schmidt, Torsten C; Sures, Bernd

    2016-12-06

    Many well-established methods for studying the degradation of brominated flame retardants are not useful when working with polymeric and water insoluble species. An example for this specific class of flame retardants is PolyFR (polymeric flame retardant; CAS No 1195978-93-8), which is used as a substituent for hexabromocyclododecane. Although it has been on the market for two years now, almost no information is available about its long time behavior in the environment. Within this study, we focus on how to determine a possible degradation of both pure PolyFR as well as PolyFR in the final insulation product, expanded polystyrene foam. Therefore, we chose UV radiation followed by analyses of the total bromine content at different time points via ICP-MS and identified possible degradation products such as 2,4,6-tribromophenol through LC-MS. These results were then linked with measurements of the adsorbable organically bound bromine and total organic carbon in order to estimate their concentrations. With respect to the obtained (1)H NMR, GPC, and contact angle results, the possibility for further degradation was discussed, as UV irradiation can influence the decomposition of molecules in combination with other environmental factors like biodegradation.

  1. Brominated flame retardants in food and environmental samples from a production area in China: concentrations and human exposure assessment.

    PubMed

    Li, Peng; Wu, Hui; Li, Qiuxu; Jin, Jun; Wang, Ying

    2015-11-01

    Human exposure to brominated flame retardants (BFRs: decabromodiphenyl ether (BDE209), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), 1,2,3,4,5-pentabromobenzene (PBBz), and 2,3,5,6-tetrabromo-p-xylene (TBX)) in a brominated flame retardant production area (Weifang, Shandong Province, China) was estimated. Thirty food samples, 14 air samples, and 13 indoor dust samples were analyzed. BDE209 and DBDPE were the dominant BFRs in all samples. Higher alternative brominated flame retardant (including DBDPE, HBB, PBEB, PBT, PBBz, and TBX) concentrations were found in vegetables than in fish and meat; thus, plant-original foods might be important alternative BFR sources in the study area. The BDE209 and alternative BFR concentrations in air were 1.5×10(4) to 2.2×10(5) and 620 to 3.6×10(4) pg/m3, respectively. Mean total BFR exposures through the diet, inhalation, and indoor dust ingestion were 570, 3000, and 69 ng/d, respectively (16, 82, and 2% of total intake, respectively). Inhalation was the dominant BFR source except for DBDPE, for which diet dominated. BDE209 contributed 85% of the total BFR intake in the study area.

  2. ENHANCED FORMATION OF CHLORINATED PICS BY THE ADDITION OF BROMINE

    EPA Science Inventory

    A systematic series of experiments were performed on a pilot-scale rotary kiln incinerator simulator in which liquid surrogate wastes containing varied levels of chlorine and bromine were burned. The surrogate wastes used were a series of mixtures of methylene chloride and methyl...

  3. 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...

  4. IN VITRO EFFECTS OF BROMINATED FLAME RETARDANS ON CALCIUM BUFFERING MECHANISMS IN RAT BRAINS.

    EPA Science Inventory

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

  5. ENHANCED FORMATION OF DIOXINS AND FURANS FROM COMBUSTION DEVICES BY ADDITION OF TRACE QUANTITIES OF BROMINE

    EPA Science Inventory

    Past pilot-scale experimental studies have shown a dramatic increase in the formation of certain chlorinated products of incomplete combustion (PICs) caused by the addition of trace amounts of bromine (Br). Emissions of trichloroethylene and tetrachloorethylene, generated as PICs...

  6. Brominated Flame Retardants, Tetrabromobisphenol A and Hexabromocyclododecane, Activate Mitogen-Activated Protein Kinases (MAPKs) in Human Natural Killer Cells

    PubMed Central

    Cato, Anita; Celada, Lindsay; Kibakaya, Esther Caroline; Simmons, Nadia; Whalen, Margaret M.

    2014-01-01

    NK cells provide a vital surveillance against virally infected cells, tumor cells, and antibody-coated cells through the release of cytolytic mediators and gamma interferon (IFN-γ). Hexabromocyclododecane (HBCD) is a brominated flame retardant used primarily in expanded (EPS) and extruded (XPS) polystyrene foams for thermal insulation in the building and construction industry. Tetrabromobisphenol A (TBBPA) is used both as a reactive and an additive flame retardant in a variety of materials. HBCD and TBBPA contaminate the environment and are found in human blood samples. In previous studies, we have shown that other environmental contaminants, such as the dibutyltin (DBT) and tributyltin (TBT), decrease NK lytic function by activating mitogen-activated protein kinases (MAPKs) in the NK cells. HBCD and TBBPA also interfere with NK cell(s) lytic function. The current study evaluates whether HBCD and/or TBBPA have the capacity to activate MAPKs and MAPK kinases (MAP2Ks). The effects of concentrations of HBCD and TBBPA that inhibited lytic function on the phosphorylation state and total levels of the MAPKs (p44/42, p38, and JNK) and the phosphorylation and total levels of the MAP2Ks (MEK1/2 and MKK3/6) were examined. Results indicate that exposure of human NK cells to 10-0.5 µM HBCD or TBBPA activate MAPKs and MAP2Ks. This HBCD and TBBPA-induced activation of MAPKs may leave them unavailable for activation by virally infected or tumor target cells and thus contributes to the observed decreases in lytic function seen in NK cells exposed to HBCD and TBBPA. PMID:25341744

  7. Feasibility study of feces for noninvasive biomonitoring of brominated flame retardants in toddlers.

    PubMed

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

    2015-01-06

    This study investigated the feasibility of using feces as a noninvasive matrix to estimate serum concentrations of brominated flame retardants (BFRs) in toddlers for biomonitoring purposes. Tri- to decabrominated diphenyl ethers (tri-decaBDEs), isomer-specific hexabromocyclododecanes, and 16 emerging BFRs were determined in feces from 22 toddlers (11-15 months of age), and results were compared to previously analyzed matched serum samples. BDE-47, -153, -196, -197, -203, -206, -207, -208, and -209 were detected in the feces creating a matched data set (feces-serum, n = 21). Tetra-octaBDE concentrations were significantly higher (Student's paired comparisons t test, α = 0.05) in serum versus feces with BDE-153 having the highest mean difference between the sample matrices. BDE-209 was found in significantly higher concentrations in feces compared to serum. Significant correlations (Pearson's, α = 0.05) between congener-specific concentrations in feces and serum were found for all BDEs except BDE-197 and -203. The feces-serum associations found can be used to estimate serum concentrations of tetra-decaBDEs from feces concentrations and enable a noninvasive sampling method for biomonitoring BDEs in toddlers.

  8. 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.

  9. QSAR modeling and prediction of the endocrine-disrupting potencies of brominated flame retardants.

    PubMed

    Papa, Ester; Kovarich, Simona; Gramatica, Paola

    2010-05-17

    In the European Union REACH regulation, the chemicals with particularly harmful behaviors, such as endocrine disruptors (EDs), are subject to authorization, and the identification of safer alternatives to these chemicals is required. In this context, the use of quantitative structure-activity relationships (QSAR) becomes particularly useful to fill the data gap due to the very small number of experimental data available to characterize the environmental and toxicological profiles of new and emerging pollutants with ED behavior such as brominated flame retardants (BFRs). In this study, different QSAR models were developed on different responses of endocrine disruption measured for several BFRs. The multiple linear regression approach was applied to a variety of theoretical molecular descriptors, and the best models, which were identified from all of the possible combinations of the structural variables, were internally validated for their performance using the leave-one-out (Q(LOO)(2) = 73-91%) procedure and scrambling of the responses. External validation was provided, when possible, by splitting the data sets in training and test sets (range of Q(EXT)(2) = 76-90%), which confirmed the predictive ability of the proposed equations. These models, which were developed according to the principles defined by the Organization for Economic Co-operation and Development to improve the regulatory acceptance of QSARs, represent a simple tool for the screening and characterization of BFRs.

  10. QSAR classification models for the prediction of endocrine disrupting activity of brominated flame retardants.

    PubMed

    Kovarich, Simona; Papa, Ester; Gramatica, Paola

    2011-06-15

    The identification of potential endocrine disrupting (ED) chemicals is an important task for the scientific community due to their diffusion in the environment; the production and use of such compounds will be strictly regulated through the authorization process of the REACH regulation. To overcome the problem of insufficient experimental data, the quantitative structure-activity relationship (QSAR) approach is applied to predict the ED activity of new chemicals. In the present study QSAR classification models are developed, according to the OECD principles, to predict the ED potency for a class of emerging ubiquitary pollutants, viz. brominated flame retardants (BFRs). Different endpoints related to ED activity (i.e. aryl hydrocarbon receptor agonism and antagonism, estrogen receptor agonism and antagonism, androgen and progesterone receptor antagonism, T4-TTR competition, E2SULT inhibition) are modeled using the k-NN classification method. The best models are selected by maximizing the sensitivity and external predictive ability. We propose simple QSARs (based on few descriptors) characterized by internal stability, good predictive power and with a verified applicability domain. These models are simple tools that are applicable to screen BFRs in relation to their ED activity, and also to design safer alternatives, in agreement with the requirements of REACH regulation at the authorization step.

  11. Occurrence and fate of four novel brominated flame retardants in wastewater treatment plants.

    PubMed

    Kim, M; Guerra, P; Alaee, M; Smyth, S A

    2014-12-01

    Four novel brominated flame retardants (NBFRs), i.e., decabromodiphenylethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), pentabromoethylbenzene (PBEB), and hexabromobenzene (HBB) were studied in 377 liquid samples and 288 solid samples collected from 20 wastewater treatment plants. Lagoon, primary, secondary, and advanced treatment processes were included, in order to investigate NBFR occurrence and the effects of WWTP operational conditions on NBFR removal. Median influent and effluent levels were 14 to 3,700 and 1.0 to 180 pg/L respectively, with DBDPE being the highest in both. Overall median removal efficiencies for DBDPE, BTBPE, HBB, and PBEB across all process types were 81 to 93, 76 to 98, 61 to 97, and 54 to 97 %, respectively with advanced treatment processes obtaining the best removals. NBFRs removal was related to retention time, surface loading rate, and biomass concentration. Median NBFR levels in treated biosolids were 80 to 32,000 pg/g, influenced by solids treatment processes.

  12. Environmental fate of three novel brominated flame retardants in aquatic mesocosms.

    PubMed

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

    2013-04-01

    Currently, little is known about the environmental fate and persistence of novel brominated flame retardants (NBFRs). The recent detection of NBFRs in sediment cores and air samples provides insight into their persistence and potential for transport. Limited numbers of laboratory studies have examined the fate and behavior of these compounds, but field-based fate studies have been especially lacking. The authors conducted an aquatic mesocosm experiment to assess the behavior of three NBFRs: bis(tribromophenoxy)ethane (BTBPE), tetrabromobisphenol A bis(2,3-dibromopropyl ether; TBBPA-DBPE), and Firemaster BZ-54, a commercial mixture containing bis(2-ethylhexyl)tetrabromophthalate (BEHTBP) and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EHTeBB) in a ratio of 1:4. Analysis by gas chromatography-mass spectrometry, operated in the electron capture negative ionization mode, revealed partitioning between the particulate and sediment phases, with BTBPE, TBBPA-DBPE, and BEHTBP identified as being environmentally persistent in both the particulate and the sediment compartments. The median dissipation times (DT50) differed in each compartment, with more rapid disappearance in the particulate (9-30 d) compared with the sediment compartment (>100 d) for each compound. The degradation products were more concentrated in the particulate compartment and corresponded to known photodegradation products. The ratio of EHTeBB to BEHTBP differed in the mesocosm compartments compared with the technical product used for treatment, indicating increased degradation of EHTeBB relative to BETHBP.

  13. 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.

  14. 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.

  15. 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.

  16. Levels and trends of brominated flame retardants in the European environment.

    PubMed

    Law, Robin J; Allchin, Colin R; de Boer, Jacob; Covaci, Adrian; Herzke, Dorte; Lepom, Peter; Morris, Steven; Tronczynski, Jacek; de Wit, Cynthia A

    2006-06-01

    In this paper, we review those data which have recently become available for brominated flame retardants (particularly the brominated diphenyl ethers (BDEs) and hexabromocyclododecane (HBCD)) in samples from the European environment. Environmental compartments studied comprise the atmosphere, sediments and soils, sewage sludges, and a variety of biological samples and food chains. This is currently a very active research area, and we cite over 70 studies reported in the literature during 2003-04. Findings include that the input of BDEs (especially BDE209) to the Baltic Sea by atmospheric deposition now exceeds that of PCBs by a factor of almost 40 times. Sewage sludge samples from both industrial and background locations show concentrations of BDEs, HBCD and tetrabromobisphenol-A (TBBP-A) that are of a similar order, indicating that the major source is from diffuse leaching from products into wastewater streams from users, households and industries generally. Point-sources from industries using BFRs (e.g. the textile industry) also generate local hot-spots. Sediment core studies identified the presence of two of the three PBDE formulations. The penta-mix formulation was clearly present from the beginning of the 1970s, but the deca-mix only appeared in the late 1970s. BDE183, BDE209 and HBCD were detected in peregrine falcons from Sweden and other birds feeding on terrestrial food chains. BDEs are found widely distributed in fish, including those from high mountain lakes in Europe, as a consequence of long-range atmospheric transport and deposition. A temporal trend study in archived freeze-dried mussels from the Seine estuary, France, indicated an exponential increase in BDE concentrations during the period 1982-1993, which levelled off in 1999 and 2001 and then began to decline after 2002. HBCD was detected in liver and blubber samples from harbour seals and harbour porpoises from the Wadden and North Seas, though very few animals yielded positive values for TBBP

  17. Emissions of brominated flame retardants in Asia: consideration of its potential risk form the view point of the Norwegian regulation

    NASA Astrophysics Data System (ADS)

    Kikuchi, Ryunosuke; Gerardo, Romeu; Gorbacheva, Tamara

    2010-05-01

    Flame retardants can be divided into two broad categories: additive or reactive, which can be further more divided into brominated or non-brominated sub-categories. These retardants are found in many commercial products such as computers, television sets, furniture, carpets, etc. They are of environmental concern due to their persistence, potential for bioaccumulation and widespread distribution via atmospheric transport, and possible adverse effects in wildlife and humans. Tetrabromobisphenol-A (TBBPA) is mainly used in electrical and electronic appliances (circuit board in particular), and the application of TBBPA accounts for about two thirds of the global production of brominated flame retardant (BFR). The European Union Risk Assessment does not support the restriction of TBBPA: i.e. no risk is identified for the reactive use of TBBPA such as in epoxy resin used in circuit boards. By contrast, in 2007 Norway notified the World Trade Organization of its intention to prohibit 18 substances from consumer goods (Notification No. 2007/9016/N), called the Prohibition on Certain Hazardous Substances in Consumer Products (PoHS). TBBPA is listed in this prohibition list. Marine conservation is recognized as a key issue in Norwegian fishery management e.g. wastewater management in the framework of the North Sea Declarations. TBBPA is very water-soluble, and dimethyl-TBBPA is lipophilic and may accumulate in fat. TBBPA is not readily biodegradable and can have long-term effects in the aquatic environment. Norwegian examples are summarized: TBBPA was found in marine sediment samples from Tromsø harbor (northern Norway) and in Atlantic cod from Lofoten and Varanger; TBBPA has been detected in Norwegian peregrine falcon and golden eagle eggs; and TBBPA has been detected in the blood in the general population of Norway. From these viewpoints, it can be considered that Norway needs to strictly control TBBPA emissions. In recent times, Asia has emerged as one of the leading

  18. Tracing organophosphorus and brominated flame retardants and plasticizers in an estuarine food web.

    PubMed

    Brandsma, Sicco H; Leonards, Pim E G; Leslie, Heather A; de Boer, Jacob

    2015-02-01

    Nine organophosphorus flame retardants (PFRs) were detected in a pelagic and benthic food web of the Western Scheldt estuary, The Netherlands. Concentrations of several PFRs were an order of magnitude higher than those of the brominated flame retardants (BFRs). However, the detection frequency of the PFRs (6-56%) was lower than that of the BFRs (50-97%). Tris(2-butoxyethyl) phosphate (TBOEP), tris(isobutyl) phosphate (TIBP) and tris(2-chloroisopropyl) phosphate (TCIPP) were the dominant PFRs in sediment with median concentrations of 7.0, 8.1 and 1.8 ng/g dry weight (dw), respectively. PFR levels in the suspended particular matter (SPM) were 2-12 times higher than that in sediment. TBOEP, TCIPP, TIBP, tris(2-chloroethyl) phosphate (TCEP) and tris(phenyl) phosphate (TPHP) were found in organisms higher in the estuarine food web. The highest PFR concentrations in the benthic food web were found in sculpin, goby and lugworm with median concentrations of 17, 7.4, 4.6 and 2.0 ng/g wet weight (ww) for TBOEP, TIBP, TCIPP and TPHP, respectively. Comparable levels were observed in the pelagic food web, BDE209 was the predominant PBDE in sediment and SPM with median concentrations up to 9.7 and 385 ng/g dw, respectively. BDE47 was predominant in the biotic compartment of the food web with highest median levels observed in sculpin and common tern eggs of 79 ng/g lipid weight (lw) (2.5 ng/g ww) and 80 ng/g lw (11 ng/g ww), respectively. Trophic magnification was observed for all PBDEs with the exception of BDE209. Indications of trophic magnification of PFRs were observed in the benthic food web for TBOEP, TCIPP and TCEP with tentative trophic magnification factors of 3.5, 2.2 and 2.6, respectively (p<0.05). Most of the other PFRs showed trophic dilution in both food webs. The relative high PFR levels in several fish species suggest high emissions and substantial exposure of organisms to PFRs in the Western Scheldt.

  19. 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.

  20. Brominated flame retardants in offices in Michigan, U.S.A.

    PubMed Central

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

    2015-01-01

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

  1. Industry-sponsored research on the potential health and environmental effects of selected brominated flame retardants.

    PubMed

    Hardy, M L; Biesemeier, J; Manor, O; Gentit, W

    2003-09-01

    Modern fire-fighting techniques, equipment and fire-resistant building design has lead to less destruction than in the previous centuries. However, a high fuel load in either a residence or a commercial building can overwhelm even the best firefighters or building construction, and factors affecting the fuel load have changed in recent decades. The fire load in a typical home has doubled over the last 50 years, furnishings typically include those made of petrochemicals that can behave as if containing built-in accelerant, and modern energy-efficient buildings are less able to disperse heat in the event of a fire. Flame retardant chemicals (FRs) are one means used to reduce the risk of fire. FRs are typically added or incorporated chemically into a polymer to slow or hinder the ignition or growth of a fire in low-to-moderate cost commodity polymers. One type of FR contains bromine atoms as the active moiety. The FR industry, either as individual companies or as consortia, has conducted a broad range of studies on the commercial deca-, octa- and pentabromodiphenyl oxide/ether, tetrabromobisphenol A and hexabromocyclododecane products. These five products have data in excess of the OECD Screening Informational Data Set (SIDS) and the U.S. High Production Volume (HPV) program, and sufficient data for the performance of formal EU risk assessments. The objective of this paper is to present the range of data developed by industry consortia and to provide sources for the information. We hope to facilitate further research by assembling references to industry consortia-sponsored research here.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. Measurements of Selected Brominated Flame Retardants in Nursing Women: Implications for Human Exposure

    PubMed Central

    2014-01-01

    We have examined several emerging brominated flame retardants (BFRs) including 2-ethyl-1-hexyl-2,3,4,5-tetrabromobenzoate (TBB), bis(2-ethylhexyl) tetrabromophthalate (TBPH), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), 4,5,6,7-tetrabromo-1,1,3-trimethyl-3-(2,3,4,5-tetrabromophenyl)-indane (OBIND), and decabromodiphenyl ethane (DBDPE) in paired human maternal serum (n = 102) and breast milk (n = 105) collected in 2008–2009 in the Sherbrooke region in Canada. Three legacy BFRs were also included in the study for comparison: decabromobiphenyl (BB-209), 2,2′,4,4′,5,5′-hexabromobiphenyl (BB-153), and 2,2′,4,4′,5,5′-hexabromodiphenyl ethers (BDE-153). TBB, BB-153, and BDE-153 had detection frequencies greater than 55% in both serum and milk samples. Their lipid weight (lw) adjusted median concentrations (ng g–1 lw) in serum and milk were 1.6 and 0.41 for TBB, 0.48 and 0.31 for BB-153, and 1.5 and 4.4 for BDE-153, respectively. The detection frequencies for the other BFRs measured in serum and milk were 16.7% and 32.4% for TBPH, 3.9% and 0.0% for BTBPE, 2.0% and 0.0% for BB-209, 9.8% and 1.0% for OBIND, and 5.9% and 8.6% for DBDPE. The ratio of TBB over the sum of TBB and TBPH (fTBB) in serum (0.23) was lower than that in milk (0.46), indicating TBB has a larger tendency than TBPH to be redistributed from blood to milk. Overall, these data confirm the presence of non-PBDE BFRs in humans, and the need to better understand their sources, routes of exposure, and potential human health effects. PMID:24992303

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Novel analytical approach for brominated flame retardants based on the use of gas chromatography-atmospheric pressure chemical ionization-tandem mass spectrometry with emphasis in highly brominated congeners.

    PubMed

    Portolés, Tania; Sales, Carlos; Gómara, Belén; Sancho, Juan Vicente; Beltrán, Joaquim; Herrero, Laura; González, María José; Hernández, Félix

    2015-10-06

    The analysis of brominated flame retardants (BFRs) commonly relies on the use of gas chromatography coupled to mass spectrometry (GC-MS) operating in electron ionization (EI) and electron capture negative ionization (ECNI) modes using quadrupole, triple quadrupole, ion trap, and magnetic sector analyzers. However, these brominated contaminants are examples of compounds for which a soft and robust ionization technique might be favorable since they show high fragmentation in EI and low specificity in ECNI. In addition, the low limits of quantification (0.01 ng/g) required by European Commission Recommendation 2014/118/EU on the monitoring of traces of BFRs in food put stress on the use of highly sensitive techniques/methods. In this work, a new approach for the extremely sensitive determination of BFRs taking profit of the potential of atmospheric pressure chemical ionization (APCI) combined with GC and triple quadrupole (QqQ) mass analyzer is proposed. The objective was to explore the potential of this approach for the BFRs determination in samples at pg/g levels, taking marine samples and a cream sample as a model. Ionization and fragmentation behavior of 14 PBDEs (congeners 28, 47, 66, 85, 99, 100, 153, 154, 183, 184, 191, 196, 197, and 209) and two novel BFRs, decabromodiphenyl ethane (DBDPE) and 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), in the GC-APCI-MS system has been investigated. The formation of highly abundant (quasi) molecular ion was the main advantage observed in relation to EI. Thus, a notable improvement in sensitivity and specificity was observed when using it as precursor ion in tandem MS. The improved detectability (LODs < 10 fg) achieved when using APCI compared to EI has been demonstrated, which is especially relevant for highly brominated congeners. Analysis of samples from an intercomparison exercise and samples from the marine field showed the potential of this approach for the reliable identification and quantification at very low

  13. Gas chromatography/mass spectrometry comprehensive analysis of organophosphorus, brominated flame retardants, by-products and formulation intermediates in water.

    PubMed

    Cristale, Joyce; Quintana, Jordi; Chaler, Roser; Ventura, Francesc; Lacorte, Silvia

    2012-06-08

    A multiresidue method based on gas chromatography coupled to quadrupole mass spectrometry was developed to determine organophosphorus flame retardants, polybromodiphenyl ethers (BDEs 28, 47, 99, 100, 153, 154, 183 and 209), new brominated flame retardants, bromophenols, bromoanilines, bromotoluenes and bromoanisoles in water. Two ionization techniques (electron ionization--EI, and electron capture negative ionization--ECNI) and two acquisition modes (selected ion monitoring--SIM, and selected reaction monitoring--SRM) were compared as regards to mass spectral characterization, sensitivity and quantification capabilities. The highest sensitivity, at expenses of identification capacity, was obtained by GC-ECNI-MS/SIM for most of the compounds analyzed, mainly for PBDEs and decabromodiphenyl ethane while GC-EI-MS/MS in SRM was the most selective technique and permitted the identification of target compounds at the pg level, and identification capabilities increased when real samples were analyzed. This method was further used to evaluate the presence and behavior of flame retardants within a drinking water treatment facility. Organophosphorus flame retardants were the only compounds detected in influent waters at levels of 0.32-0.03 μg L⁻¹, and their elimination throughout the different treatment stages was evaluated.

  14. Brominated flame retardants (BFRs) in air and dust from electronic waste storage facilities in Thailand.

    PubMed

    Muenhor, Dudsadee; Harrad, Stuart; Ali, Nadeem; Covaci, Adrian

    2010-10-01

    This study reports concentrations of brominated flame retardants in dust samples (n=25) and in indoor (n=5) and outdoor air (n=10) (using PUF disk passive air samplers) from 5 electronic and electrical waste (e-waste) storage facilities in Thailand. Concentrations of Sigma(10)PBDEs (BDEs 17, 28, 47, 49, 66, 85, 99, 100, 153 and 154) in outdoor air in the vicinity of e-waste storage facilities ranged from 8 to 150 pg m(-3). Indoor air concentrations ranged from 46 to 350 pg m(-3), with highest concentrations found in a personal computer and printer waste storage room at an e-waste storage facility. These are lower than reported previously for electronic waste treatment facilities in China, Sweden, and the US. Concentrations of Sigma(21)PBDEs (Sigma(10)PBDEs+BDEs 181, 183, 184, 191, 196, 197, 203, 206, 207, 208 and 209), decabromodiphenylethane (DBDPE), decabromobiphenyl (BB-209) in dust were 320-290,000, 43-8700 and <20-2300 ng g(-1) respectively, with the highest concentrations of Sigma(21)PBDEs, BDE-209 and DBDPE in a room used to house discarded TVs, stereos and radios. PBDE concentrations in dust were slightly higher but within the range of those detected in workshop floor dust from an e-waste recycling centre in China. The highest concentration of BB-209 was detected in a room storing discarded personal computers and printers. Consistent with recent reports of elevated ratios of BDE-208:BDE-209 and BDE-183:BDE-209 in household electronics from South China, percentage ratios of BDE-208:BDE-209 (0.64-2.9%) and of BDE-208:BDE-183 (2.8-933%) in dust samples exceeded substantially those present in commercial deca-BDE and octa-BDE formulations. This suggests direct migration of BDE-208 and other nonabrominated BDEs from e-waste to the environment. Under realistic high-end scenarios of occupational exposure to BDE-99, workers in the facilities were exposed above a recently-published Health Based Limit Value for this congener. Reassuringly, estimated exposures to BDE

  15. 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.

  16. Estimation of human percutaneous uptake for two novel brominated flame retardants, 2-ethylhexyl tetrabromobenzoate (TBB) and bis(2-ethylhexyl) tetrabromophthalate (TBPH) using the parallelogram method

    EPA Science Inventory

    2-ethylhexyl- tetrabromobenzoate (TBB) and bis(2-ethylhexyl)-tetrabromobenzoate (TBPH) are novel brominated flame retardants (FRs). TBPH is used as a plasticizer or with TBB in polyurethane foam FRs. TBB & TBPH have been detected in both indoor and outdoor environmental sampl...

  17. 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...

  18. 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.

  19. The NBS Reaction: A Simple Explanation for the Predominance of Allylic Substitution over Olefin Addition by Bromine at Low Concentrations.

    ERIC Educational Resources Information Center

    Wamser, Carl C.; Scott, Lawrence T.

    1985-01-01

    Examines mechanisms related to use of N-bromosuccinimide (NBS) for bromination at an allylic position. Also presents derived rate laws for three possible reactions of molecular bromine with an alkene: (1) free radical substitution; (2) free radical addition; and (3) electrophilic addition. (JN)

  20. Rapid identification of polystyrene foam wastes containing hexabromocyclododecane or its alternative polymeric brominated flame retardant by X-ray fluorescence spectroscopy.

    PubMed

    Schlummer, Martin; Vogelsang, Jörg; Fiedler, Dominik; Gruber, Ludwig; Wolz, Gerd

    2015-07-01

    The brominated flame retardant hexabromocyclododecane (HBCDD) was added to Annex A of the list of persistent organic pollutants (POPs) of the Stockholm Convention. Thus, production and use of HBCDD will be banned, and the recycling of HBCDD-containing foam waste will be restricted. In reaction a special polymeric brominated flame retardant (PolyFR) was developed to replace HBCDD in expanded and extruded polystyrene foams for building and construction applications. A decision has to be made at some future time whether expanded and extruded polystyrene foam waste is to be subjected to incineration (with HBCDD) or to recycling (without HBCDD). Therefore, an appropriate and rapid field method is required to distinguish between foams containing HBCDD and foams free from HBCDD. Here we present a screening method for identifying HBCDD containing expanded and extruded polystyrene foams. The test principle is based on the fact that PolyFR (a brominated polymeric macromolecule) is not extractable whereas HBCDD (a low molecular weight substance) is extractable. Following rapid extraction of HBCDD the brominated flame retardant is identified and quantified via bromine analysis using a handheld X-ray fluorescence instrument. The method was applied successfully to 27 expanded and extruded polystyrene foam samples (foams and extruded polystyrene foam raw materials), which were provided without any information about the applied flame retardant. The presence of HBCDD was confirmed for all HBCDD-positive samples in the test. A robustness test revealed a high degree of correctness and a high repeatability for the test system: samples containing HBCDD and HBCDD-free samples were identified correctly with relative standard deviations of quantitative results below 14%. Moreover, X-ray fluorescence spectroscopy test results agree well with HBCDD determinations performed in a laboratory with a gas chromatograph coupled to a flame ionisation detector.

  1. 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.

  2. Toughening reinforced epoxy composites with brominated polymeric additives

    NASA Technical Reports Server (NTRS)

    Nir, Z.; Gilwee, W. J., Jr. (Inventor)

    1985-01-01

    Cured polyfunctional epoxy resins including tris (hydroxyphenyl) methane triglycidyl ether are toughened by addition of polybrominated polymeric additives having an EE below 1500 to the pre-cure composition. Carboxy terminated butadiene acrylonitrile rubber is optionally present in the precure mixture as such or as a pre-formed copolymer with other reactants. Reinforced composites, particularly carbon reinforced composites, of these resins are disclosed and shown to have improved toughness.

  3. Toughening reinforced epoxy composites with brominated polymeric additives

    NASA Technical Reports Server (NTRS)

    Nir, Z. (Inventor); Gilwee, W. J., Jr. (Inventor)

    1985-01-01

    Cured polyfunctional epoxy resins including tris(hydroxyphenyl)methane triglycidyl ether are toughened by addition of polybrominated polymeric additives having an EE below 1500 to the pre-cure composition. Carboxy-terminated butadiene-acrylonitrile rubber is optionally present in the pre-cure mixture as such or as a pre-formed copolymer with other reactants. Reinforced composites, particularly carbon-reinforced composites, of these resins are disclosed and shown to have improved toughness.

  4. Exposure of Female Rats to an Environmentally Relevant Mixture of Brominated Flame Retardants Targets the Ovary, Affecting Folliculogenesis and Steroidogenesis1

    PubMed Central

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

    2015-01-01

    Brominated flame retardants (BFRs) are incorporated into various consumer products to prevent flame propagation. These compounds leach into the domestic environment, resulting in chronic exposure and contamination. Pregnancy failure is associated with high levels of BFRs in human follicular fluid, raising serious questions regarding their impact on female reproductive health. The goal of this study is to elucidate the effects of an environmentally relevant BFR mixture on female rat ovarian functions (i.e., folliculogenesis and steroidogenesis). A BFR dietary mixture formulated to mimic the relative BFR congener levels in North American house dust was administered to adult female Sprague-Dawley rats from 2 to 3 wk before mating until Gestational Day 20; these diets were designed to deliver nominal doses of 0, 0.06, 20, or 60 mg/kg/day of the BFR mixture. Exposure to BFRs triggered an approximately 50% increase in the numbers of preantral and antral follicles and an enlargement of the antral follicles in the ovaries of the dams. A significant reduction in the expression of catalase, an antioxidant enzyme, and downregulation of the expression of insulin-like factor 3 (Insl3) and 17alpha-hydroxylase (Cyp17a1) were observed in the ovary. In addition, BFR exposure affected steroidogenesis; we observed a significant decrease in circulating 17-hydroxypregnenolone and an increase in testosterone concentrations in BFR-exposed dams. Thus, BFRs target ovarian function in the rat, adversely affecting both folliculogenesis and steroidogenesis. PMID:26607716

  5. Characterization of PBDEs and novel brominated flame retardants in seawater near a coastal mariculture area of the Bohai Sea, China.

    PubMed

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

    2017-02-15

    The concentrations and distributions of PBDEs and novel brominated flame retardants (NBFRs) in dissolved phase of surface seawater near a coastal mariculture area of the Bohai Sea were investigated. The total concentrations of PBDE and NBFRs were in the range of 15.4-65.5 and 2.12-13.6ng/L, respectively. The highest concentration was discovered in the water near an anchorage ground, whereas concentrations in water samples from offshore cage-culture area were not elevated. Relatively high concentrations of BDE28, 99, and 100 were discovered in the medium range of distance from shore, where is the path of tidal or coastal current. This suggested that inputs from ships or through tidal current rather than mariculture activities may be the main sources of BFRs in this area. BDE209, BDE47, hexabromobenzene (HBB), and 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) were the most abundant BFR congeners. Relatively high proportions of these BFRs may originate from discharge of wastewater nearby or degradation from higher brominated PBDEs. No correlations were found between BFR concentrations and water dissolved organic carbon, suggesting that concentrations and distributions of BFRs in this area were source-dependent. The relatively high concentrations in this study emphasized the importance of monitoring and managing BFR contaminations in mariculture areas of China.

  6. Effects of the brominated flame retardant TBCO on fecundity and profiles of transcripts of the HPGL-axis in Japanese medaka.

    PubMed

    Saunders, David M V; Podaima, Michelle; Wiseman, Steve; Giesy, John P

    2015-03-01

    The novel brominated flame retardant, 1,2,5,6-tetrabromocyclooctane (TBCO) is an additive flame retardant which is marketed under the trade name Saytex BCL-48. TBCO has recently been investigated as a potential alternative to the major use brominated flame retardant, hexabromocyclododecane (HBCD), which could have major implications for significant increases in amounts of TBCO used. Yet there is a lack of information regarding potential toxicities of TBCO. Recently, results of in vitro experiments have demonstrated the potential of TBCO to modulate endocrine function through interaction with estrogen and androgen receptors and via alterations to the synthesis of 17-β-estradiol and testosterone. Further research is required to determine potential endocrine disrupting effects of TBCO in vivo. In this experiment a 21-day fecundity assay with Japanese medaka (Oryzias latipes) was conducted to examine endocrine disrupting effects of TBCO in vivo. Medaka were fed a diet containing either 607 or 58μg TBCO/g food, wet mass (wm). Fecundity, measured as cumulative deposition of eggs and fertilization of eggs, as well as abundances of transcripts of 34 genes along the hypothalamus-pituitary-gonadal-liver (HPGL) axis were measured as indicators of holistic endocrine disruption and to determine mechanisms of effects, respectively. Cumulative fecundity was 18% lesser by medaka exposed to 58μg TBCO/g, wm food. However, fecundity of medaka exposed to 607μg TBCO/g, wm food was not significantly different from that of controls. Organ-specific and dose-dependent alterations to abundances of transcripts were observed in male and female medaka. A pattern of down-regulation of expression of genes involved in steroidogenesis, metabolism of cholesterol, and regulatory feedback mechanisms was observed in gonads from male and female medaka which had been exposed to the greater concentration of TBCO. However, these effects on expression of genes were not manifested in effects on

  7. Neurobehavioral effects of tetrabromobisphenol A, a brominated flame retardant, in mice.

    PubMed

    Nakajima, Akira; Saigusa, Daisuke; Tetsu, Naomi; Yamakuni, Tohru; Tomioka, Yoshihisa; Hishinuma, Takanori

    2009-08-25

    Tetrabromobisphenol A (TBBPA) is widely used as a flame retardant and is suspected to be stable in the environment with possible widespread human exposures. In the present study, we investigated the behavioral effects of TBBPA and measured the levels of TBBPA in the brain after oral administration in mice. Acute treatment with TBBPA (5mg/kg body weight) 3h before the open-field test induced an increase in the horizontal movement activities. In contextual fear conditioning paradigm, mice treated with TBBPA (0.1mg/kg or 5mg/kg body weight) showed more freezing behavior than vehicle-treated mice. In addition, TBBPA (0.1mg/kg body weight) significantly increased the spontaneous alternation behavior in the Y-maze test. The levels of TBBPA in the brain following TBBPA treatment were determined by using LC/ESI-MS/MS system. In the brain regions examined, high amounts of TBBPA were detected in the striatum after treatment with 0.1mg/kg or 5mg/kg body weight TBBPA, whereas non-specific accumulation of TBBPA in the brain was found after treatment with 250 mg/kg body weight TBBPA. These results suggest that TBBPA accumulates in brain regions including the striatum and induces the behavioral alterations. Together, the possibility of widespread human exposure to TBBPA warrants further studies to characterize its neurotoxicity.

  8. Dynamics of brominated flame retardants removal in contaminated wastewater sewage sludge under anaerobic conditions.

    PubMed

    Stiborova, Hana; Vrkoslavova, Jana; Pulkrabova, Jana; Poustka, Jan; Hajslova, Jana; Demnerova, Katerina

    2015-11-15

    Disposal of solid waste to landfills from waste water sewage treatment plants (WWTPs) serves as a potential source of contamination by polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). Native microbial communities have been found to degrade a variety of xenobiotics, such as PBDEs and HBCDs. This study investigates the potential of autochthonous microflora to remove 11 PBDE congeners and HBCDs in waste water sludge under anaerobic conditions. Laboratory microcosms were constructed with sewage sludge from the WWTPs of Hradec Kralove and Brno. BDE 209 was detected as the prevailing congener in concentrations 685 and 1403 ng/g dw and the total amounts of 10 lower PBDEs (BDE 28, 47, 49, 66, 85, 99, 100, 153, 154, 183) were 605 and 205 ng/g dw in sludge from Hradec Kralove and Brno, respectively. The levels of HBCD were detected in both sludge lower than 24 ng/g dw. The experiment was carried out for 15 months. After three months of incubation, HBCD was completely degraded to below detection limits. In sewage from both WWTPs, the higher brominated DEs were removed faster than the lower brominated congeners. One exception was tri-BDE, which was degraded completely within 15 months of cultivation. A significant increase in congener tetra-BDE 49 concentrations was observed over the course of the experiment in all tested sewage. The relative distribution of individual congeners among all PBDEs changed after 15 months of the incubation in favour of lower brominated congeners. This indicates that debromination is the major mechanism of anaerobic biodegradation. Despite of the increase of BDE 49, the overall removal of all 11 PBDEs achieved the levels of 47.4 and 68.7% in samples from WWTPs Hradec Kralove and Brno, respectively.

  9. 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.

  10. 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...

  11. 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.

  12. In vitro endocrine disruption and TCDD-like effects of three novel brominated flame retardants: TBPH, TBB, & TBCO.

    PubMed

    Saunders, David M V; Higley, Eric B; Hecker, Markus; Mankidy, Rishikesh; Giesy, John P

    2013-11-25

    The novel brominated flame retardants (NBFRs), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB), Bis(2-ethylhexyl)-2,3,4,5-tetrabromophtalate (TBPH), and 1,2,5,6-tetrabromocyclooctane (TBCO) are components of flame retardant mixtures including Firemaster 550 and Saytex BC-48. Despite the detection of these NBFRs in environmental and biotic matrices, studies regarding their toxicological effects are poorly represented in the literature. The present study examined endocrine disruption by these three NBFRs using the yeast YES/YAS reporter assay and the mammalian H295R steroidogenesis assay. Activation of the aryl hydrocarbon receptor (AhR) was also assessed using the H4IIE reporter assay. The NBFRs produced no TCDD-like effects in the H4IIE assay or agonistic effects in the YES/YAS assays. TBB produced a maximal antiestrogenic effect of 62% at 0.5mgL(-1) in the YES assay while TBPH and TBCO produced maximal antiandrogenic effects of 74% and 59% at 300mgL(-1) and 1500mgL(-1), respectively, in the YAS assay. Significant effects were also observed in the H295R assay. At 0.05mgL(-1), 15mgL(-1), and 15mgL(-1) TBB, TBPH, and TBCO exposures, respectively resulted in a 2.8-fold, 5.4-fold, and 3.3-fold increase in concentrations of E2. This is one of the first studies to demonstrate the in vitro endocrine disrupting potentials of TBB, TBPH, and TBCO.

  13. Development and validation of a multi-residue method for the analysis of brominated and organophosphate flame retardants in indoor dust.

    PubMed

    He, Chang; Wang, Xianyu; Thai, Phong; Mueller, Jochen F; Gallen, Christie; Li, Yan; Baduel, Christine

    2017-03-01

    Flame retardants are associated to numerous adverse health effects, can accumulate in humans and have been used intensively worldwide. Recently, dust has been identified as a major human exposure route for flame retardants. The aim of this study was to develop a multi-residue method using a two-step SPE purification. It enabled us to effectively limit co-extracted matrix/interferets and therefore a simultaneous analysis of brominated and organophosphate flame retardants for indoor dust was achieved. The optimized method was validated according to standard protocol and achieved good accuracy and reproducibility (percent error ranged from -29% to 28%). Standard Reference Material (SRM) for dust was also analysed, and good agreement was found with reported brominated and organophosphate flame retardants (OPFRs) concentrations. The applicability of the validated method was demonstrated by the analysis of ten indoor dust samples from ten Australian homes. Overall 89% of the analytes were detected in these samples. The average concentrations of ∑OPFRs and ∑PBDEs in those samples were 41 and 3.6μg/g, respectively. Tris(2-butoxyethyl) phosphate and tris(2-chloroisopropyl) phosphate were the most abundant OPFRs, accounting for 57-92% ∑OPFRs, while decabromodiphenyl ether dominated the Polybrominated diphenyl ethers (PBDE) congeners contributing between 71-94% to the ∑PBDEs.

  14. 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.

  15. 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.

  16. 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.

  17. 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 (

  18. 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

  19. 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.

  20. 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.

  1. Evaluation of 3D-human skin equivalents for assessment of human dermal absorption of some brominated flame retardants.

    PubMed

    Abdallah, Mohamed Abou-Elwafa; Pawar, Gopal; Harrad, Stuart

    2015-11-01

    Ethical and technical difficulties inherent to studies in human tissues are impeding assessment of the dermal bioavailability of brominated flame retardants (BFRs). This is further complicated by increasing restrictions on the use of animals in toxicity testing, and the uncertainties associated with extrapolating data from animal studies to humans due to inter-species variations. To overcome these difficulties, we evaluate 3D-human skin equivalents (3D-HSE) as a novel in vitro alternative to human and animal testing for assessment of dermal absorption of BFRs. The percutaneous penetration of hexabromocyclododecanes (HBCD) and tetrabromobisphenol-A (TBBP-A) through two commercially available 3D-HSE models was studied and compared to data obtained for human ex vivo skin according to a standard protocol. No statistically significant differences were observed between the results obtained using 3D-HSE and human ex vivo skin at two exposure levels. The absorbed dose was low (less than 7%) and was significantly correlated with log Kow of the tested BFR. Permeability coefficient values showed increasing dermal resistance to the penetration of γ-HBCD>β-HBCD>α-HBCD>TBBPA. The estimated long lag times (>30 min) suggests that frequent hand washing may reduce human exposure to HBCDs and TBBPA via dermal contact.

  2. 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.

  3. The brominated flame retardants, PBDEs and HBCD, in Canadian human milk samples collected from 1992 to 2005; concentrations and trends.

    PubMed

    Ryan, John Jake; Rawn, Dorothea F K

    2014-09-01

    Human milk samples were collected from individuals residing in various regions across Canada mostly in the years 1992 to 2005. These included five large cities in southern Canada as well as samples from Nunavik in northern Quebec. Comparative samples were also collected from residents of Austin, Texas, USA in 2002 and 2004. More than 300 milk samples were analysed for the brominated flame retardants (BFRs), PBDEs and HBCD, by extraction, purification and quantification using either isotope dilution gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-MS. The Canadian total PBDE values in the years 2002-2005 show median levels of about 20μg/kg on a lipid basis; a value significantly higher than in the 1980s and 1990s. Milk samples from Inuit donors in the northern region of Nunavik were slightly lower in PBDE concentrations than those from populated regions in the south of Quebec. Milk samples from Ontario contained slightly lower amounts of PBDEs in two time periods than those from Texas. HBCD levels in most milk samples were usually less than 1ppb milk lipid and dominated by the α-isomer. This large data set of BFRs in Canadian human milk demonstrates an increase in the last few decades in human exposure to BFRs which now appears to have stabilized.

  4. Simultaneous determination of 16 brominated flame retardants in food and feed of animal origin by fast gas chromatography coupled to tandem mass spectrometry using atmospheric pressure chemical ionisation.

    PubMed

    Bichon, E; Guiffard, I; Vénisseau, A; Lesquin, E; Vaccher, V; Brosseaud, A; Marchand, P; Le Bizec, B

    2016-08-12

    A gas chromatography tandem mass spectrometry method using atmospheric pressure chemical ionisation was developed for the monitoring of 16 brominated flame retardants (7 usually monitored polybromodiphenylethers (PBDEs) and BDE #209 and 8 additional emerging and novel BFRs) in food and feed of animal origin. The developed analytical method has decreased the run time by three compared to conventional strategies, using a 2.5m column length (5% phenyl stationary phase, 0.1mm i.d., 0.1μmf.t.), a pulsed split injection (1:5) with carrier gas helium flow rate at 0.48mLmin(-1) in one run of 20 min. For most BFRs, analytical data were compared with the current analytical strategy relying on GC/EI/HRMS (double sector, R=10000 at 10% valley). Performances in terms of sensitivity were found to meet the Commission recommendation (118/2014/EC) for nBFRs. GC/APCI/MS/MS represents a promising alternative for multi-BFRs analysis in complex matrices, in that it allows the monitoring of a wider list of contaminants in a single injection and a shorter run time.

  5. The sarcoplasmic-endoplasmic reticulum Ca(2+)-ATPase (SERCA) is the likely molecular target for the acute toxicity of the brominated flame retardant hexabromocyclododecane (HBCD).

    PubMed

    Al-Mousa, Fawaz; Michelangeli, Francesco

    2014-01-25

    Hexabromocyclododecane (HBCD) is a widely utilised brominated flame retardant (BFR). It has been shown to bio-accumulate within organisms, including man, and possibly cause neurological disorders. The acute neurotoxicity of HBCD, and six other unrelated BFRs, were assessed in SH-SY5Y human neuroblastoma cells by 24h viability assays and HBCD proved to be the most lethal (LC50, 3μM). In addition, the effects of these BFRs were also assessed for their potency at inhibiting the sarcoplasmic-endoplasmic reticulum Ca(2+) ATPase (SERCA) derived from the SH-SY5Y cells and again HBCD was the most potent (IC50, 2.7μM). The data for the other BFRs tested showed a direct correlation (coefficient 0.94) between the potencies of inducing cell death and inhibiting the Ca(2+) ATPase, indicating that SERCA is likely to be the molecular target for acute toxicity. Mechanistic studies of HBCD on the Ca(2+) ATPase suggest that it affects ATP binding, phosphorylation as well as the E2 to E1 transition step.

  6. Prenatal exposure to the brominated flame retardant hexabromocyclododecane (HBCD) impairs measures of sustained attention and increases age-related morbidity in the Long-Evans rat.

    PubMed

    Miller-Rhodes, Patrick; Popescu, Maria; Goeke, Calla; Tirabassi, Toni; Johnson, Lauren; Markowski, Vincent P

    2014-01-01

    Hexabromocyclododecane (HBCD) is a brominated flame retardant that is widely-used in foam building materials and to a lesser extent, furniture and electronic equipment. After decades of use, HBCD and its metabolites have become globally-distributed environmental contaminants that can be measured in the atmosphere, water bodies, wildlife, food staples and human breastmilk. Emerging evidence suggests that HBCD can affect early brain development and produce behavioral consequences for exposed organisms. The current study examined some of the developmental and lifelong neurobehavioral effects of prenatal HBCD exposure in a rat model. Pregnant rats were gavaged with 0, 3, 10, or 30mg/kg HBCD from gestation day 1 to parturition. A functional observation battery was used to assess sensorimotor behaviors in neonates. Locomotor and operant responding under random ratio and Go/no-go schedules of food reinforcement were examined in cohorts of young adult and aged rats. HBCD exposure was associated with increased reactivity to a tailpinch in neonates, decreased forelimb grip strength in juveniles, and impaired sustained attention indicated by Go/no-go responding in aged rats. In addition, HBCD exposure was associated with a significant increase in morbidity in the aged cohort. One health complication, a progressive loss of hindleg function, was observed only in the aged, 3mg/kg HBCD animals. These effects suggest that HBCD is a developmental neurotoxicant that can produce long-term behavioral impairments that emerge at different points in the lifespan following prenatal exposure.

  7. 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.

  8. Transcriptomic responses of European flounder (Platichthys flesus) liver to a brominated flame retardant mixture.

    PubMed

    Williams, Tim D; Diab, Amer M; Gubbins, Matt; Collins, Catherine; Matejusova, Iveta; Kerr, Rose; Chipman, James K; Kuiper, Raoul; Vethaak, A Dick; George, Stephen G

    2013-10-15

    Male European flounder (Platichthys flesus) were exposed to a technical mixture of brominated diphenyl ethers (PDBEs, DE-71, Pentamix) that had been purified to remove contaminating dioxins. Controls were exposed to carrier solvent alone. Fish were exposed to decadally increasing concentrations of Pentamix via both sediment and spiked food. The GENIPOL P. flesus cDNA microarray, differentially expressed gene profiling (DEG) and quantitative PCR were employed to detect hepatic transcriptional differences between exposed fish and controls. Gene transcriptional changes were more sensitive to Pentamix exposure than biomarkers measured previously. Pentamix exposure induced transcripts coding for enzymes of xenobiotic metabolism (CYP1A, aldo-keto reductases) and elicited endocrine disruption (vitellogenin and thyroid hormone receptor alpha), with effects on CYP1A and VTG occurring at the highest exposure. Ontology analysis clearly showed dose-responsive changes indicative of oxidative stress, induction of mitochondrial dysfunction, and apoptosis. We conclude that exposure to PBDEs in both sediment and food has a significant adverse effect on a broad range of crucial biochemical processes in the livers of this widely distributed estuarine fish species, the flounder.

  9. 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.

  10. 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.

  11. Cats' Internal Exposure to Selected Brominated Flame Retardants and Organochlorines Correlated to House Dust and Cat Food.

    PubMed

    Norrgran Engdahl, J; Bignert, A; Jones, B; Athanassiadis, I; Bergman, Å; Weiss, J M

    2017-03-07

    Pet cats may be used as a biomarker for assessing exposures to organohalogen compounds (OHCs) adsorbed to household dust in home environments. This study explores two exposure routes of OHCs, ingestion of OHCs (i) via house dust and (ii) via cat food. House dust from 17 Swedish homes and serum from the participating families' pet cats were collected, and cat food was purchased matching the diet reported. Paired samples of cat serum, house dust, and cat food were analyzed for brominated flame retardants/natural products (polybrominated diphenyl ethers (PBDEs), decabromobiphenyl (BB-209), decabromodiphenyl ethane (DBDPE), 2,4,6-tribromophenol (2,4,6-TBP), OH-PBDEs) and organochlorines (polychlorinated biphenyls (PCBs), 1,1-bis(4,4'-dichlorodiphenyl)-2,2,2-trichloroethane (4,4'-DDT), 1,1-bis(4,4'-dichlorodiphenyl)-2,2-dichloroethene (4,4'-DDE), hexachlorobenzene (HCB), pentachlorophenol (PCP)). Significant correlations were found between serum and dust samples from the living rooms for BDE-47 (p < 0.035), BDE-99 (p < 0.035), and BDE-153 (p < 0.039), from the adult's bedroom for BDE-99 (p < 0.019) and from all rooms for BDE-99 (p < 0.020) and BB-209 (p < 0.048). This is the first time a correlation between cat serum levels and household dust has been established, a finding that supports the hypothesis that dust is a significant exposure route for cats. Serum levels were also significantly correlated with concentrations found in cat food for 6-OH-BDE47 (p < 0.002), 2,4,6-TBP (p < 0.035), and BB-209 (p < 0.007). DBDPE was found in high concentrations in all dust (median 154 pmol/g) and food samples (median 0.7 pmol/g lw) but was below detection in serum samples, suggesting low or no bioavailability for DBDPE in cats.

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

    PubMed

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

    2016-06-01

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

  13. Occurrence and fate of PBDEs and novel brominated flame retardants in a wastewater treatment plant in Harbin, China.

    PubMed

    Li, Bo; Sun, Shao-Jing; Huo, Chun-Yan; Li, Wen-Long; Zhu, Ning-Zheng; Qi, Hong; Kong, Ling-Jun; Li, Yi-Fan; Ma, Wan-Li

    2016-10-01

    Wastewater treatment plant (WWTP) is considered to be an important medium for the transport and transformation of organic pollutants. This study attempted to comprehensively investigate polybrominated diphenyl ethers (PBDEs) and novel brominated flame retardants (NBFRs) in a WWTP in Harbin, one of the main "Old Industrial Base" in China. The mean concentrations of the total PBDEs in the influent, effluent, and sludge were 152 ng/L, 16.2 ng/L, and 503 g/g dw, respectively, which were at the low end of the global range. BDE-209 was the most abundant congener, with contributions to the total PBDE ranging from 90.5 to 98.5 %. The level of the total NBFRs ranged from 24.5 to 107 ng/L, 0.95 to 20.3 ng/L, and 305 to 1202 ng/g dw in the influent, effluent, and sludge, respectively. For NBFRs, DBDPE was the most abundant congener (38.8-50.5 %), followed by BEHTBP (11.0-35.0 %). The ratio for DBDPE/BDE-209 (0.62 ± 0.42) was found less than 1 in sludge, which indicated that Deca-BDE is still the major BFR product in this city. Source identification suggested that indoor dust should be an important source of BFRs in the WWTP. Approximately 20.8 and 7.79 kg of PBDEs and NBFRs on annual basis were removed with the sludge. Biodegradation could play an important role on the fate of BFRs in the WWTP, which is required for future research.

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

    PubMed

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

    2016-07-01

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

  15. Effects of dietary exposure to brominated flame retardant BDE-47 on thyroid condition, gonadal development and growth of zebrafish.

    PubMed

    Torres, Leticia; Orazio, Carl E; Peterman, Paul H; Patiño, Reynaldo

    2013-10-01

    Little is known about the effects of brominated flame retardants in teleosts and some of the information currently available is inconsistent. This study examined effects of dietary exposure to 2,2',4,4'-tetrabromodiphenyl ether (BDE-47) on thyroid condition, body mass and size, and gonadal development of zebrafish. Pubertal, 49-day-old (posthatch) fish were fed diets without BDE-47 (control) or with 1, 5 or 25 μg/g BDE-47/diet. Treatments were conducted in triplicate 30-L tanks each containing 50 zebrafish, and 15 fish per treatment (5 per tank) were sampled at days 40, 80 and 120 of exposure. Measurements were taken of body mass, standard length, head depth and head length. Sex (at 40-120 days of exposure), germ cell stage (at 40 days) and thyroid condition (at 120 days; follicular cell height, colloid depletion, angiogenesis) were histologically determined. Whole-body BDE-47 levels at study completion were within the high end of levels reported in environmentally exposed (wild) fishes. Analysis of variance was used to determine differences among treatments at each sampling time. No effects were observed on thyroid condition or germ cell stage in either sex. Reduced head length was observed in females exposed to BDE-47 at 80 days but not at 40 or 120 days. In males, no apparent effects of BDE-47 were observed at 40 and 80 days, but fish exposed to 25 μg/g had lower body mass at 120 days compared to control fish. These observations suggest that BDE-47 at environmentally relevant whole-body concentrations does not affect thyroid condition or pubertal development of zebrafish but does affect growth during the juvenile-to-adult transition, especially in males.

  16. Effects of dietary exposure to brominated flame retardant BDE-47 on thyroid condition, gonadal development and growth of zebrafish

    USGS Publications Warehouse

    Torres, Leticia; Orazio, Carl E.; Peterman, Paul H.; Patino, Reynaldo

    2013-01-01

    Little is known about the effects of brominated flame retardants in teleosts and some of the information currently available is inconsistent. This study examined effects of dietary exposure to 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) on thyroid condition, body mass and size, and gonadal development of zebrafish. Pubertal, 49-day-old (posthatch) fish were fed diets without BDE-47 (control) or with 1, 5 or 25 μg/g BDE-47/diet. Treatments were conducted in triplicate 30-L tanks each containing 50 zebrafish, and 15 fish per treatment (5 per tank) were sampled at days 40, 80 and 120 of exposure. Measurements were taken of body mass, standard length, head depth and head length. Sex (at 40–120 days of exposure), germ cell stage (at 40 days) and thyroid condition (at 120 days; follicular cell height, colloid depletion, angiogenesis) were histologically determined. Whole-body BDE-47 levels at study completion were within the high end of levels reported in environmentally exposed (wild) fishes. Analysis of variance was used to determine differences among treatments at each sampling time. No effects were observed on thyroid condition or germ cell stage in either sex. Reduced head length was observed in females exposed to BDE-47 at 80 days but not at 40 or 120 days. In males, no apparent effects of BDE-47 were observed at 40 and 80 days, but fish exposed to 25 μg/g had lower body mass at 120 days compared to control fish. These observations suggest that BDE-47 at environmentally relevant whole-body concentrations does not affect thyroid condition or pubertal development of zebrafish but does affect growth during the juvenile-to-adult transition, especially in males.

  17. [Effects of perinatal exposure to the brominated flame-retardant hexabromocyclododecane (HBCD) on the developing immune system in rats].

    PubMed

    Hachisuka, Akiko; Nakamura, Ryosuke; Sato, Yuji; Nakamura, Rika; Shibutani, Makoto; Teshima, Reiko

    2010-01-01

    To evaluate the developmental immunotoxicity of brominated flame retardant, hexabromocyclododecane (HBCD) , maternal Sprague-Dawley rats were given HBCD at dietary concentrations of 0, 100, 1000, 10000 ppm from gestational day 10 to postnatal day 21 (postnatal week 3, PNW3). At PNW3 and PNW11, lymphocytes in the spleen, thymus, and peripheral blood of male pups were subjected to flow cytometric analyses for expression of surface markers (CD3, CD4, CD8a, CD25, CD45RA, CD71, and CD161 (NKRP1A)). The spleen and thymus weights, and number of white blood cells of two organs did not change between HBCD-exposed and control groups at PNW3 and PNW11. A significant decrease in thyroid hormone T3 and increase in serum albumin concentration were observed at PNW3 and lasted until PNW11. By flow cytometric analysis, the dramatic change was not observed in the population of the splenic and thymic T/B lymphocyte between the HBCD treated groups and control group. In the peripheral blood of BNW3 rats, the population of activated T cells was decreased and that of inactivated B cells was increased. And the population of NK cells in the spleen was decreased. All of these changes were mild in degree, and returned to the normal levels by PNW11. Production of anti-KLH IgG antibody after KLH immunization was reduced by the 10000 ppm HBCD treatment. These results suggest that developmental exposure to the highest dose of HBCD had a weak immunomodulatory effect at PNW3, and most of the immunomodulatory effect had recovered to normal levels by PNW11.

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

    PubMed

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

    2014-12-01

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

  19. 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.

  20. 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.

  1. Development and validation of a multiresidue method for the analysis of polybrominated diphenyl ethers, new brominated and organophosphorus flame retardants in sediment, sludge and dust.

    PubMed

    Cristale, Joyce; Lacorte, Silvia

    2013-08-30

    This study presents a multiresidue method for simultaneous extraction, clean-up and analysis of priority and emerging flame retardants in sediment, sewage sludge and dust. Studied compounds included eight polybrominated diphenyl ethers congeners, nine new brominated flame retardants and ten organophosphorus flame retardants. The analytical method was based on ultrasound-assisted extraction with ethyl acetate/cyclohexane (5:2, v/v), clean-up with Florisil cartridges and analysis by gas chromatography coupled to tandem mass spectrometry (GC-EI-MS/MS). Method development and validation protocol included spiked samples, certified reference material (for dust), and participation in an interlaboratory calibration. The method proved to be efficient and robust for extraction and determination of three families of flame retardants families in the studied solid matrices. The method was applied to river sediment, sewage sludge and dust samples, and allowed detection of 24 among the 27 studied flame retardants. Organophosphate esters, BDE-209 and decabromodiphenyl ethane were the most ubiquitous contaminants detected.

  2. 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.

  3. 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

  4. 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.

  5. 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

  6. Investigation of Fuel Additive Effects on Sooting Flames

    DTIC Science & Technology

    1989-07-28

    Ndubizu, C. C., and B. T. Zinn : Effects of Metallic Aditive Upon Soot Formation in Polymer Diffusion Flames. Combust, Flame 46, 301-314 (1982). 3.4...Plenum Press, New York, p. 143 (1981). 3.28 Wersborg, B. L., .1. B. Howard , and G. C. Williams: Physical Mechanisms in Carbon 3 Formation in Flames

  7. 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

  8. Contamination of indoor dust and air by polychlorinated biphenyls and brominated flame retardants and relevance of non-dietary exposure in Vietnamese informal e-waste recycling sites.

    PubMed

    Tue, Nguyen Minh; Takahashi, Shin; Suzuki, Go; Isobe, Tomohiko; Viet, Pham Hung; Kobara, Yuso; Seike, Nobuyasu; Zhang, Gan; Sudaryanto, Agus; Tanabe, Shinsuke

    2013-01-01

    This study investigated the occurrence of polychlorinated biphenyls (PCBs), and several additive brominated flame retardants (BFRs) in indoor dust and air from two Vietnamese informal e-waste recycling sites (EWRSs) and an urban site in order to assess the relevance of these media for human exposure. The levels of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), 1,2-bis-(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenyl ethane (DBDPE) in settled house dust from the EWRSs (130-12,000, 5.4-400, 5.2-620 and 31-1400 ng g(-1), respectively) were significantly higher than in urban house dust but the levels of PCBs (4.8-320 ng g(-1)) were not higher. The levels of PCBs and PBDEs in air at e-waste recycling houses (1000-1800 and 620-720 pg m(-3), respectively), determined using passive sampling, were also higher compared with non-e-waste houses. The composition of BFRs in EWRS samples suggests the influence from high-temperature processes and occurrence of waste materials containing older BFR formulations. Results of daily intake estimation for e-waste recycling workers are in good agreement with the accumulation patterns previously observed in human milk and indicate that dust ingestion contributes a large portion of the PBDE intake (60%-88%), and air inhalation to the low-chlorinated PCB intake (>80% for triCBs) due to their high levels in dust and air, respectively. Further investigation of both indoor dust and air as the exposure media for other e-waste recycling-related contaminants and assessment of health risk associated with exposure to these contaminant mixtures is necessary.

  9. Brominated flame retardants in U.S. biosolids from the EPA national sewage sludge survey and chemical persistence in outdoor soil mesocosms

    PubMed Central

    Venkatesan, Arjun K.; Halden, Rolf U.

    2014-01-01

    We determined national baseline levels and release inventories of 77 traditional and novel brominated flame retardants (BFRs) in biosolids composites (prepared from 110 samples) from the U.S. Environmental Protection Agency’s 2001 national sewage sludge survey (NSSS). Additionally, analyses were performed on archived samples from a 3-year outdoor mesocosm study to determine the environmental persistence of BFRs in biosolids-amended soil. The total polybrominated diphenylether (PBDE) concentration detected in biosolids composites was 9,400±960 μg/kg dry weight, of which deca-BDE constituted 57% followed by nona- and penta-BDE at 18 and 13%, respectively. The annual mean loading rate estimated from the detected concentrations and approximate annual biosolids production and disposal numbers in the U.S., of the sum of PBDEs and non-BDE BFRs was calculated to be 47,900–60,100 and 12,900–16,200 kg/year, of which 24,000–36,000 and 6,400–9,700 kg/year are applied on land, respectively. Mean concentration of PBDEs were higher in the 2001 samples compared to levels reported in EPA’s 2006/7 Targeted NSSS, reflecting on-going efforts in phasing-out PBDEs in the U.S. In outdoor soil mesocosms, >99% of the initial BFRs mass in the biosolids/soil mixtures (1:2) persisted over the monitoring duration of three years. Estimates of environmental releases may be refined in the future by analyzing individual rather than composited samples, and by integrating currently unavailable data on disposal of biosolids on a plant-specific basis. This study informs the risk assessment of BFRs by furnishing national inventories of BFR occurrence and environmental release via biosolids application on land. PMID:24607311

  10. Magnetic solid phase extraction of brominated flame retardants and pentachlorophenol from environmental waters with carbon doped Fe3O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Yang, Jing; Li, Jia-yuan; Qiao, Jun-qin; Cui, Shi-hai; Lian, Hong-zhen; Chen, Hong-yuan

    2014-12-01

    Carbon doped Fe3O4 nanoparticles (Fe3O4/C) prepared by a facile hydrothermal reaction of glucose with iron resource have been applied as magnetic solid-phase extraction (MSPE) sorbent, for the first time, to extract trace brominated flame retardants (BFRs) and pentachlorophenol (PCP) from environmental waters. Various MSPE parameters were optimized including amount of Fe3O4/C nanoparticles, pH of sample solution, enrichment factor of analytes and reusability of Fe3O4/C sorbent. The reliability of the MSPE method was evaluated by the recoveries of BFRs and PCP in spiked water samples. Good recoveries (80.0-110.0%) were achieved with the relative standard deviations range from 0.3% to 6.8%. In this paper, the extraction characteristics of Fe3O4/C sorbent were further elucidated. It is found that the adsorption process of Fe3O4/C to analytes predominates the MSPE efficiency. There is hybrid hydrophobic interaction and hydrogen bonding or dipole-dipole attraction between Fe3O4/C and analytes. Notably, the chemical components of carbon layer on the surface of Fe3O4 nanoparticles were identified by X-ray photoelectron spectroscopy and thermogravimetry-mass spectrometry, and in consequence the covalent bonds between Fe3O4 and the coated carbon have been observed. In addition, the straight influence of synthesis condition of Fe3O4/C nanoparticles including glucose concentration and hydrothermal reaction time on extraction performance for BFRs and PCP has been investigated. It is confirmed that the existence of organic carbon containing functional groups over Fe3O4/C sorbent is responsible for the MSPE extraction.

  11. PILOT-SCALE STUDIES ON THE EFFECT OF BROMINE ADDITION ON THE EMISSIONS OF CHLORINATED ORGANIC COMBUSTION BY-PRODUCTS

    EPA Science Inventory

    The addition of brominated organic compounds to the feed of a pilot-scale incinerator burning chlorinated waste has been found previously, under some circumstances, to enhance emissions of volatile and semivolatile organic chlorinated products of incomplete combustion (PiCs) incl...

  12. [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.

  13. Body burdens of brominated flame retardants and other persistent organo-halogenated compounds and their descriptors in US girls

    SciTech Connect

    Windham, Gayle C.; Pinney, Susan M.; Sjodin, Andreas; Lum, Raymond; Jones, Richard S.; Needham, Larry L.; Biro, Frank M.; Hiatt, Robert A.; Kushi, Lawrence H.

    2010-04-15

    Background: Levels of brominated flame retardants are increasing in US populations, yet little data are available on body burdens of these and other persistent hormonally active agents (HAAs) in school-aged children. Exposures to such chemicals may affect a number of health outcomes related to development and reproductive function. Objective: Determine the distribution of biomarkers of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and organo-chlorinated pesticides (OCPs), such as DDT/DDE, in children, and their variation by key descriptor variables. Methods: Ethnically diverse cohorts of girls 6-8 y old at baseline are being followed for growth and pubertal development in a multi-site, longitudinal study. Nearly 600 serum samples from the California and Ohio sites were analyzed for lipids, 35 PCB congeners, 11 PBDE congeners, and 9 OCPs. The biomarker distributions were examined and geometric means compared for selected analytes across categories of age, race, site, body mass index (BMI), parental education, maternal age at delivery, and breast feeding in adjusted models. Results: Six PBDE congeners were detected among greater than 70% of samples, with BDE-47 having the highest concentration (median 42.2, range 4.9-855 ng/g lipid). Girls in California had adjusted geometric mean (GM) PBDE levels significantly higher than girls in Ohio. Furthermore, Blacks had significantly higher adjusted GMs of all six PBDE congeners than Whites, and Hispanics had intermediate values. GMs tended to be lower among more obese girls, while other variables were not strongly associated. In contrast, GMs of the six PCB congeners most frequently detected were significantly lower among Blacks and Hispanics than Whites. PCBs and the three pesticides most frequently detected were also consistently lower among girls with high BMI, who were not breast-fed, whose mothers were younger, or whose care-givers (usually parents) were less educated. Girls in California had

  14. Brominated Flame Retardants and Other Persistent Organohalogenated Compounds in Relation to Timing of Puberty in a Longitudinal Study of Girls

    PubMed Central

    Pinney, Susan M.; Voss, Robert W.; Sjödin, Andreas; Biro, Frank M.; Greenspan, Louise C.; Stewart, Susan; Hiatt, Robert A.; Kushi, Lawrence H.

    2015-01-01

    Background Exposure to hormonally active chemicals could plausibly affect pubertal timing, so we are investigating this in the Breast Cancer and the Environment Research Program. Objectives Our goal was to examine persistent organic pollutants (POPs) in relation to pubertal onset. Methods Ethnically diverse cohorts of 6- to 8-year-old girls (n = 645) provided serum for measure of polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and lipids. Tanner stages [breast (B) and pubic hair (PH)], and body mass index (BMI) were measured at up to seven annual clinic visits. Using accelerated failure time models, we calculated time ratios (TRs) for age at Tanner stages 2 or higher (2+) and POPs quartiles (Q1–4), adjusting for confounders (race/ethnicity, site, caregiver education, and income). We also calculated prevalence ratios (PRs) of Tanner stages 2+ at time of blood sampling. Results Cross-sectionally, the prevalence of B2+ and PH2+ was inversely related to chemical serum concentrations; but after adjustment for confounders, only the associations with B2+, not PH2+, were statistically significant. Longitudinally, the age at pubertal transition was consistently older with greater chemical concentrations; for example: adjusted TR for B2+ and Q4 for ΣPBDE = 1.05; 95% CI: 1.02, 1.08, for ΣPCB = 1.05; 95% CI: 1.01, 1.08, and for ΣOCP = 1.10; 95% CI: 1.06, 1.14, indicating median ages of about 6 and 11 months older than least exposed, and with similar effect estimates for PH2+. Adjusting for BMI attenuated associations for PCBs and OCPs but not for PBDEs. Conclusions This first longitudinal study of puberty in girls with serum POPs measurements (to our knowledge) reveals a delay in onset with higher concentrations. Citation Windham GC, Pinney SM, Voss RW, SjÖdin A, Biro FM, Greenspan LC, Stewart S, Hiatt RA, Kushi LH. 2015. Brominated flame retardants and other persistent organohalogenated compounds in relation to

  15. Identification of a group of brominated flame retardants as novel androgen receptor antagonists and potential neuronal and endocrine disrupters.

    PubMed

    Kharlyngdoh, Joubert Banjop; Pradhan, Ajay; Asnake, Solomon; Walstad, Anders; Ivarsson, Per; Olsson, Per-Erik

    2015-01-01

    Brominated flame-retardants (BFRs) are used in industrial products to reduce the risk of fire. However, their continuous release into the environment is a concern as they are often persistent, bioaccumulating and toxic. Information on the impact these compounds have on human health and wildlife is limited and only a few of them have been identified to disrupt hormone receptor functions. In the present study we used in silico modeling to determine the interactions of selected BFRs with the human androgen receptor (AR). Three compounds were found to dock into the ligand-binding domain of the human AR and these were further tested using in vitro analysis. Allyl 2,4,6-tribromophenyl ether (ATE), 2-bromoallyl 2,4,6-tribromophenyl ether (BATE) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE) were observed to act as AR antagonists. These BFRs have recently been detected in the environment, in house dust and in aquatic animals. The compounds have been detected at high concentrations in both blubber and brain of seals and we therefore also assessed their impact on the expression of L-type amino acid transporter system (LAT) genes, that are needed for amino acid uptake across the blood-brain barrier, as disruption of LAT gene function has been implicated in several brain disorders. The three BFRs down-regulated the expression of AR target genes that encode for prostate specific antigen (PSA), 5α-reductases and β-microseminoprotein. The potency of PSA inhibition was of the same magnitude as the common prostate cancer drugs, demonstrating that these compounds are strong AR antagonists. Western blot analysis of AR protein showed that ATE, BATE and DPTE decreased the 5α-dihydrotestosterone-induced AR protein levels, further confirming that these BFRs act as AR antagonists. The transcription of the LAT genes was altered by the three BFRs, indicating an effect on amino-acid uptake across cellular membranes and blood-brain barrier. This study demonstrated that ATE, BATE

  16. Controlled flame synthesis of αFe2O3 and Fe3O4 nanoparticles: effect of flame configuration, flame temperature, and additive loading

    NASA Astrophysics Data System (ADS)

    Buyukhatipoglu, K.; Morss Clyne, A.

    2010-05-01

    Superparamagnetic iron oxide nanoparticles are used in diverse applications, including optical magnetic recording, catalysts, gas sensors, targeted drug delivery, magnetic resonance imaging, and hyperthermic malignant cell therapy. Combustion synthesis of nanoparticles has significant advantages, including improved nanoparticle property control and commercial production rate capability with minimal post-processing. In the current study, superparamagnetic iron oxide nanoparticles were produced by flame synthesis using a coflow flame. The effect of flame configuration (diffusion and inverse diffusion), flame temperature, and additive loading on the final iron oxide nanoparticle morphology, elemental composition, and particle size were analyzed by transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), energy dispersive spectroscopy (EDS), and Raman spectroscopy. The synthesized nanoparticles were primarily composed of two well known forms of iron oxide, namely hematite αFe2O3 and magnetite Fe3O4. We found that the synthesized nanoparticles were smaller (6-12 nm) for an inverse diffusion flame as compared to a diffusion flame configuration (50-60 nm) when CH4, O2, Ar, and N2 gas flow rates were kept constant. In order to investigate the effect of flame temperature, CH4, O2, Ar gas flow rates were kept constant, and N2 gas was added as a coolant to the system. TEM analysis of iron oxide nanoparticles synthesized using an inverse diffusion flame configuration with N2 cooling demonstrated that particles no larger than 50-60 nm in diameter can be grown, indicating that nanoparticles did not coalesce in the cooler flame. Raman spectroscopy showed that these nanoparticles were primarily magnetite, as opposed to the primarily hematite nanoparticles produced in the hot flame configuration. In order to understand the effect of additive loading on iron oxide nanoparticle morphology, an Ar stream carrying titanium-tetra-isopropoxide (TTIP) was flowed through the

  17. Brominated flame retardants in serum from U.S. blood donors.

    PubMed

    Sjödin, A; Patterson, D G; Bergman, A

    2001-10-01

    Serum samples collected in 1988 from U.S. blood donors were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated and polybrominated biphenyls (PCBs and PBBs). The levels of the PBDEs are reported for the first time in serum from the U.S. population. The median concentrations and range of 2,2',4,4'-tetrabromodiphenyl ether (BDE-47); 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153); 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183); and decabromodiphenyl ether (BDE-209) were 1.3 (<0.8-49); 0.54 (0.13-3.1); 0.24 (0.12-1.8); and <1 (<1-35) pmol/g lipid weight (l.w.), respectively. In addition we also measured detectable levels of nine additional PBDE congeners in many of the serum samples. The median concentrations and ranges of 2,2',4,4',5,5'-hexachloro- and hexabromobiphenyl (CB-153 and BB-153) were 190 (21-2600) and 19 (4.2-84) pmol/g l.w. The levels of PBDEs and CB-153 found in the U.S. samples were similar to background levels reported in the serum of Swedish hospital cleaners collected 10 years later, i.e., 1997. The BB-153 congener measured in the U.S. samples was not found in the Swedish samples. The difference in exposure to this congener could not be assessed in this study, although might be related to the 1973 BB-153 (FireMaster BP-6) animal and human contamination incident in the State of Michigan.

  18. Radiation of nitrogen molecules in a dielectric barrier discharge with small additives of chlorine and bromine

    SciTech Connect

    Avtaeva, S. V.; Avdeev, S. M.; Sosnin, E. A.

    2010-08-15

    Spectral and energy characteristics of nitrogen molecule radiation in dielectric barrier discharges in Ar-N{sub 2}, Ar-N{sub 2}-Cl{sub 2}, and Ar-N{sub 2}-Br{sub 2} mixtures were investigated experimentally. Small additives of molecular chlorine or bromine to an Ar-N{sub 2} mixture are found to increase the radiation intensity of the second positive system of nitrogen. The conditions at which the radiation spectrum predominantly consists of vibronic bands of this system are determined. Using a numerical model of plasmachemical processes, it is shown that, at electron temperatures typical of gas discharges (2-4 eV), a minor additive of molecular chlorine to an Ar-N{sub 2} mixture leads to an increase in the concentrations of electrons, positive ions, and metastable argon atoms. In turn, collisional energy transfer from metastable argon atoms to nitrogen molecules results in the excitation of the N{sub 2}(C{sup 3{Pi}}{sub u}) state.

  19. Maternal transfer of organochlorines and brominated flame retardants in blue tits (Cyanistes caeruleus).

    PubMed

    Van den Steen, Evi; Jaspers, Veerle L B; Covaci, Adrian; Neels, Hugo; Eens, Marcel; Pinxten, Rianne

    2009-01-01

    Although eggs have frequently been used as a biomonitoring tool for contamination with organohalogenated pollutants (OHPs), few studies have investigated the processes of maternal transfer in birds. Here, maternal transfer of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) was investigated through comparison of the concentrations and profiles between whole homogenised female blue tits (Cyanistes caeruleus) and their eggs. In addition, we examined if there was an effect of laying order on the concentrations of PCBs, OCPs and PBDEs. PCBs were the most abundant contaminants in female blue tits and their eggs, followed by OCPs and PBDEs. Among the OCPs, p,p'-DDE was the most dominant compound and accounted for more than 80% of the sum OCPs. Egg concentrations decreased significantly in relation to the laying order from 1623+/-148 ng/g lipid weight (lw) to 1040+/-47 ng/g lw for the sum PCBs, from 342+/-24 ng/g lw to 235+/-17 ng/g lw for the sum OCPs and from 49+/-5 ng/g lw to 27+/-5 ng/g lw for the sum PBDEs. When reviewing all studies investigating laying order effects of OHPs in birds, no clear patterns emerged, which may be due to differences in study species and methodology among studies. Despite the fact that there were laying order effects in blue tit clutches, the variance in concentrations of PCBs and PBDEs was larger among clutches than within clutches. Variance in OCP concentrations among clutches was similar to the variance within clutches. These results suggest that one randomly collected blue tit egg from a clutch is useful as biomonitoring tool for PCBs and PBDEs, while for OCPs it is recommended to consistently use the same egg from the laying sequence as a biomonitoring tool. Lipid-normalized concentrations of sum PCBs, sum OCPs and sum PBDEs in female blue tits after clutch completion were comparable to the concentrations in the first-laid eggs. The egg/female lipid concentration ratios for

  20. Concentrations and trophic interactions of novel brominated flame retardants, HBCD, and PBDEs in zooplankton and fish from Lake Maggiore (Northern Italy).

    PubMed

    Poma, Giulia; Volta, Pietro; Roscioli, Claudio; Bettinetti, Roberta; Guzzella, Licia

    2014-05-15

    Following the release of the international regulations on PBDEs and HBCD, the aim of this study is to evaluate the concentrations of novel brominated flame retardants (NBFRs), including 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB), in an Italian subalpine lake located in a populated and industrial area. The study investigated specifically the potential BFR biomagnification in a particular lake's pelagic food web, whose structure and dynamics were evaluated using the Stable Isotope Analysis. The potential BFR biomagnification was investigated by using the trophic-level adjusted BMFs and Trophic Magnification Factors (TMFs), confirming that HBCD and some PBDE congeners are able to biomagnify within food webs. Comparing the calculated values of BMFTL and TMF, a significant positive correlation was observed between the two factors, suggesting that the use of BMFTL to investigate the biomagnification potential of organic chemical compounds might be an appropriate approach when a simple food web is considered.

  1. Towards development of a rapid and effective non-destructive testing strategy to identify brominated flame retardants in the plastics of consumer products.

    PubMed

    Gallen, Christie; Banks, Andrew; Brandsma, Sicco; Baduel, Christine; Thai, Phong; Eaglesham, Geoff; Heffernan, Amy; Leonards, Pim; Bainton, Paul; Mueller, Jochen F

    2014-09-01

    Polybrominated diphenyl ethers (PBDEs) are a class of brominated flame retardants (BFRs) once extensively used in the plastics of a wide range of consumer products. The listing of certain congeners that are constituents of commercial PBDE mixtures (including c-octaBDE) in the Stockholm Convention and tightening regulation of many other BFRs in recent years have created the need for a rapid and effective method of identifying BFR-containing plastics. A three-tiered testing strategy comparing results from non-destructive testing (X-ray fluorescence (XRF)) (n=1714), a surface wipe test (n=137) and destructive chemical analysis (n=48) was undertaken to systematically identify BFRs in a wide range of consumer products. XRF rapidly identified bromine in 92% of products later confirmed to contain BFRs. Surface wipes of products identified tetrabromobisphenol A (TBBPA), c-octaBDE congeners and BDE-209 with relatively high accuracy (>75%) when confirmed by destructive chemical analysis. A relationship between the amounts of BFRs detected in surface wipes and subsequent destructive testing shows promise in predicting not only the types of BFRs present but also estimating the concentrations present. Information about the types of products that may contain persistent BFRs will assist regulators in implementing policies to further reduce the occurrence of these chemicals in consumer products.

  2. Effects of the brominated flame retardant hexabromocyclododecane (HBCD) on dopamine-dependent behavior and brainstem auditory evoked potentials in a one-generation reproduction study in Wistar rats.

    PubMed

    Lilienthal, Hellmuth; van der Ven, Leo T M; Piersma, Aldert H; Vos, Josephus G

    2009-02-25

    Hexabromocyclododecane (HBCD) is a widely used brominated flame retardant which has been recently detected in many environmental matrices. Data from a subacute toxicity study indicated dose-related effects particularly on the pituitary thyroid-axis and retinoids in female rats. Brominated and chlorinated aromatic hydrocarbons are also reported to exert effects on the nervous system. Several investigations revealed a pronounced sensitivity of the dopaminergic system and auditory functions to polychlorinated biphenyls. Therefore, the present experiment should examine, whether or not HBCD affects these targets. Rats were exposed to 0, 0.1, 0.3, 1, 3, 10, 30 or 100 mg HBCD/kg body weight via the diet. Exposure started before mating and was continued during mating, gestation, lactation, and after weaning in offspring. Haloperidol-induced catalepsy and brainstem auditory evoked potentials (BAEPs) were used to assess dopamine-dependent behavior and hearing function in adult male and female offspring. On the catalepsy test, reduced latencies to movement onset were observed mainly in female offspring, indicating influences on dopamine-dependent behavior. The overall pattern of BAEP alterations, with increased thresholds and prolonged latencies of early waves, suggested a predominant cochlear effect. Effects were dose-dependent with lower bounds of benchmark doses (BMDL) between < or =1 and 10 mg/kg body weight for both catalepsy and BAEP thresholds. Tissue concentrations at the BMDL values obtained in this study were 3-4 orders of magnitude higher than current exposure levels in humans.

  3. 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.

  4. Preparation of poly(trimethyl-2-methacroyloxyethylammonium chloride-co-ethylene glycol dimethacrylate) monolith and its application in solid phase microextraction of brominated flame retardants.

    PubMed

    Yang, Ting-ting; Zhou, Lin-feng; Qiao, Jun-qin; Lian, Hong-zhen; Ge, Xin; Chen, Hong-yuan

    2013-05-24

    A capillary poly(trimethyl-2-methacroyloxyethylammonium chloride-co-ethylene glycol dimethacrylate) monolith was in situ synthesized by thermally initiated free radical co-polymerization using trimethyl-2-methacroyloxyethylammonium chloride (MATE) and ethylene glycol dimethacrylate (EGDMA) as functional monomer and cross-linker, respectively. N,N-dimethylformamide and polyethylene glycol 6000 were used as solvent and porogen, respectively. The morphology and porous structure of the resulting monoliths were assessed by scanning electron microscope. In order to prepare practically useful poly(MATE-co-EGDMA) monoliths with low flow resistance and good mechanical strength, some parameters such as PEG-6000 to DMF ratio, total monomer to porogen ratio, and crosslinker to monomer ratio were optimized systematically. Moreover, the extraction mechanism was evaluated using two series of compounds, alkylbenzenes and weak acids, as model compounds on poly(MATE-co-EGDMA) monoliths as liquid chromatographic stationary phase. Finally, the monoliths were applied as the solid phase microextraction medium, and a simple off-line method for simultaneous determination of three brominated flame retardants, 2,4,6-tribromophenol (TBP), tetrabromobisphenol A (TBBPA) and 4,4'-dibrominated diphenyl ether (DBDPE), in environmental waters was developed by coupling the polymer monolith microextraction to HPLC with UV detection. The regression equations for these three brominated flame retardants showed good linearity from their limit of quantification to 5000ng/mL. The limits of detection were 0.20, 0.15 and 0.10ng/mL for TBP, TBBPA and DBDPE, respectively. The recovery of the proposed method was 78.7-106.1% with intra-day relative standard deviation of 1.3-4.4%.

  5. Estrogenic and androgenic activities of TBBA and TBMEPH, metabolites of novel brominated flame retardants, and selected bisphenols, using the XenoScreen XL YES/YAS assay.

    PubMed

    Fic, Anja; Žegura, Bojana; Gramec, Darja; Mašič, Lucija Peterlin

    2014-10-01

    The present study investigated and compared the estrogenic and androgenic activities of the three different classes of environmental pollutants and their metabolites using the XenoScreen XL YES/YAS assay, which has advantages compared with the original YES/YAS protocol. Contrary to the parent brominated flame retardants TBB and TBPH, which demonstrated no or very weak (anti)estrogenic or (anti)androgenic activities, their metabolites, TBBA and TBMEPH, exhibited anti-estrogenic (IC50 for TBBA=31.75 μM and IC50 for TBMEPH=0.265 μM) and anti-androgenic (IC50 for TBBA=73.95 μM and IC50 for TBMEPH=2.92 μM) activities. These results reveal that metabolism can enhance the anti-estrogenic and anti-androgenic effects of these two novel brominated flame retardants. Based on the activities of BPAF, BPF, BPA and MBP, we can conclude that the XenoScreen XL YES/YAS assay gives comparable results to the (anti)estrogenic or (anti)androgenic assays that are reported in the literature. For BPA, it was confirmed previously that the metabolite formed after an ipso-reaction (hydroxycumyl alcohol) exhibited higher estrogenic activity compared with the parent BPA, but this was not confirmed for BPAF and BPF ipso-metabolites, which were not active in the XenoScreen YES/YAS assay. Among the substituted BPA analogues, bis-GMA exhibited weak anti-estrogenic activity, BADGE demonstrated weak anti-estrogenic and anti-androgenic activities (IC50=13.73 μM), and the hydrolysed product BADGE·2H2O demonstrated no (anti)estrogenic or (anti)androgenic activities.

  6. Bromine radical-mediated sequential radical rearrangement and addition reaction of alkylidenecyclopropanes.

    PubMed

    Kippo, Takashi; Hamaoka, Kanako; Ryu, Ilhyong

    2013-01-16

    Bromine radical-mediated cyclopropylcarbinyl-homoallyl rearrangement of alkylidenecyclopropanes was effectively accomplished by C-C bond formation with allylic bromides, which led to the syntheses of 2-bromo-1,6-dienes. A three-component coupling reaction comprising alkylidenecyclopropanes, allylic bromides, and carbon monoxide also proceeded well to give 2-bromo-1,7-dien-5-ones in good yield.

  7. 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.

  8. Occurrence of brominated flame retardants in black thermo cups and selected kitchen utensils purchased on the European market.

    PubMed

    Samsonek, J; Puype, F

    2013-01-01

    In order to screen for the presence of a recycled polymer waste stream from waste electric and electronic equipment (WEEE), a market survey was conducted on black plastic food-contact articles (FCA). An analytical method was applied combining X-ray fluorescence spectrometry (XRF) with thermal desorption gas chromatography coupled with mass spectrometry (thermal desorption GC-MS). Firstly, XRF spectrometry was applied to distinguish bromine-positive samples. Secondly, bromine-positive samples were submitted for identification by thermal desorption GC-MS. Generally, the bromine-positive samples contained mainly technical decabromodiphenyl ether (decaBDE). Newer types of BFRs such as tetrabromobisphenol A (TBBPA), tetrabromobisphenol A bis(2,3-dibromopropyl), ether (TBBPA-BDBPE) and decabromodiphenylethane (DBDPE), replacing the polybrominated diphenyleters (PBDEs) and polybrominated diphenyls (PBBs), were also identified. In none of the tested samples were PBBs or hexabromocyclododecane (HBCD) found. Polymer identification was carried out using Fourier-transformed infrared spectroscopy measurement (FTIR) on all samples. The results indicate that polypropylene-polyethylene copolymers (PP-PE) and mainly styrene-based food-contact materials, such as acrylonitrile-butadiene-styrene (ABS) have the highest risk of containing BFRs.

  9. 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.

  10. TSCA Work Plan Chemical Technical Supplement – Physicochemical Properties and Environmental Fate of the Brominated Phthalates Cluster (BPC) Chemicals

    EPA Pesticide Factsheets

    TSCA Work Plan Chemical Technical Supplement – Physicochemical Properties and Environmental Fate of the Brominated Phthalates Cluster (BPC) Chemicals -- Brominated Phthalates Cluster Flame Retardants.

  11. Temporal trends of brominated flame retardants in coastal waters of Japan and South China: retrospective monitoring study using archived samples from es-Bank, Ehime University, Japan.

    PubMed

    Tanabe, Shinsuke

    2008-01-01

    The present paper is a summary of studies conducted at the Center for Marine Environmental Studies, Ehime University, on temporal trends of brominated flame retardants (BFRs) in coastal waters of Japan and South China. Archived marine mammal fat tissues and dated sediment cores were used to evaluate temporal trends of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in relation to their usage in the region. The results indicate that environmental concentrations of these BFRs in Japan and South China increased significantly during the last several decades. Temporal trends in the contaminant concentrations were consistent with historical consumption of the corresponding BFRs. PBDE levels in marine mammals and sediments from Japan, after showing peak concentrations in the 1990s, appear to be leveling off in recent years, in accordance with the discontinued usage of Tetra- and Octa-BDEs in Japan from the 1990s. The change in concentration levels was also accompanied by changes in PBDE congener profiles, i.e. shift towards increased proportion of higher brominated BDEs. Furthermore, in recent years HBCD concentrations in marine mammals from Japan appear to exceed those of PBDEs, presumably reflecting increasing usage of HBCDs over PBDEs. In finless porpoises from the South China Sea, PBDE levels were much higher than HBCD concentrations both in the past and recent years, implying consumption of HBCDs was not as high as that of PBDEs in China. In dated sediment cores from Tokyo Bay, concentrations increased exponentially with doubling times of 4.6-7.9 years, 6.1-12 years and 7.1-12 years for BDE-209, SigmaPBDEs and HBCDs, respectively.

  12. Effects of chronic exposure to an environmentally relevant mixture of brominated flame retardants on the reproductive and thyroid system in adult male rats.

    PubMed

    Ernest, Sheila R; Wade, Michael G; Lalancette, Claudia; Ma, Yi-Qian; Berger, Robert G; Robaire, Bernard; Hales, Barbara F

    2012-06-01

    Brominated flame retardants (BFRs) are incorporated into a wide variety of consumer products, are readily released into home and work environments, and are present in house dust. Studies using animal models have revealed that exposure to polybrominated diphenyl ethers (PBDEs) may impair adult male reproductive function and thyroid hormone physiology. Such studies have generally characterized the outcome of acute or chronic exposure to a single BFR technical mixture or congener but not the impact of environmentally relevant BFR mixtures. We tested whether exposure to the BFRs found in house dust would have an adverse impact on the adult male rat reproductive system and thyroid function. Adult male Sprague Dawley rats were exposed to a complex BFR mixture composed of three commercial brominated diphenyl ethers (52.1% DE-71, 0.4% DE-79, and 44.2% decaBDE-209) and hexabromocyclododecane (3.3%), formulated to mimic the relative congener levels in house dust. BFRs were delivered in the diet at target doses of 0, 0.02, 0.2, 2, or 20 mg/kg/day for 70 days. Compared with controls, males exposed to the highest dose of BFRs displayed a significant increase in the weights of the kidneys and liver, which was accompanied by induction of CYP1A and CYP2B P450 hepatic drug-metabolizing enzymes. BFR exposure did not affect reproductive organ weights, serum testosterone levels, testicular function, or sperm DNA integrity. The highest dose caused thyroid toxicity as indicated by decreased serum thyroxine (T4) and hypertrophy of the thyroid gland epithelium. At lower doses, the thickness of the thyroid gland epithelium was reduced, but no changes in hormone levels (T4 and thyroid-stimulating hormone) were observed. Thus, exposure to BFRs affected liver and thyroid physiology but not male reproductive parameters.

  13. Patterns and trends in brominated flame retardants in bald eagle nestlings from the upper midwestern United States.

    PubMed

    Route, William T; Dykstra, Cheryl R; Rasmussen, Paul W; Key, Rebecca L; Meyer, Michael W; Mathew, John

    2014-11-04

    We report on patterns and trends in polybrominated diphenyl ethers (PBDEs) in the plasma of 284 bald eagle nestlings sampled between 1995 and 2011 at six study areas in the upper Midwestern United States. Geometric mean concentrations of total PBDEs (Σ of nine congeners) ranged from 1.78 ng/mL in the upper St. Croix River watershed to 12.0 ng/mL on the Mississippi River. Lake Superior nestlings fell between these two extremes. Between 2006 and 2011, trends differed among study areas with three declining, two remaining stable, and one increasing. Variation in ΣPBDE trends among study areas was linked to trends in individual congeners. The lower brominated PBDEs (BDE-47, -99, and -100) declined 4-10% while the higher brominated congeners (BDE-153 and -154) increased by about 7.0% annually from 2006 to 2011. This increase was the greatest in nestlings from the St. Croix River and below its confluence with the Mississippi River. Region-wide, our data suggest ΣPBDEs increased in bald eagle nestlings from 1995 through the mid-2000s and then declined by 5.5% annually from 2006 to 2011. These regional trends are consistent with the removal of penta- and octa-PBDEs from the global market.

  14. 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.

  15. Brominated flame retardants and organochlorine contaminants in winter flounder, harp and hooded seals, and North Atlantic right whales from the Northwest Atlantic Ocean.

    PubMed

    Montie, Eric W; Letcher, Robert J; Reddy, Christopher M; Moore, Michael J; Rubinstein, Belinda; Hahn, Mark E

    2010-08-01

    Various brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs) and current-use, non-PBDE BFRs, as well as organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs), were measured in winter flounder, harp and hooded seals, and North Atlantic right whales from the Eastern United States and Canada. The concentrations of PBDEs in winter flounder and right whales were similar in magnitude to the levels of PCBs, which was unlike the pattern observed in seals. In these marine mammals, the levels of PBDEs were orders of magnitude lower than the levels of OCs and PCBs detected. Evidence existed for the accumulation of methoxylated (MeO)-PBDEs of natural origin in seals and right whales. Current-use, non-PBDE BFRs (including hexabromocyclododecane, pentabromoethylbenzene, hexabromobenzene, and pentabromotoluene) were detected in winter flounder and marine mammals. Future research should focus on monitoring PBDEs, current-use, non-PBDE BFRs, and MeO-BDEs of natural origin in marine organisms from Massachusetts and Cape Cod Bays.

  16. 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.

  17. 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).

  18. Brominated flame retardants and polychlorinated biphenyls in human breast milk from several locations in India: potential contaminant sources in a municipal dumping site.

    PubMed

    Devanathan, Gnanasekaran; Subramanian, Annamalai; Sudaryanto, Agus; Takahashi, Shin; Isobe, Tomohiko; Tanabe, Shinsuke

    2012-02-01

    This study investigated the status of contamination of organohalogen compounds (OCs) such as polychlorinated biphenyls (PCBs) and brominated flame retardant (BFRs), including polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) in human milk samples from several locations in India. The levels of OCs were significantly higher in the milk of mothers living in and near municipal dumping site than other locations indicating that the open dumping sites for municipal wastes act as potential sources of these contaminants in India. The PCB concentrations observed in this study tended to decrease compared to those in the matched locations reported previously, probably due to the restriction of technical PCB usage in India. PBDE levels in human milk were two to three folds lower than those of PCBs in all the sampling locations investigated. Congener profiles of PCBs and PBDEs were different between samples from the dumping site mothers and general populations in other areas suggesting the presence of region-specific sources and pathways. HBCDs were detected in human milk from only two sites, with much lower concentrations and detection frequencies compared to PCBs and PBDEs. When hazard quotients (HQs) of PCBs and PBDEs were estimated for infant health risk, the HQs in some milk samples from the dumping site exceeded the threshold value (HQ>1) of PCBs, indicating the potential risk for infants in the specific site.

  19. Magnetic solid-phase extraction of brominated flame retardants from environmental waters with graphene-doped Fe3O4 nanocomposites.

    PubMed

    Yang, Jing; Qiao, Jun-qin; Cui, Shi-hai; Li, Jia-yuan; Zhu, Jin-jin; Yin, He-xing; Zhan, Cheng-yan; Lian, Hong-zhen

    2015-06-01

    Graphene-doped Fe3O4 nanocomposites were prepared by a solvothermal reaction of an iron source with graphene. The nanocomposites were characterized by transmission electron microscopy, atomic force microscopy, X-ray diffraction, superconducting quantum interference, Raman spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. This nanomaterial has been used as a magnetic solid-phase extraction sorbent to extract trace brominated flame retardants from environmental waters. Various extraction parameters were optimized including dosage and reusability of the nanocomposites, and pH of sample matrix. The reliability of the magnetic solid-phase extraction protocol based on graphene-doped Fe3O4 nanocomposites was evaluated by investigating the recoveries of 2,4,6-tribromophenol, tetrabromobisphenol A, 4-bromodiphenyl ether, and 4,4'-dibromodiphenyl ether in water samples. Good recoveries (85.0-105.0%) were achieved with the relative standard deviation ranging from 1.1-7.1%. Moreover, it is speculated from characterization and magnetic solid-phase extraction experiment that there is not only π-π stacking but also possible hydrophobic interaction between the graphene-doped Fe3O4 nanocomposites and analytes.

  20. Brominated flame retardants and perfluoroalkyl acids in groundwater, tile drainage, soil, and crop grain following a high application of municipal biosolids to a field.

    PubMed

    Gottschall, N; Topp, E; Edwards, M; Payne, M; Kleywegt, S; Lapen, D R

    2017-01-01

    Dewatered municipal biosolids (DMB) were applied at a rate of 22Mgdwha(-1) to an agricultural field in fall 2008. Concentrations of polybrominated diphenyl ethers (PBDEs; BDE-47, -99, -100, -153, -154, -183, -197, -207, -209), other brominated flame retardants (BFRs; HBB, PBEB, DBDPE, BTBPE) and perfluoroalkyl acids (PFAAs; PFHxS, PFOS, PFDS, PFOSA, PFHpA, PFOA, PFNA, PFDA, PFUnA, PFDoA, PFTA) were monitored in tile drainage, groundwater (2m, 4m and 6m depth), soil cores (0-0.3m) pre- and post-application, DMB aggregates incorporated into the soil post-application, and in wheat (Triticum spp.) planted post-application. Several compounds were detected in soil and water pre-application and on a reference field plot. PBDEs, other BFRs and PFAAs were detected in tile drainage and 2m groundwater throughout the post-application study period; a few PBDEs were also detected sporadically at lower depths in groundwater. Some of these compounds had not been detected pre-application, while some exceeded reference field plot/pre-application levels (some significantly (p<0.05) in tile drainage); both cases indicating biosolid-based water contamination. In DMB aggregates, several PBDE congeners were found to have dissipated exponentially, with reductions >90% in many of them within 1year post-application. Exponential dissipation of other BFRs and PFAAs in DMB aggregates were not significant. No PBDEs, other BFRs, or PFAAs were detected in wheat grain.

  1. Brominated flame retardants, polychlorinated biphenyls, and organochlorine pesticides in captive giant panda (ailuropoda melanoleuca) and red panda (Ailurus fulgens) from China.

    PubMed

    Hu, Guo-Cheng; Luo, Xiao-Jun; Dai, Jia-Yin; Zhang, Xiu-Lan; Wu, Hua; Zhang, Cheng-Lin; Guo, Wei; Xu, Mu-Qi; Mai, Bi-Xian; Weit, Fu-Wen

    2008-07-01

    Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and brominated flame retardants (BFRs) were investigated in captive giant and red panda tissues from China. The total concentrations of OCPs, PCBs, and polybrominated diphenyl ethers (PBDEs) in tissues ranged from 16.3 to 888 ng/g lipid weight (lw), 24.8 to 854 ng/g lw, and 16.4 to 2158 ng/g lw, respectively. p,p'-DDE and beta-HCH were major OCP contaminants. PCBs 99, 118, 153/132, 170, 180, and 209 were the major contributing congeners determined. Among PBDEs, congener BDE-209 was the most frequent and abundant, followed by BDE-206, BDE-208, BDE-207, BDE-203, BDE-47, and BDE-153. Decabromodiphenyl ethane (DeBDethane) was detected in 87 and 71% of the giant and red panda samples with concentrations up to 863 ng/g lw, respectively. The remarkable levels and dominance of BDE-209 and DeBDethane may relate to significant production, usage, or disposal of BFRs in China. The positive significant correlation between concentrations of PBDEs and PCBs in captive pandas may suggest that the exposure routes of PBDEs and PCBs to panda are similar. To our knowledge, this is the first report of the occurrence of DeBDethane in captive wildlife samples. Therefore, further studies are warranted to better understand DeBDethane production, transport, uptake, and toxicological effect.

  2. Use of the SPARC software program to calculate hydrolysis rate constants for the polymeric brominated flame retardants BC-58 and FR-1025.

    PubMed

    Rayne, Sierra; Forest, Kaya

    2016-01-01

    The SPARC software program was used to estimate the acid-catalyzed, neutral, and base-catalyzed hydrolysis rate constants for the polymeric brominated flame retardants BC-58 and FR-1025. Relatively rapid hydrolysis of BC-58, producing 2,4,6-tribromophenol-and ultimately tetrabromobisphenol A-as the hydrolytically stable end products from all potential hydrolysis reactions, is expected in both environmental and biological systems with starting material hydrolytic half-lives (t(1/2,hydr)) ranging from less than 1 h in marine systems, several hours in cellular environments, and up to several weeks in slightly acid fresh waters. Hydrolysis of FR-1025 to give 2,3,4,5,6-pentabromobenzyl alcohol is expected to be slower (t(1/2,hydr) less than 0.5 years in marine systems up to several years in fresh waters) than BC-58, but is also expected to occur at rates that will contribute significantly to environmental and in vivo loadings of this compound.

  3. In vitro assessment of human nuclear hormone receptor activity and cytotoxicity of the flame retardant mixture FM 550 and its triarylphosphate and brominated components.

    PubMed

    Belcher, Scott M; Cookman, Clifford J; Patisaul, Heather B; Stapleton, Heather M

    2014-07-15

    Firemaster(®) 550 (FM 550) is a mixture of brominated and triarylphosphate flame retardants used in polyurethane foam-based products. The primary components are also used in numerous other applications and are thus common household and industrial contaminants. Our previous animal studies suggested that FM 550 exposure may alter metabolism and cause weight gain. Employing human nuclear receptor (NR) luciferase reporter assays, the goal of this study was to evaluate the agonist actions of FM 550 and its constituent compounds at NRs with known roles in establishing or regulating energy balance. FM 550 was found to have significant agonist activity only at the master regulator of adipocyte differentiation PPARγ. As a result, the concentration response relationships and relative activities of FM 550 at PPARγ were investigated in more detail with the contribution of each chemical component defined and compared to the activities of the prototypical PPARγ environmental ligands triphenyltin and tributyltin. The resulting data indicated that the primary metabolic disruptive effects of FM 550 were likely mediated by the activity of the triarylphosphates at PPARγ, and have identified TPP as a candidate metabolic disruptor that also acts as a cytotoxicant.

  4. In vitro assessment of human nuclear hormone receptor activity and cytotoxicity of the flame retardant mixture FM 550 and its triarylphosphate and brominated components

    PubMed Central

    Belcher, Scott M.; Cookman, Clifford J.; Patisaul, Heather B.; Stapleton, Heather M.

    2014-01-01

    Firemaster® 550 (FM 550) is a mixture of brominated and triarylphosphate flame retardants used in polyurethane foam-based products. The primary components are also used in numerous other applications and are thus common household and industrial contaminants. Our previous animal studies suggested that FM 550 exposure may alter metabolism and cause weight gain. Employing human nuclear receptor (NR) luciferase reporter assays, the goal of this study was to evaluate the agonist actions of FM 550 and its constituent compounds at NRs with known roles in establishing or regulating energy balance. FM 550 was found to have significant agonist activity only at the master regulator of adipocyte differentiation PPARγ. As a result, the concentration response relationships and relative activities of FM 550 at PPARγ were investigated in more detail with the contribution of each chemical component defined and compared to the activities of the prototypical PPARγ environmental ligands triphenyltin and tributylytin. The resulting data indicated that the primary metabolic disruptive effects of FM 550 were likely mediated by the activity of the triarylphosphates at PPARγ, and have identified TPP as a candidate metabolic disruptor that also acts as a cytotoxicant. PMID:24786373

  5. Modification and calibration of a passive air sampler for monitoring vapor and particulate phase brominated flame retardants in indoor air: application to car interiors.

    PubMed

    Abdallah, Mohamed Abou-Elwafa; Harrad, Stuart

    2010-04-15

    A passive air sampler was modified to monitor both vapor and particulate phase brominated flame retardants (BFRs) in indoor air using polyurethane foam disks and glass fiber filters (GFF). Significant correlation (p < 0.01) was observed between passive (ng day(-1)) and active sampler (ng m(-3)) derived BFR concentrations in an office microenvironment (r = 0.94 and 0.89 for vapor and particulate phase BFRs, respectively). A calibration experiment was performed where concentrations of target BFRs were obtained for an office using a low volume active sampler operated over a 50 day period alongside passive samplers. The passive uptake rates of each studied BFR ranged between (0.558-1.509 ng day(-1)) and (0.448-0.579 ng day(-1)) for vapor and particulate phases, respectively. The passive entrapment of particles by the GFF was investigated using environmental scanning electron microscopy which revealed gravitational deposition of particles as the main mechanism involved. The developed sampler was applied to monitor BFR concentrations in 21 cars. Average concentrations of SigmaHBCDs, TBBP-A, and Sigmatetra-deca BDEs were 400, 3, and 2200 pg m(-3) in cabins and 400, 1, and 1600 pg m(-3) in trunks. No significant differences (p < 0.05) were observed between levels of SigmaHBCDs and Sigmatrito hexa- BDEs in cabins and trunks. However, TBBP-A, BDE-209, and SigmaPBDEs concentrations were significantly higher in vehicle cabins.

  6. Distribution of metals and brominated flame retardants (BFRs) in sediments, soils and plants from an informal e-waste dismantling site, South China.

    PubMed

    Wang, Junxia; Liu, Lili; Wang, Jinfu; Pan, Bishu; Fu, Xiaoxu; Zhang, Gang; Zhang, Long; Lin, Kuangfei

    2015-01-01

    Brominated flame retardants (BFRs, including polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol-A (TBBPA)) and metals (Cu, Zn, Pb, Cd, Ni, Hg and As) in sediments, soils and herb plants from unregulated e-waste disposal sites were examined. The metal concentrations, ∑PBDE and TBBPA concentrations in all samples from the examined e-waste dismantling sites were relatively high in comparison with those of rural and urban areas around the world. The PBDE and TBBPA levels in soils significantly decreased with increasing distance from the e-waste dismantling sites, indicating that PBDEs and TBBPA had similar transport potential from the e-waste dismantling process as a point source to the surrounding region. BDE-209 and TBBPA predominated in all samples, which is consistent with the evidence that the deca-BDE and TBBPA commercial mixtures were extensively used in electronic products. Metals, PBDEs and TBBPA displayed significant positive correlations with TOC, whereas the correlations with pH were insignificant, indicating that TOC was a major factor governing the spatial distribution, transportation and fate in sediments and soils. A significant relationship between log-transformed metals and BFR concentrations indicated common pollution sources. Moreover, cluster analysis and principal component analysis further confirmed that the metals and BFRs had a common source, and penta- and deca-BDE commercial products may be two sources of PBDEs in this region.

  7. Concentration of novel brominated flame retardants and HBCD in leachates and sediments from selected municipal solid waste landfill sites in Gauteng Province, South Africa.

    PubMed

    Olukunle, O I; Okonkwo, O J

    2015-09-01

    In this study leachate and sediment samples were collected from six municipal solid waste landfill sites across Gauteng Province in South Africa to determine the levels of 2-ethylhexyl 2,3,4,5 tetrabromobenzoate (EH-TBB), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenyl ethane (DBDPE), bis(2-ethylhexyl)-3,4,5,6-tetrabromo-phthalate (BEH-TEBP) and hexabromocyclododecane (HBCD). Soxhlet as well as liquid-liquid extraction were employed for sediment and leachates respectively followed by GC-EIMS analysis. Concentrations of novel brominated flame retardants (NBFRs) ranged from below detection (

  8. A mixture of the novel brominated flame retardants TBPH and TBB affects fecundity and transcript profiles of the HPGL-axis in Japanese medaka.

    PubMed

    Saunders, David M V; Podaima, Michelle; Codling, Garry; Giesy, John P; Wiseman, Steve

    2015-01-01

    The novel brominated flame retardants (NBFRs), bis(2-ethylhexyl)-2,3,4,5-tetrabromophthalate (TBPH) and 2-ethylhexyl-2,3,4,5 tetrabromobenzoate (TBB) are components of the flame retardant mixture Firemaster 550 and both TBPH and TBB have recently been listed as high production volume chemicals by the US EPA. These NBFRs have been detected in several environmental matrices but very little is known about their toxic effects or potencies. Results of in vitro assays demonstrated potentials of these NBFRs to modulate endocrine function through interactions with estrogen (ER) and androgen receptors (AR) and via alterations to synthesis of 17-β-estradiol (E2) and testosterone (T), but in vivo effects of these chemicals on organisms are not known. Therefore a 21-day short term fish fecundity assay with Japanese medaka (Oryzias latipes) was conducted to investigate if these NBFRs affect endocrine function in vivo. Medaka were fed a diet containing either 1422 TBPH:1474 TBB or 138:144 μg/g food, wet weight (w/w). Cumulative production of eggs was used as a measure of fecundity and abundances of transcripts of 34 genes along the hypothalamus-pituitary-gonadal-liver (HPGL) axis were quantified to determine mechanisms of observed effects. Cumulative fecundity was impaired by 32% in medaka exposed to the greatest dose of the mixture of TBPH/TBB. A pattern of global down-regulation of gene transcription at all levels of the HPGL axis was observed, but effects were sex-specific. In female medaka the abundance of transcripts of ERβ was lesser in livers, while abundances of transcripts of VTG II and CHG H were greater. In male medaka, abundances of transcripts of ERα, ERβ, and ARα were lesser in gonads and abundances of transcripts of ERβ and ARα were lesser in brain. Abundances of transcripts of genes encoding proteins for synthesis of cholesterol (HMGR), transport of cholesterol (HDLR), and sex hormone steroidogenesis (CYP 17 and 3β-HSD) were significantly lesser in male

  9. 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.

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

    PubMed

    van Leeuwen, Stefan P J; de Boer, Jacob

    2008-02-01

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

  11. A numerical study on the effect of hydrogen/reformate gas addition on flame temperature and NO formation in strained methane/air diffusion flames

    SciTech Connect

    Guo, Hongsheng; Neill, W. Stuart

    2009-02-15

    This paper investigates the effects of hydrogen/reformate gas addition on flame temperature and NO formation in strained methane/air diffusion flames by numerical simulation. The results reveal that flame temperature changes due to the combined effects of adiabatic temperature, fuel Lewis number and radiation heat loss, when hydrogen/reformate gas is added to the fuel of a methane/air diffusion flame. The effect of Lewis number causes the flame temperature to increase much faster than the corresponding adiabatic equilibrium temperature when hydrogen is added, and results in a qualitatively different variation from the adiabatic equilibrium temperature as reformate gas is added. At some conditions, the addition of hydrogen results in a super-adiabatic flame temperature. The addition of hydrogen/reformate gas causes NO formation to change because of the variations in flame temperature, structure and NO formation mechanism, and the effect becomes more significant with increasing strain rate. The addition of a small amount of hydrogen or reformate gas has little effect on NO formation at low strain rates, and results in an increase in NO formation at moderate or high strain rates. However, the addition of a large amount of hydrogen increases NO formation at all strain rates, except near pure hydrogen condition. Conversely, the addition of a large amount of reformate gas results in a reduction in NO formation. (author)

  12. PILOT-SCALE STUDIES ON THE EFFECT OF BROMINE ADDITION ON THE EMISSIONS OF CHLORINATED ORGANIC COMBUSTION BY-PRODUCTS

    EPA Science Inventory

    The paper reports on a study to evaluate organic combustion by-product emissions while feeding varying amounts of bromine (Br) and chlorine (Cl) into a pilot-scale incinerator burning surrogate waste materials. (NOTE: Adding brominated organic compounds to a pilot-scale incinerat...

  13. High throughput sample preparation in combination with gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-MS/MS): a smart procedure for (ultra)trace analysis of brominated flame retardants in fish.

    PubMed

    Kalachova, Kamila; Cajka, Tomas; Sandy, Chris; Hajslova, Jana; Pulkrabova, Jana

    2013-02-15

    In this study, gas chromatography (GC) coupled to triple quadrupole tandem mass spectrometry (MS/MS) operated in electron ionisation mode (EI) has been shown to be an effective tool for the (ultra)trace analysis of several representative brominated flame retardants (BFRs) including polybrominated diphenyl ethers (PBDEs), pentabromotoluene (PBT), pentabromoethylbenzene (PBEB), etc. in complex food and environmental matrices. Using this type of instrumentation, improved selectivity and sensitivity of the instrumental analysis was achieved. In addition to GC-MS/MS (EI), a GC-MS method employing QqQ as a single quadrupole in negative chemical ionisation (NCI) mode was also developed, as this technique might be preferred for those compounds where EI did not provide suitable (intensive enough) mass transitions (e.g., decabromodiphenyl ethane). Following the development of the GC-MS/MS method, a substantial simplification of the sample preparation method was achieved by employing an ethyl acetate QuEChERS-based extraction followed by silica minicolumn clean-up. Using this novel approach, six samples may be prepared in approx. one hour, thus significant time savings were achieved compared to routinely used methods. In addition, the method employs the reduced amounts of organic solvent and other chemicals. Under the optimised conditions, recoveries of all target analytes using both GC-MS/MS (EI) and GC-MS (NCI) were within the range of 70-119% and repeatabilities of the analytical procedure were ≤ 16% at all three spiking levels (0.1, 1 and 5 μg kg(-1)). Regarding quantification limits (LOQs), as expected, a single quadruple operated in NCI provided significantly lower LOQs compared to EI. However, using the triple quadrupole mass analyser, comparable LOQs were achieved for both methods (0.005-1 μg kg(-1) and 0.005-0.1 μg kg(-1) for GC-MS/MS (EI) and GC-MS (NCI), respectively). Moreover, when highly selective mass transitions in GC-MS/MS (EI) were used for

  14. Exposure to the androgenic brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)-cyclohexane alters reproductive and aggressive behaviors in birds.

    PubMed

    Marteinson, Sarah C; Letcher, Robert J; Fernie, Kimberly J

    2015-10-01

    Detected in environmental samples, 1,2-dibromo-4-(1,2-dibromoethyl) cyclohexane (DBE-DBCH) is a bioaccumulative isomer of a current-use brominated flame retardant. All 4 structural isomers are androgen agonists; however, little toxicological information exists for this compound. The objective of the present study was to determine if β-DBE-DBCH, the isomer found most prominently in animal tissue, affects androgen-dependent behavior of breeding American kestrels (Falco sparverius). The authors hypothesized that if β-DBE-DBCH acts as an androgen agonist in kestrels, androgen-dependent behaviors (i.e., copulation, courtship, aggression) would increase and behaviors inhibited by androgens (i.e., parental care behaviors) would decrease. Sixteen captive experimental kestrel pairs were exposed to 0.239 ng β-DBE-DBCH/g kestrel/d by diet from 4 wk prior to pairing until their nestlings hatched (mean 82 d) and compared with vehicle only-exposed control pairs (n = 15). Androgen-dependent behaviors were significantly increased in β-DBE-DBCH-exposed birds, consistent with the authors' hypothesis. These behavioral changes included copulation and other sexual behaviors in males and females and aggression in males, suggesting that β-DBE-DBCH may have acted like an androgen agonist in these birds. Parental behaviors were not reduced in exposed birds as predicted, although dietary exposure had ceased before chicks hatched. Further assessment of β-DBE-DBCH is recommended given these behavioral changes and the previously reported reproductive changes in the same birds.

  15. Improving the accuracy of hand-held X-ray fluorescence spectrometers as a tool for monitoring brominated flame retardants in waste polymers.

    PubMed

    Guzzonato, A; Puype, F; Harrad, S J

    2016-09-01

    An optimised method for Br quantification as a metric of brominated flame retardant (BFR) concentrations present in Waste Electrical and Electronic Equipment (WEEE) polymers is proposed as an alternative to the sophisticated, yet time consuming GC-MS methods currently preferred. A hand-held X-ray fluorescence (XRF) spectrometer was validated with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). Customized standard materials of specific BFRs in a styrenic polymer were used to perform an external calibration for hand-held XRF ranging from 0.08 to 12 wt% of Br, and cross-checking with LA-ICP-MS having similar LODs (0.0004 wt% for LA-ICP-MS and 0.0011 wt% for XRF). The "thickness calibration" developed here for hand-held XRF and the resulting correction, was applied to 28 real samples and showed excellent (R(2) = 0.9926) accordance with measurements obtained via LA-ICP-MS. This confirms the validity of hand-held XRF as an accurate technique for the determination of Br in WEEE plastics. This is the first use of solid standards to develop a thickness-corrected quantitative XRF measurement of Br in polymers using LA-ICP-MS for method evaluation. Thermal desorption gas chromatography mass spectrometry (TD-GC-MS) was used to confirm the presence of specific BFRs in WEEE polymer samples. We propose that expressing limit values for BFRs in waste materials in terms of Br rather than BFR concentration (based on a conservative assumption about the BFR present), presents a practical solution to the need for an accurate, yet rapid and inexpensive technique capable of monitoring compliance with limit values in situ.

  16. Evaluation of spatial distribution and accumulation of novel brominated flame retardants, HBCD and PBDEs in an Italian subalpine lake using zebra mussel (Dreissena polymorpha).

    PubMed

    Poma, Giulia; Binelli, Andrea; Volta, Pietro; Roscioli, Claudio; Guzzella, Licia

    2014-01-01

    Because of the reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD), novel brominated flame retardants (NBFRs), including 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB), started to be marketed as alternatives to the banned formulations. In this study, the spatial distribution and accumulation of NBFRs, PBDEs, and HBCD in the biota have been investigated in the littoral compartment of a large and deep subalpine lake (Lake Maggiore, Northern Italy), using zebra mussel Dreissena polymorpha and roach (Rutilus rutilus) as bioindicators. To our knowledge, this is the first study reporting the contamination of NBFRs in the freshwater invertebrate D. polymorpha. Contamination of zebra mussel due to PBEB, HBB, and BTBPE was low, ranging from 0.9 to 2.9 ng/g lipid weight, from 1.1 to 2.9 ng/g l.w., and from 3.5 to 9.5 ng/g l.w., respectively. PBEB and BTBPE in roach were always below the detection limit, while the contamination of HBB ranged from < limits of detection (LOD) to 1.74 ng/g l.w., indicating a weak contamination. DBDPE was < LOD in all the considered biological samples. Finally, HBCD was detected in all organic tissues with mean concentrations up to 74.4 ng/g l.w. PBDE results, supported by principal component analysis elaboration, suggested a possible contamination due to the congeners composing the penta- and deca-BDE technical formulations, which are present in the Lake Maggiore basin. The biomagnification factor values showed that tetra- and penta-BDE biomagnified, while octa-, nona-, and deca-BDE were still bioavailable and detectable in the fish muscles, but they do not biomagnified. Considering the other BFRs, only HBCD showed a moderate biomagnification potential.

  17. Serum levels of brominated flame retardants (BFRs: PBDE, HBCD) and influence of dietary factors in a population-based study on Swedish adults.

    PubMed

    Bjermo, Helena; Aune, Marie; Cantillana, Tatiana; Glynn, Anders; Lind, P Monica; Ridefelt, Peter; Darnerud, Per Ola

    2017-01-01

    The aim of this study was to investigate associations between serum concentrations of brominated flame retardants and personal characteristics, including diet, in adults participating in a population-based study in Sweden 2010-11. Moreover, observed concentrations were used in a health risk assessment, using published health-based reference values. Serum samples of 170 adult individuals of both sexes were analyzed for 10 PBDE congeners and HBCD by GC-MS. When including concentrations between LOD and LOQ, highest median serum concentration was observed for BDE-153 (1.2 ng/g serum lipid), followed by BDE-209 (0.95 ng/g lipid), BDE-47 (0.49 ng/g lipid) and BDE-100 (0.21 ng/g lipid). Median concentration of HBCD was 0.10 ng/g lipid. A few markedly elevated concentrations of BDE-209, HBCD (77-78 ng/g lipid) and BDE-47 (44 ng/g lipid) were observed. The only statistical significant findings were higher BDE-153 concentrations in men than in women, and positive associations between serum BDE-153 concentrations and consumption of fish (total), beef, mutton and poultry. PBDE concentrations were in accordance with concentrations reported in other European countries but generally lower than those found in North America. Median PBDE serum concentrations observed in adults from Sweden suggest sufficient health protection, when compared with published health-based reference values, although some outliers with high serum concentrations had lower safety margins.

  18. Effects of metals on the transformation of hexabromocyclododecane (HBCD) in solvents: implications for solvent-based recycling of brominated flame retardants.

    PubMed

    Zhong, Yin; Peng, Ping'an; Yu, Zhiqiang; Deng, Haopeng

    2010-09-01

    The management of electronic wastes (e-wastes) has become a global issue as it may release large quantities of hazardous materials such as heavy metals and brominated flame retardants (BFRs) to the environment. Solvent-based recycling is a newly developed, efficient and environmentally beneficial technology for the removal or recovery of BFRs from e-wastes. However, little is known about the behavior of BFRs in the solvents and to what extent they may be affected by co-existing heavy metals. This study quantified the rates of transformation of hexabromocyclododecane (HBCD), a widely used BFR, in the presence of different solvents (i.e. acetone, methanol or toluene) and metals (i.e. Ni, Cu, Zn, Fe or Al). Our experimental results showed that less than 20% of HBCD was transformed in all pure solvent systems within 24h at 50 degrees C. The presence of Ni greatly increased the transformation of HBCD (45-99%) in these solvent systems, whereas other metals had little or no effect on extraction process. The kinetics study showed that transformation of HBCD in Ni-containing systems followed pseudo-first-order kinetics and that the highest transformation rate constant (1.2+/-0.1h(-1)) of HBCD was recorded in the Ni+acetone system. The formation of HBr and pentabromocyclododecene in the acetone+Ni system suggested that transformation of HBCD proceeded via dehydrobromination. Collectively, these results indicated that acetone should not be applied in the recycling or extraction of HBCD from Ni-rich e-wastes, as debromination of HBCD may occur during these processes, even at mild extraction temperatures.

  19. Distribution and fate of HBCD and TBBPA brominated flame retardants in North Sea estuaries and aquatic food webs.

    PubMed

    Morris, Steven; Allchin, Colin R; Zegers, Bart N; Haftka, Joris J H; Boon, Jan P; Belpaire, Claude; Leonards, Pim E G; Van Leeuwen, Stefan P J; De Boer, Jacob

    2004-11-01

    Tetrabromobisphenol A (TBBPA) and hexabromocyclododecane diastereoisomers (alpha-, beta/-, and gamma-HBCD) were investigated in effluents from sewage treatment works, landfill leachates, sediments, and food web organisms of the North Sea basin. Residues were quantified by liquid chromatography-mass spectrometry. Both flame retardants were enriched in sewage sludges, where a maximum total (sigma) HBCD concentration of 9.1 mg/kg (dry weight; d.w.) was found; TBBPA was at levels of 102 microg/kg. Landfill leachates from The Netherlands showed up to 36 mg (sigmaHBCD)/ kg (d.w.). gamma-HBCD dominated isomeric profiles in sediments, and concentrations were elevated near to a site of HBCD manufacture. alpha-HBCD was the primary congener detected in marine mammals; however, very few samples exhibited TBBPA. sigmaHBCD ranged from 2.1 to 6.8 mg/kg (lipid weight; l.w.) in liver and blubber of harbor porpoises (Phocoena phocoena) and seals (Phoca vitulina). TBBPA levels in cormorant (Phalacrocorax carbo) livers were up to 1 order of magnitude lower compared to sigmaHBCD. HBCD in eels (Anguilla anguilla) from the Scheldt basin (Belgium) reflected the spatial distribution of concentrations in local sediments. This study shows evidence of HBCD bioaccumulation at the trophic level and biomagnification in the ascending aquatic food chain, and these findings justify risk assessment studies at the ecosystem level.

  20. Mineral resource of the month: bromine

    USGS Publications Warehouse

    ,

    2009-01-01

    The article offers information on bromine, a natural element considered as a dissolved species in seawater, saltwater lakes and underground brines linked with petroleum deposits. Bromine belongs to the halogen group of elements and is characterized with brownish-red color and beach-like odor. It is commonly used in flame retardants, agriculture and drilling.

  1. Brominated and phosphorus flame retardants in White-tailed Eagle Haliaeetus albicilla nestlings: bioaccumulation and associations with dietary proxies (δ¹³C, δ¹⁵N and δ³⁴S).

    PubMed

    Eulaers, Igor; Jaspers, Veerle L B; Halley, Duncan J; Lepoint, Gilles; Nygård, Torgeir; Pinxten, Rianne; Covaci, Adrian; Eens, Marcel

    2014-04-15

    Very little is known on the exposure of high trophic level species to current-use brominated (BFRs) and phosphorus flame retardants (PFRs), although observations on their persistence, bioaccumulation potential, and toxicity have been made. We investigated the accumulation of BFRs and PFRs, and their associations with dietary proxies (δ(13)C, δ(15)N and δ(34)S), in plasma and feathers of White-tailed Eagle Haliaeetus albicilla nestlings from Trøndelag, Norway. In addition to accumulation of a wide range of polybrominated diphenyl ether (PBDE) congeners in both plasma and feathers, all non-PBDE BFRs and PFRs could be measured in feathers, while in plasma only two of six PFRs, i.e. tris-(2-chloroisopropyl) phosphate (TCIPP) and tris-(2,3-dichloropropyl) phosphate (TDCPP) were detected. PFR concentrations in feathers (0.95-3,000 ng g(-1)) were much higher than selected organochlorines (OCs), such as polychlorinated biphenyl 153 (CB 153; 2.3-15 ng g(-1)) and dichlorodiphenyldichloroethylene (p,p'-DDE; 2.3-21 ng g(-1)), PBDEs (0.03-2.3 ng g(-1)) and non-PBDE BFRs (0.03-1.5 ng g(-1)). Non-significant associations of PFR concentrations in feathers with those in plasma (P ≥ 0.74), and their similarity to reported atmospheric PFR concentrations, may suggest atmospheric PFR deposition on feathers. Most OCs and PBDEs, as well as tris(chloroethyl) phosphate (TCEP), tris(phenyl) phosphate (TPHP) and tri-(2-butoxyethyl) phosphate (TBOEP) were associated to δ(15)N and/or δ(13)C (all P ≤ 0.02). Besides δ(15)N enrichment, δ(34)S was depleted in nestlings from fjords, inherently close to an urbanised centre. As such, both may have been a spatial proxy for anthropogenic disturbance, possible confounding their use as dietary proxy.

  2. Heterogeneous nano-Fe/Ca/CaO catalytic ozonation for selective surface hydrophilization of plastics containing brominated and chlorinated flame retardants (B/CFRs): separation from automobile shredder residue by froth flotation.

    PubMed

    Mallampati, Srinivasa Reddy; Lee, Byoung Ho; Mitoma, Yoshiharu; Simion, Cristian

    2017-02-01

    One method of weakening the inherently hydrophobic surface of plastics relevant to flotation separation is heterogeneous nano-Fe/Ca/CaO catalytic ozonation. Nano-Fe/Ca/CaO-catalyzed ozonation for 15 min efficiently decreases the surface hydrophobicity of brominated and chlorinated flame retardant (B/CFR)-containing plastics (such as acrylonitrile-butadienestyrene (ABS), high-impact polystyrene (HIPS), and polyvinyl chloride (PVC)) in automobile shredder residue (ASR) to such an extent that their flotation ability is entirely depressed. Such a hydrophilization treatment also stimulates the ABS, HIPS, and PVC surface roughness, wetting of the surface, and the thermodynamic equilibrium conditions at the surface and ultimately changes surface polarity. SEM-EDS, AFM, and XPS analyses of the PVC and ABS surfaces demonstrated a marked decrease in [Cl/Br] and a significant increase in the number of hydrophilic groups, such as C-O, C=O, and (C=O)-O. Under froth flotation conditions at 50 rpm, about 99.5 % of ABS and 99.5 % of HIPS in ASR samples settled out, resulting in a purity of 98 and 98.5 % for ABS and HIPS in ASR samples, respectively. Furthermore, at 150 rpm, we also obtained 100 % PVC separation in the settled fraction, with 98 % purity in ASR. Total recovery of non-B/CFR-containing plastics reached nearly 100 % in the floating fraction. The amount of nano-Fe/Ca/CaO reagent employed during ozonation is very small, and additional removal of surface contaminants from the recycled ASR plastic surfaces by ozonation makes the developed process simpler, greener, and more effective.

  3. Lithium/bromine cell systems

    SciTech Connect

    Howard, W.G.; Skarstad, P.M.; Hayes, T.G.; Owens, B.B.

    1980-01-01

    Bromine is attractive as a cathode material because cells with a high energy density and high cell voltage are theoretically possible. The addition of small amounts of certain salts or organic compounds results in bromine solutions of sufficient conductivity for cathode applications. However, given these highly conductive bromine cathodes, lithium/bromine cells are limited in rate and practical available capacity by the high resistivity of the discharge product. The rate of resistance increase for the best bromine cells in this study is more than one order of magnitude greater than that observed for corresponding lithium/iodine cells. Lithium/bromine cells can function at pacemaker rates and they may be superior to cells used in early pacemakers. However, the authors have not found the lithium/bromine cells described to be superior to existing lithium/iodine cells available for cardiac pacemakers. 17 refs.

  4. Effects of the brominated flame retardant tetrabromobisphenol-A (TBBPA) on cell signaling and function of Mytilus hemocytes: involvement of MAP kinases and protein kinase C.

    PubMed

    Canesi, Laura; Lorusso, Lucia Cecilia; Ciacci, Caterina; Betti, Michele; Gallo, Gabriella

    2005-11-10

    Brominated flame retardants (BFRs) are a large group of compounds added to or applied as a treatment to polymeric materials to prevent fires. Tetrabisphenol A (TBBPA) is the most important individual BFR used in industry. Although TBBPA and its derivatives can be found in environmental samples, data are very limited on the presence of this compound in biota. Research on mammals indicates that TBBPA has low toxicity in vivo; however, in vitro TBBPA can act as a cytotoxicant, neurotoxicant, immunotoxicant, thyroid hormone agonist and has a weak estrogenic activity; in particular, the effects of TBBPA have been recently ascribed to its interactions with cellular signaling pathways, in particular with mitogen activated protein kinases (MAPKs). TBBPA has high acute toxicity to aquatic organisms, such as algae, molluscs, crustaceans and fish; however, little is known on the mechanisms of action of this compound in the cells of aquatic species. In this work, we investigated the possible effects and mechanisms of action of TBBPA on the immune cells, the hemocytes, of the marine mussel Mytilus galloprovincialis. The results demonstrate that TBBPA in the low micromolar range induces hemocyte lysosomal membrane destabilization. The effect was reduced or prevented by hemocyte pre-treatment by specific inhibitors of MAPKs and of protein kinase C (PKC). TBBPA stimulated phosphorylation of MAPK members and PKC, as evaluated by electrophoresis and Western blotting with anti-phospho-antibodies, although to a different extent and with distinct time-courses. A rapid (from 5 min) and transient increase in phosphoryation of the stress-activated JNK MAPKs and of PKC was observed, followed by a later increase (at 30-60 min) in phosphorylation of extracellularly regulated MAPKs (ERK2 MAPK) and of the stress-activated p38 MAPK. TBBPA significantly stimulated the hemocyte microbicidal activity towards E. coli, lysosomal enzyme release, phagocytic activity and extracellular superoxide (O2

  5. 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

  6. Recover bromine on site

    SciTech Connect

    Schubert, P.; Mahajan, S.; Beatty, R.D.; Rostrup-Nielsen, T.; Schubert, D.W.; Lu, Phat Tan

    1993-04-01

    Chemists have long recognized the importance of recovering bromine from waste streams, and attempts to do so catalytically date back more than 50 years. Although the early interest in bromine recovery was driven primarily by economics, increased environmental pressures are providing additional incentives to recycle this element. As the acceptability of discharging wastes into the environment decreases, the cost of doing so increases, creating a need for alternative handling. The authors interest in waste bromine recovery was driven by both economic and environmental factors. In their evaluation of a research program that included a bromination step as part of a synthesis process, Catalytica researchers found that the process would be feasible commercially only if the waste HBr produced were recycled on site to bromine. A nonbromine route was eventually adopted for this particular research program, but the need for an economical and environmentally sound process for recycling HBr to bromine was recognized. The development of this process became a project in its own right. This process eliminates the need to form and ship aqueous sodium bromide offsite. It converts the waste HBr directly to bromine by catalytic oxidation.

  7. Effects of CO addition on the characteristics of laminar premixed CH{sub 4}/air opposed-jet flames

    SciTech Connect

    Wu, C.-Y.; Chao, Y.-C.; Chen, C.-P.; Ho, C.-T.; Cheng, T.S.

    2009-02-15

    The effects of CO addition on the characteristics of premixed CH{sub 4}/air opposed-jet flames are investigated experimentally and numerically. Experimental measurements and numerical simulations of the flame front position, temperature, and velocity are performed in stoichiometric CH{sub 4}/CO/air opposed-jet flames with various CO contents in the fuel. Thermocouple is used for the determination of flame temperature, velocity measurement is made using particle image velocimetry (PIV), and the flame front position is measured by direct photograph as well as with laser-induced predissociative fluorescence (LIPF) of OH imaging techniques. The laminar burning velocity is calculated using the PREMIX code of Chemkin collection 3.5. The flame structures of the premixed stoichiometric CH{sub 4}/CO/air opposed-jet flames are simulated using the OPPDIF package with GRI-Mech 3.0 chemical kinetic mechanisms and detailed transport properties. The measured flame front position, temperature, and velocity of the stoichiometric CH{sub 4}/CO/air flames are closely predicted by the numerical calculations. Detailed analysis of the calculated chemical kinetic structures reveals that as the CO content in the fuel is increased from 0% to 80%, CO oxidation (R99) increases significantly and contributes to a significant level of heat-release rate. It is also shown that the laminar burning velocity reaches a maximum value (57.5 cm/s) at the condition of 80% of CO in the fuel. Based on the results of sensitivity analysis, the chemistry of CO consumption shifts to the dry oxidation kinetics when CO content is further increased over 80%. Comparison between the results of computed laminar burning velocity, flame temperature, CO consumption rate, and sensitivity analysis reveals that the effect of CO addition on the laminar burning velocity of the stoichiometric CH{sub 4}/CO/air flames is due mostly to the transition of the dominant chemical kinetic steps. (author)

  8. Electrophilic Anti Addition of Bromine to 2-Methylbut-2-Ene with the N-Methylpyrrolidin-2-One Hydrotribromide Complex

    ERIC Educational Resources Information Center

    Berrien, Jean-Francois; Provot, Olivier; Joseph, Delphine; Bekaert, Alain

    2004-01-01

    The N-methylpyrrolidin-2-one hydrotribromide complex (MPHT) is a stable solid that can be stored several months at room temperature. The MPHT is not corrosive, not necrosing, less toxic and easier to handle for students as compared to the molecular bromine.

  9. Halogenated flame retardants in the Great Lakes environment.

    PubMed

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

    2015-07-21

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

  10. Application of dual carbon-bromine isotope analysis for investigating abiotic transformations of tribromoneopentyl alcohol (TBNPA).

    PubMed

    Kozell, Anna; Yecheskel, Yinon; Balaban, Noa; Dror, Ishai; Halicz, Ludwik; Ronen, Zeev; Gelman, Faina

    2015-04-07

    Many of polybrominated organic compounds, used as flame retardant additives, belong to the group of persistent organic pollutants. Compound-specific isotope analysis is one of the potential analytical tools for investigating their fate in the environment. However, the isotope effects associated with transformations of brominated organic compounds are still poorly explored. In the present study, we investigated carbon and bromine isotope fractionation during degradation of tribromoneopentyl alcohol (TBNPA), one of the widely used flame retardant additives, in three different chemical processes: transformation in aqueous alkaline solution (pH 8); reductive dehalogenation by zero-valent iron nanoparticles (nZVI) in anoxic conditions; oxidative degradation by H2O2 in the presence of CuO nanoparticles (nCuO). Two-dimensional carbon-bromine isotope plots (δ(13)C/Δ(81)Br) for each reaction gave different process-dependent isotope slopes (Λ(C/Br)): 25.2 ± 2.5 for alkaline hydrolysis (pH 8); 3.8 ± 0.5 for debromination in the presence of nZVI in anoxic conditions; ∞ in the case of catalytic oxidation by H2O2 with nCuO. The obtained isotope effects for both elements were generally in agreement with the values expected for the suggested reaction mechanisms. The results of the present study support further applications of dual carbon-bromine isotope analysis as a tool for identification of reaction pathway during transformations of brominated organic compounds in the environment.

  11. On the effect of carbon monoxide addition on soot formation in a laminar ethylene/air coflow diffusion flame

    SciTech Connect

    Guo, Hongsheng; Thomson, Kevin A.; Smallwood, Gregory J.

    2009-06-15

    The effect of carbon monoxide addition on soot formation in an ethylene/air diffusion flame is investigated by experiment and detailed numerical simulation. The paper focuses on the chemical effect of carbon monoxide addition by comparing the results of carbon monoxide and nitrogen diluted flames. Both experiment and simulation show that although overall the addition of carbon monoxide monotonically reduces the formation of soot, the chemical effect promotes the formation of soot in an ethylene/air diffusion flame. The further analysis of the details of the numerical result suggests that the chemical effect of carbon monoxide addition may be caused by the modifications to the flame temperature, soot surface growth and oxidation reactions. Flame temperature increases relative to a nitrogen diluted flame, which results in a higher surface growth rate, when carbon monoxide is added. Furthermore, the addition of carbon monoxide increases the concentration of H radical owing to the intensified forward rate of the reaction CO + OH = CO{sub 2} + H and therefore increases the surface growth reaction rates. The addition of carbon monoxide also slows the oxidation rate of soot because the same reaction CO + OH = CO{sub 2} + H results in a lower concentration of OH. (author)

  12. Modelling of flame propagation in the gasoline fuelled Wankel rotary engine with hydrogen additives

    NASA Astrophysics Data System (ADS)

    Fedyanov, E. A.; Zakharov, E. A.; Prikhodkov, K. V.; Levin, Y. V.

    2017-02-01

    Recently, hydrogen has been considered as an alternative fuel for a vehicles power unit. The Wankel engine is the most suitable to be adapted to hydrogen feeding. A hydrogen additive helps to decrease incompleteness of combustion in the volumes near the apex of the rotor. Results of theoretical researches of the hydrogen additives influence on the flame propagation in the combustion chamber of the Wankel rotary engine are presented. The theoretical research shows that the blend of 70% gasoline with 30% hydrogen could accomplish combustion near the T-apex in the stoichiometric mixture and in lean one. Maps of the flame front location versus the angle of rotor rotation and hydrogen fraction are obtained. Relations of a minimum required amount of hydrogen addition versus the engine speed are shown on the engine modes close to the average city driving cycle. The amount of hydrogen addition that could be injected by the nozzle with different flow sections is calculated in order to analyze the capacity of the feed system.

  13. Fire-retardant coatings based on organic bromine/phenoxy or brominated epoxy systems

    SciTech Connect

    Hoffman, D.M.; Chiu, Ing L.

    1989-06-01

    Thin phenoxy and brominated epoxy/curing agent films were prepared by solvent casting on Mylar and Kapton. Thicknesses were approximated assuming volume additivity. Important parameters were uniformity of thickness, distribution of the bromine-containing fire retardant, adhesion to carrier substrate (either Mylar or Kapton), and uniformity of the coating, i.e., absence of pinholes, blush, blistering, etc. Wetting behavior was modified using fluoro, silicone or polyurea surfactants. Several solvent systems were examined and a ternary solvent system was ultimately used. Distribution of fire-retardant bromine was analyzed using electron microprobe, x-ray fluorescence and wet chemical methods. Significant discrepancies in the /mu/m-scale analyses of the microprobe measurements have not been resolved. Some of the brominated fire retardants were insoluble in the resin systems and the phase separation was immediately obvious. Similarly, some of the crystallizable epoxies could not be cast easily into homogeneous, amorphous films. Castings were made on a standard 8'' /times/ 10'' aluminum vacuum plate polished with jeweler's rouge prior to every casting. Solvent was removed in a forced air or vacuum oven. Removal and/or curing was accelerated with temperature. The fire-retardant bromine was required to be stable in alcohol/salt solutions. Final formulation used after a significant amount of testing was phenoxy resin PKHC in a ternary solvent system composed of methylethyl ketone, cellosolve acetate and toluene. Tetrabromobisphenol A was used as the flame retardant with FC-430 as surfactant. The dying schedule was 30 minutes at 150/degree/C. 4 refs., 6 figs., 3 tabs.

  14. Quantitative Study of the Effects of Chemical Additives in Propellant Flames

    DTIC Science & Technology

    2008-11-02

    sensitive test of details of the kinetic model . The dependence on equivalence ratio of the characteristic reaction paths in DME flames is examined within... kinetic model for DME combustion [Zhao et al., Int. J. Chem. Kinetics , 2008, 40, 1-18] that has been extensively tested against laminar flame speed...Westmoreland, "Composition of reaction intermediates for stoichiometric and fuel-rich dimethyl ether flames: Flame-sampling mass spectrometry and modeling

  15. Effect of Nitrogen Additives on Flame Retardant Action of Tributyl Phosphate: Phosphorus – Nitrogen Synergism

    SciTech Connect

    Gaan, Sabyasachi; Sun, Gang; Hutches, Katherine; Engelhard, Mark H.

    2008-01-01

    The effect of nitrogen additives like urea, guanidine carbonate and melamine formaldehyde on the flame retardant efficacy of tributyl phosphate (TBP) has been investigated. From the LOI tests on treated cotton it is clear that the nitrogen additives have synergistic action. Estimation of activation energy of decomposition of treated cotton indicated that nitrogen additives enhance the thermal stability during the burning process. SEM pictures of chars formed after LOI test showed the formation of protective polymeric coating on the surface. The surface of chars formed were evaluated using FTIR-ATR and XPS analysis which showed that the coating was composed of Phosphorus-Nitrogen-Oxygen containing species. Formation of this coating during the burning process could lead to the synergistic interaction of phosphorus and nitrogen. Based on the experimental data we have further proposed several reaction mechanisms which could contribute to synergistic action and formation of protective coating on the surface of char.

  16. In Vitro Metabolism of the Brominated Flame Retardants 2-Ethylhexyl-2,3,4,5-Tetrabromobenzoate (TBB) and Bis(2-Ethylhexyl) 2,3,4,5-Tetrabromophthalate (TBPH) in Human and Rat Tissues

    PubMed Central

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

    2012-01-01

    Due to the phaseout of polybrominated diphenyl ether (PBDE) flame retardants, new chemicals, such as 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (TBB) and bis(2-ethylhexyl) 2,3,4,5-tetrabromophthalate (TBPH), have been used as replacements in some commercial flame retardant mixtures. Both chemicals have been detected in indoor dust at concentrations approaching the concentrations of PBDEs; however, little is known about their fate, metabolism, or toxicity. The goal of this study was to investigate the potential metabolism of these two brominated flame retardants in human and rat tissues by conducting in vitro experiments with liver and intestinal subcellular fractions. In all the experiments, TBB was consistently metabolized to 2,3,4,5-tetrabromobenzoic acid (TBBA) via cleavage of the 2-ethylhexyl chain without requiring any added cofactors. TBBA was also formed in purified porcine carboxylesterase, but at a much faster rate of 6.29 ± 0.58 nmol min-1 mg protein-1. The estimated Km and Vmax values for TBB metabolism in human microsomes were 11.1 ± 3.9 μM and 0.644 ± 0.144 nmol min-1 mg protein-1, respectively. A similar Km of 9.3 ± 2.2 μM was calculated for porcine carboxylesterase, indicating similar enzyme specificity. While the rapid formation of TBBA may reduce the bioaccumulation potential of TBB in mammals and may be useful as a biomarker of TBB exposure, the toxicity of this brominated benzoic acid is unknown and may be a concern based on its structural similarity to other toxic pollutants. In contrast to TBB, no metabolites of TBPH were detected in human or rat subcellular fractions. However, a metabolic product of TBPH, mono(2-ethylhexyl) tetrabromophthalate (TBMEHP), was formed in purified porcine carboxylesterase at an approximate rate of 1.08 pmol min-1 mg protein-1. No Phase II metabolites of TBBA or TBMEHP were observed. More research is needed to understand the in vivo toxicokinetics and health effects of these compounds given their current

  17. Alkaline reforming of brominated fire-retardant plastics: fate of bromine and antimony.

    PubMed

    Onwudili, Jude A; Williams, Paul T

    2009-02-01

    High-impact polystyrene (HIPS) flame retarded with decabromodiphenyl ether (DDE), has been reacted in supercritical water from 380 to 450 degrees C and 21.5 to 31.0 MPa pressure in a batch reactor. Different concentrations of sodium hydroxide additive were used in situ to neutralize the corrosive inorganic bromine species released during the reactions. It appeared that supercritical water conditions lowered the decomposition temperature of both the fire-retardant DDE and HIPS. The reaction products included oils (up to 76 wt%), char (up to 18 wt%) and gas (up to 2.4 wt%) which was mainly methane. The presence of the alkaline water led to up to 97 wt% debromination of the product oil, producing virtually bromine-free oil feedstock. The removal of antimony from the oil product during processing was of the order of 98 wt%. The oil consisted of many single- and multiple-ringed aromatic compounds, many of which had alkyl substituents and/or aliphatic C(n)-bridges (n=1-4). The major single-ringed compounds included toluene, xylenes, ethylbenzene, propylbenzene and alpha-methylstyrene. Bibenzyl (diphenylethane), stilbene, diphenylmethane, diphenylpropane, diphenylcyclopropane, diphenylpropene, diphenylbutane, diphenylbutene and diphenylbuta-1,3-diene were the major C(n)-bridged compounds. Diphenyl ether and acetophenone were the major oxygenated compounds found. The process thus has the potential to produce bromine-free and antimony-free oils from fire-retardant plastics.

  18. Lithium-Ion Electrolytes Containing Phosphorous-Based, Flame-Retardant Additives

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Smith, Kiah A.; Bugga, Ratnakumar V.; Prakash, G. K. Surya

    2010-01-01

    Future NASA missions aimed at exploring Mars, the Moon, and the outer planets require rechargeable batteries that can operate over a wide temperature range (-60 to +60 C) to satisfy the requirements of various applications. In addition, many of these applications will require improved safety, due to their use by humans. Currently, the state-of-the-art lithium-ion (Li-ion) system has been demonstrated to operate over a wide range of temperatures (-40 to +40 C); however, abuse conditions can often lead to cell rupture and fire. The nature of the electrolyte can greatly affect the propensity of the cell/battery to catch fire, given the flammability of the organic solvents used within. Li-ion electrolytes have been developed that contain a flame-retardant additive in conjunction with fluorinated co-solvents to provide a safe system with a wide operating temperature range. Previous work incorporated fluorinated esters into multi-component electrolyte formulations, which were demonstrated to cover a temperature range from 60 to +60 C. This work was described in Fluoroester Co-Solvents for Low-Temperature Li+ Cells (NPO-44626), NASA Tech Briefs, Vol. 33, No. 9 (September 2009), p. 37; and Optimized Li-Ion Electrolytes Con tain ing Fluorinated Ester Co-Solvents (NPO-45824), NASA Tech Briefs, Vol. 34, No. 3 (March 2010), p. 48. Other previous work improved the safety characteristics of the electrolytes by adding flame-retardant additives such as triphenyl phosphate (TPhPh), tri-butyl phosphate (TBuPh), triethyl phosphate (TEtPh), and bis(2,2,2-trifluoroethyl) methyl phosphonate (TFMPo). The current work involves further investigation of other types of flame-retardant additives, including tris(2,2,2-trifluoroethyl) phosphate, tris(2,2,2-trifluoroethyl) phosphite, triphenylphosphite, diethyl ethylphosphonate, and diethyl phenylphosphonate added to an electrolyte composition intended for wide operating temperatures. In general, many of the formulations investigated in this

  19. Brominated dibenzofurans

    Integrated Risk Information System (IRIS)

    Brominated dibenzofurans ; no CASRN Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Ef

  20. The effects of hydrodynamic stretch on the flame propagation enhancement of ethylene by addition of ozone.

    PubMed

    Pinchak, Matthew; Ombrello, Timothy; Carter, Campbell; Gutmark, Ephraim; Katta, Viswanath

    2015-08-13

    The effect of O(3) on C(2)H(4)/synthetic-air flame propagation at sub-atmospheric pressure was investigated through detailed experiments and simulations. A Hencken burner provided an ideal platform to interrogate flame speed enhancement, producing a steady, laminar, nearly one-dimensional, minimally curved, weakly stretched, and nearly adiabatic flame that could be accurately compared with simulations. The experimental results showed enhancement of up to 7.5% in flame speed for 11 000 ppm of O(3) at stoichiometric conditions. Significantly, the axial stretch rate was also found to affect enhancement. Comparison of the flames for a given burner exit velocity resulted in the enhancement increasing almost 9% over the range of axial stretch rates that was investigated. Two-dimensional simulations agreed well with the experiments in terms of flame speed, as well as the trends of enhancement. Rate of production analysis showed that the primary pathway for O(3) consumption was through reaction with H, leading to early heat release and increased production of OH. Higher flame stretch rates resulted in increased flux through the H+O(3) reaction to provide increased enhancement, due to the thinning of the flame that accompanies higher stretch, and thus results in decreased distance for the H to diffuse before reacting with O(3).

  1. 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...

  2. The Effects of Hydrodynamic Stretch on the Flame Propagation Enhancement of Ethylene by Addition of Ozone

    DTIC Science & Technology

    2015-07-13

    enhancement increasing almost 9% over the range of axial stretch rates that was investigated. Two- dimensional simulations agreed well with the...experiments in terms of flame speed, as well as the trends of enhancement. Rate of production analysis showed that the primary pathway for O3 consumption was...directly into a flame front or into the reactants. Over the past several decades, the application of plasma to combustion systems has been shown to help

  3. Bromine Safety

    SciTech Connect

    Meyers, B

    2001-04-09

    The production and handling in 1999 of about 200 million kilograms of bromine plus substantial derivatives thereof by Great Lakes Chemical Corp. and Albemarle Corporation in their southern Arkansas refineries gave OSHA Occupational Injury/Illness Rates (OIIR) in the range of 0.74 to 1.60 reportable OIIRs per 200,000 man hours. OIIRs for similar industries and a wide selection of other U.S. industries range from 1.6 to 23.9 in the most recent OSHA report. Occupational fatalities for the two companies in 1999 were zero compared to a range in the U.S.of zero for all computer manufacturing to 0.0445 percent for all of agriculture, forestry and fishing in the most recent OSHA report. These results show that bromine and its compounds can be considered as safe chemicals as a result of the bromine safety standards and practices at the two companies. The use of hydrobromic acid as an electrical energy storage medium in reversible PEM fuel cells is discussed. A study in 1979 of 20 megawatt halogen working fluid power plants by Oronzio de Nora Group found such energy to cost 2 to 2.5 times the prevailing base rate at that time. New conditions may reduce this relative cost. The energy storage aspect allows energy delivery at maximum demand times where the energy commands premium rates. The study also found marginal cost and performance advantages for hydrobromic acid over hydrochloric acid working fluid. Separate studies in the late 70s by General Electric also showed marginal performance advantages for hydrobromic acid.

  4. Accumulation of polychlorinated biphenyls and brominated flame retardants in breast milk from women living in Vietnamese e-waste recycling sites.

    PubMed

    Tue, Nguyen Minh; Sudaryanto, Agus; Minh, Tu Binh; Isobe, Tomohiko; Takahashi, Shin; Viet, Pham Hung; Tanabe, Shinsuke

    2010-04-01

    This study investigated the contamination status of PCBs, PBDEs and HBCDs in human and possible exposure pathways in three Vietnamese e-waste recycling sites: Trang Minh (suburb of Hai Phong city), Dong Mai and Bui Dau (Hung Yen province), and one reference site (capital city Hanoi) by analysing human breast milk samples and examining the relationships between contaminant levels and lifestyle factors. Levels of PBDEs, but not PCBs and HBCDs, were significantly higher in Trang Minh and Bui Dau than in the reference site. The recyclers from Bui Dau had the highest levels of PBDEs (20-250 ng g(-1) lipid wt.), higher than in the reference group by two orders of magnitude and more abundant than PCBs (28-59 ng g(-1) lipid wt.), and were also the only group with significant exposure to HBCDs (1.4-7.6 ng g(-1) lipid wt.). A specific accumulation, unrelated to diet, of low-chlorinated PCBs and high-brominated PBDEs was observed in e-waste recyclers, suggesting extensive exposure to these compounds during e-waste recycling activities, possibly through inhalation and ingestion of dust. The estimated infant intake dose of PBDEs from breast milk of some mothers occupationally involved in e-waste recycling were close to or higher than the reference doses issued by the U.S. EPA.

  5. Optimized Li-Ion Electrolytes Containing Triphenyl Phosphate as a Flame-Retardant Additive

    NASA Technical Reports Server (NTRS)

    Smart, Marshall C.; Bugga, Ratnakumar V.; Prakash, G. K. Surya; Krause, Frederick C.

    2011-01-01

    A number of future NASA missions involving the exploration of the Moon and Mars will be human-rated and thus require high-specific-energy rechargeable batteries that possess enhanced safety characteristics. Given that Li-ion technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. There is also a strong desire to develop Li-ion batteries with improved safety characteristics for terrestrial applications, most notably for hybrid electric vehicle (HEV) and plug-in hybrid electric vehicle (PHEV) automotive applications. Therefore, extensive effort has been devoted recently to developing non-flammable electrolytes to reduce the flammability of the cells/battery. A number of electrolyte formulations have been developed, including systems that (1) incorporate greater concentrations of the flame-retardant additive (FRA); (2) use di-2,2,2-trifluoroethyl carbonate (DTFEC) as a co-solvent; (3) use 2,2,2- trifluoroethyl methyl carbonate (TFEMC); (4) use mono-fluoroethylene carbonate (FEC) as a co-solvent and/or a replacement for ethylene carbonate in the electrolyte mixture; and (5) utilize vinylene carbonate as a "SEI promoting" electrolyte additive, to build on the favorable results previously obtained. To extend the family of electrolytes developed under previous work, a number of additional electrolyte formulations containing FRAs, most notably triphenyl phosphate (TPP), were investigated and demonstrated in experimental MCMB (mesocarbon micro beads) carbon- LiNi(0.8)Co(0.2)O2 cells. The use of higher concentrations of the FRA is known to reduce the flammability of the electrolyte solution, thus, a concentration range was investigated (i.e., 5 to 20 percent by volume). The desired concentration of the FRA is the highest amount tolerable without adversely affecting the performance in terms of reversibility, ability to operate over a wide temperature range, and

  6. Bromination of Phenol

    ERIC Educational Resources Information Center

    Talbot, Christopher

    2013-01-01

    This "Science note" examines the bromination of phenol, a reaction that is commonly taught at A-level and IB (International Baccalaureate) as an example of electrophilic substitution. Phenol undergoes bromination with bromine or bromine water at room temperature. A white precipitate of 2,4,6-tribromophenol is rapidly formed. This…

  7. Levels of brominated diphenylether, dibenzo-P-dioxin, and dibenzofuran in flue gases of a municipal waste combustor

    EPA Science Inventory

    Due to the extensive use of brominated flame retardants (BFRs), including brominated diphenylether (BDE) formulations, for various domestic and industrial applications, the presence of brominated chemicals in the waste stream is to be expected for decades. As much as 40% to 50% o...

  8. 21 CFR 180.30 - Brominated vegetable oil.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Brominated vegetable oil. 180.30 Section 180.30... Requirements for Certain Food Additives § 180.30 Brominated vegetable oil. The food additive brominated vegetable oil may be safely used in accordance with the following prescribed conditions: (a) The...

  9. Analytical method for biomonitoring of endocrine-disrupting compounds (bisphenol A, parabens, perfluoroalkyl compounds and a brominated flame retardant) in human hair by liquid chromatography-tandem mass spectrometry.

    PubMed

    Martín, Julia; Santos, Juan Luis; Aparicio, Irene; Alonso, Esteban

    2016-11-16

    In this paper, a method for the determination of four groups of endocrine-disrupting compounds in human hair is proposed. Target compounds were a plastic monomer (bisphenol A), three parabens commonly used as preservatives (methylparaben, ethylparaben and propylparaben), six perfluoroalkyl compounds commonly used as water, oil and dirt repellents (perfluorooctane sulfonic acid and five perfluoroalkyl carboxylic acids, with alkyl chains from four to eight carbon atoms) and a brominated flame retardant (hexabromocyclododecane). All of them are of especial concern to human health because they are utilized in many everyday products. The method is based on hair incubation with methanol/acetic acid solution (85:15, v/v), extraction with acetone for 15 min in an ultrasonic bath and analysis by liquid chromatography-electrospray-tandem mass spectrometry in negative ionization mode. Limits of quantification in hair samples ranged from 0.6 ng g(-1) to 6.1 ng g(-1), except for hexabromocyclododecane (36 ng g(-1)). Recoveries were higher than 69%. Intra-day and inter-day precision, expressed as relative standard deviation, were lower than 15% and 10%, respectively. The applicability of the method was proven by analyzing the target compounds in hair samples from six volunteers. High frequencies of detection and concentrations were obtained for bisphenol A (83% of samples; concentrations up to 158 ng g(-1)) and parabens (100% of samples; concentrations up to 624 ng g(-1)). Lower concentrations were detected for the perfluoroalkyl compounds (up to 13 ng g(-1)). Hexabromocyclododecane was not detected.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  11. 49 CFR 173.228 - Bromine pentafluoride or bromine trifluoride.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Bromine pentafluoride or bromine trifluoride. 173... Class 1 and Class 7 § 173.228 Bromine pentafluoride or bromine trifluoride. (a) Bromine pentafluoride and bromine trifluoride are authorized in packagings as follows: (1) Specification 3A150,...

  12. 49 CFR 173.228 - Bromine pentafluoride or bromine trifluoride.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 2 2010-10-01 2010-10-01 false Bromine pentafluoride or bromine trifluoride. 173... Class 1 and Class 7 § 173.228 Bromine pentafluoride or bromine trifluoride. (a) Bromine pentafluoride and bromine trifluoride are authorized in packagings as follows: (1) Specification 3A150,...

  13. 49 CFR 173.228 - Bromine pentafluoride or bromine trifluoride.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Bromine pentafluoride or bromine trifluoride. 173... Class 1 and Class 7 § 173.228 Bromine pentafluoride or bromine trifluoride. (a) Bromine pentafluoride and bromine trifluoride are authorized in packagings as follows: (1) Specification 3A150,...

  14. 49 CFR 173.228 - Bromine pentafluoride or bromine trifluoride.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Bromine pentafluoride or bromine trifluoride. 173... Class 1 and Class 7 § 173.228 Bromine pentafluoride or bromine trifluoride. (a) Bromine pentafluoride and bromine trifluoride are authorized in packagings as follows: (1) Specification 3A150,...

  15. 49 CFR 173.228 - Bromine pentafluoride or bromine trifluoride.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Bromine pentafluoride or bromine trifluoride. 173... Class 1 and Class 7 § 173.228 Bromine pentafluoride or bromine trifluoride. (a) Bromine pentafluoride and bromine trifluoride are authorized in packagings as follows: (1) Specification 3A150,...

  16. 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.

  17. Rodent Thyroid, Liver, and Fetal Testis Toxicity of the Monoester Metabolite of Bis-(2-ethylhexyl) Tetrabromophthalate (TBPH), a Novel Brominated Flame Retardant Present in Indoor Dust

    PubMed Central

    Springer, Cecilia; Dere, Edward; Hall, Susan J.; McDonnell, Elizabeth V.; Roberts, Simon C.; Butt, Craig M.; Stapleton, Heather M.; Watkins, Deborah J.; McClean, Michael D.; Webster, Thomas F.; Schlezinger, Jennifer J.

    2012-01-01

    Background: Bis-(2-ethylhexyl) tetrabromophthalate (TBPH) is widely used as a replacement for polybrominated diphenyl ethers (PBDEs) in commercial flame retardant mixtures such as Firemaster 550. It is also used in a commercial mixture called DP 45. Mono-(2-ethyhexyl) tetrabromophthalate (TBMEHP) is a potentially toxic metabolite. Objectives: We used in vitro and rodent in vivo models to evaluate human exposure and the potential metabolism and toxicity of TBPH. Methods: Dust collected from homes, offices, and cars was measured for TBPH by gas chromatography followed by mass spectrometry. Pregnant rats were gavaged with TBMEHP (200 or 500 mg/kg) or corn oil on gestational days 18 and 19, and dams and fetuses were evaluated histologically for toxicity. We also assessed TBMEHP for deiodinase inhibition using rat liver microsomes and for peroxisome proliferator-activated receptor (PPAR) α and γ activation using murine FAO cells and NIH 3T3 L1 cells. Results: TBPH concentrations in dust from office buildings (median, 410 ng/g) were higher than in main living areas in homes (median, 150 ng/g). TBPH was metabolized by purified porcine esterases to TBMEHP. Two days of TBMEHP exposure in the rat produced maternal hypothyroidism with markedly decreased serum T3 (3,3´,5-triiodo-l-thyronine), maternal hepatotoxicity, and increased multinucleated germ cells (MNGs) in fetal testes without antiandrogenic effects. In vitro, TBMEHP inhibited deiodinase activity, induced adipocyte differentiation in NIH 3T3 L1 cells, and activated PPARα- and PPARγ-mediated gene transcription in NIH 3T3 L1 cells and FAO cells, respectively. Conclusions: TBPH a) is present in dust from indoor environments (implying human exposure) and b) can be metabolized by porcine esterases to TBMEHP, which c) elicited maternal thyrotoxic and hepatotoxic effects and d) induced MNGs in the fetal testes in a rat model. In mouse NIH 3T3 L1 preadipocyte cells, TBMEHP inhibited rat hepatic microsome deiodinase

  18. 21 CFR 180.30 - Brominated vegetable oil.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false Brominated vegetable oil. 180.30 Section 180.30... Brominated vegetable oil. The food additive brominated vegetable oil may be safely used in accordance with... used on an interim basis as a stabilizer for flavoring oils used in fruit-flavored beverages, for...

  19. 21 CFR 180.30 - Brominated vegetable oil.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false Brominated vegetable oil. 180.30 Section 180.30... Brominated vegetable oil. The food additive brominated vegetable oil may be safely used in accordance with... used on an interim basis as a stabilizer for flavoring oils used in fruit-flavored beverages, for...

  20. 21 CFR 180.30 - Brominated vegetable oil.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Brominated vegetable oil. 180.30 Section 180.30... Brominated vegetable oil. The food additive brominated vegetable oil may be safely used in accordance with... used on an interim basis as a stabilizer for flavoring oils used in fruit-flavored beverages, for...

  1. 21 CFR 180.30 - Brominated vegetable oil.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Brominated vegetable oil. 180.30 Section 180.30... Brominated vegetable oil. The food additive brominated vegetable oil may be safely used in accordance with... used on an interim basis as a stabilizer for flavoring oils used in fruit-flavored beverages, for...

  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. A GC/ECNI-MS method for the identification of lipophilic anthropogenic and natural brominated compounds in marine samples.

    PubMed

    Vetter, W

    2001-10-15

    GC/ECNI-MS in both the full scan and selected ion monitoring modes was applied to study the patterns of brominated compounds in the blubber of marine mammals from a variety of locations. The adipose tissue of one polar bear was also studied. Occurrence of three major residues originating from the use of brominated flame-retardants (PBDE 47, 99, and 100) and several potential naturally occurring brominated compounds was studied in the samples. A series of three major natural brominated compounds (BC-1, BC-2, BC-3) recently identified in dolphins from Australia was included in this study. Two further brominated compounds, BC-10 and BC-11, were studied for the first time. ECNI-MS full scan spectra were obtained for BC-3 and BC-10. A natural mixed halogenated compound (MHC-1) and an unknown brominated compound (UBC-1) were investigated as well. Evidence for the natural production of these secondary metabolites and their bioaccumulation in higher organisms as well as analytical protocols for their detection in the environment are presented. Some of these naturally occurring compounds may be misinterpreted as anthropogenic brominated compounds. In ECNI-MS, brominated compounds are usually identified by the detection of the fragment ions m/z 79 ([79Br]-) and m/z 81 ([81Br]-). In this work, it is shown that monitoring of additional ion traces corresponding to [Br2]- (160 type), [HBr2]- (161 type), [BrCl]- (116 type), and [HBrCl]- (117 type) fragment ions allows distinguishing between different classes of brominated compounds. This technique was used to demonstrate that UBC-1 is neither a PBDE nor a PBB congener, whereas a second mixed halogenated compound (MHC-2) was identified as a result of the ECNI-MS response at m/z 114/116. Studies on blubber extracts of marine mammals from four continents resulted in the detection of significant differences in the global distribution of brominated compounds. Our results suggest that naturally occurring organobromines are more

  4. Triple flame structure and diffusion flame stabilization

    NASA Technical Reports Server (NTRS)

    Veynante, D.; Vervisch, L.; Poinsot, T.; Linan, A.; Ruetsch, G.

    1994-01-01

    The stabilization of diffusion flames is studied using asymptotic techniques and numerical tools. The configuration studied corresponds to parallel streams of cold oxidizer and fuel initially separated by a splitter plate. It is shown that stabilization of a diffusion flame may only occur in this situation by two processes. First, the flame may be stabilized behind the flame holder in the wake of the splitter plate. For this case, numerical simulations confirm scalings previously predicted by asymptotic analysis. Second, the flame may be lifted. In this case a triple flame is found at longer distances downstream of the flame holder. The structure and propagation speed of this flame are studied by using an actively controlled numerical technique in which the triple flame is tracked in its own reference frame. It is then possible to investigate the triple flame structure and velocity. It is shown, as suggested from asymptotic analysis, that heat release may induce displacement speeds of the triple flame larger than the laminar flame speed corresponding to the stoichiometric conditions prevailing in the mixture approaching the triple flame. In addition to studying the characteristics of triple flames in a uniform flow, their resistance to turbulence is investigated by subjecting triple flames to different vortical configurations.

  5. NOx reduction in diesel fuel flames by additions of water and CO{sub 2}

    SciTech Connect

    Li, S.C.

    1997-12-31

    Natural gas has the highest heating value per unit mass (50.1 MJ/kg, LHV) of any of the hydrocarbon fuels (e.g., butane, liquid diesel fuel, gasoline, etc.). Since it has the lowest carbon content per unit mass, combustion of natural gas produces much less carbon dioxide, soot particles, and oxide of nitrogen than combustion of liquid diesel fuel. In view of anticipated strengthening of regulations on pollutant emissions from diesel engines, alternative fuels, such as compressed natural gas (CNG) and liquefied natural gas (LNG) have been experimentally introduced to replace the traditional diesel fuels in heavy-duty trucks, transit buses, off-road vehicles, locomotives, and stationary engines. To help in applying natural gas in Diesel engines and increasing combustion efficiency, the emphasis of the present paper is placed on the detailed flame chemistry of methane-air combustion. The present work is the continued effort in finding better methods to reduce NO{sub x}. The goal is to identify a reliable chemical reaction mechanism for natural gas in both premixed and diffusion flames and to establish a systematic reduced mechanism which may be useful for large-scale numerical modeling of combustion behavior in natural gas engines.

  6. Measurements of bromine containing organic compounds at the tropical tropopause

    NASA Astrophysics Data System (ADS)

    Schauffler, S. M.; Atlas, E. L.; Flocke, F.; Lueb, R. A.; Stroud, V.; Travnicek, W.

    The amount of bromine entering the stratosphere from organic source gases is a primary factor involved in determining the magnitude of bromine catalyzed loss of ozone. Thirty two whole air samples were collected at the tropical tropopause during the NASA STRAT Campaign in Feb., Aug., and Dec., 1996 and were analyzed for brominated organic compounds. Total organic bromine was 17.4±0.9 ppt with 55% from methyl bromide, 38% from the Halons, 6% from dibromomethane, and 0.8% from bromochloromethane and dichlorobromomethane. One flight showed the presence of 0.42 ppt of additional organic bromine from bromoform and dibromochloromethane.

  7. HEALTH EFFECTS OF BROMINATED FLAME RETARDANTS (BFRS)

    EPA Science Inventory

    BFRs are a broad class of compounds providing fire safety. Because of high production and usage and recent findings that they are ubiquitous in environmental samples and biota, concerns exist about potential health effects. Some of the major commercial products, such as tetrabr...

  8. Polyfunctional epoxies. I - Rubber-toughened brominated and nonbrominated formulations for graphite composites. II - Nonrubber versus rubber-toughened brominated formulations for graphite composites

    NASA Technical Reports Server (NTRS)

    Nir, Z.; Gilwee, W. J.; Kourtides, D. A.; Parker, J. A.

    1985-01-01

    A new trifunctional epoxy resin, Tris-(hydroxyphenyl) methane triglycidyl ether, is compared to a state-of-the-art tetraglycidyl 4,4'-diaminodiphenyl methane (TGDDM), in graphite composites. Rubber-toughened brominated formulations of the epoxy resin are compared to nonbrominated ones in terms of their mechanical performance, environmental stability, thermochemical behavior, and flame retardancy. It is shown that the new resin performs almost the same way as the TGDDM does, but has improved glass transition temperature and environmental properties. Brominated polymeric additives (BPA) of different molecular weights are tested as a Br source to flame retardant graphite epoxy composites. The optimal molecular weight of the BPA and its polymeric backbone length are derived and compared with a 10 percent rubber-toughened formulation of the epoxy resin. Results indicate that when the Br content in the graphite composite is increased without the use of rubber, the mechanical properties improved. The use of BPAs as tougheners for graphite composites is also considered.

  9. Effect of flame-retarding additives on surface chemistry in Li-ion batteries

    SciTech Connect

    Nam, N.D.; Park, I.J.; Kim, J.G.; Kim, H.S.

    2012-10-15

    This study examined the properties of 1 wt.% vinylene carbonate (VC), vinyl ethylene carbonate (VEC), and diphenyl octyl phosphate (DPOF) additive electrolytes as a promising way of beneficially improving the surface and cell resistance of Li-ion batteries. Surface film formation on the negative and positive electrodes was analyzed by electrochemical impedance spectroscopy (EIS), Fourier transform infrared (FT-IR) spectroscopy, and scanning electron microscopy (SEM). In conclusion, EIS, FT-IR spectroscopy and SEM results confirmed that DPOF is an excellent additive to the electrolyte in the Li-ion batteries due to the improved co-intercalation of the solvent molecules.

  10. EFFECT OF OXYGEN ADDITION ON POLYCYCLIC AROMATIC HYDROCARBON FORMATION IN 1,3 BUTADIENE COUNTER-FLOW DIFFUSION FLAMES. (R828193)

    EPA Science Inventory

    The effect of 3% O2 addition to the fuel on detailed chemical structure of a 1,3 butadiene counter-flow diffusion flame has been investigated by using heated microprobe sampling and online gas chromatography mass spectrometry. Centerline gas temperature and species ...

  11. The Evaluation of Triphenyl Phosphate as a Flame Retardant Additive to Improve the Safety of Lithium-Ion Battery Electrolytes

    NASA Technical Reports Server (NTRS)

    Smart, M. C.; Krause, F. C.; Hwang, C.; West, W. C.; Soler, J.; Prakash, G. K. S.; Ratnakumar, B. V.

    2011-01-01

    With the intent of improving the safety characteristics of lithium ion cells, electrolytes containing flame retardant additives have been investigated. A number of triphenyl phosphate-containing electrolytes were evaluated in both coin cells and experimental three electrode lithium-ion cells (containing reference electrodes). A number of chemistries were investigated, including MCMB carbon/LiNi(0.8)Co(0.2)O2 (NCO), graphite/LiNi(0.8)Co(0.15)Al(0.05)O2 (NCA), Li/Li(Li(0.17)Ni(0.25)Mn(0.58))O2, Li/LiNiMnCoO2 (NMC) and graphite/LiNiMnCoO2 (NMC), to study the effect that different electrolyte compositions have upon performance. A wide range of TPP-containing electrolytes were demonstrated to have good compatibility with the C/NCO, C/NCA, and Li/NMC systems, however, poor performance was initially observed with the high voltage C/NMC system. This necessitated the development of improved electrolytes with stabilizing additives, leading to formulations containing lithium bis(oxalato)borate (LiBOB) that displayed substantially improved performance.

  12. 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

  13. A non-intrusive method for temperature measurements in flames produced by milligram-sized solid samples

    NASA Astrophysics Data System (ADS)

    Frances, Colleen Elizabeth

    Fires are responsible for the loss of thousands of lives and billions of dollars in property damage each year in the United States. Flame retardants can assist in the prevention of fires through mechanisms which either prevent or greatly inhibit flame spread and development. In this study samples of both brominated and non-brominated polystyrene were tested in the Milligram-scale Flaming Calorimeter and images captured with two DSL-R cameras were analyzed to determine flame temperatures through use of a non-intrusive method. Based on the flame temperature measurement results, a better understanding of the gas phase mechanisms of flame retardants may result, as temperature is an important diagnostic in the study of fire and combustion. Measurements taken at 70% of the total flame height resulted in average maximum temperatures of about 1656 K for polystyrene and about 1614 K for brominated polystyrene, suggesting that the polymer flame retardant may reduce flame temperatures.

  14. Measurements of stratospheric bromine

    NASA Technical Reports Server (NTRS)

    Sedlacek, W. A.; Lazrus, A. L.; Gandrud, B. W.

    1984-01-01

    From 1974 to 1977, molecules containing acidic bromine were sampled in the stratosphere by using tetrabutyl ammonium hydroxide impregnated filters. Sampling was accomplished by WB-57F aircraft and high-altitude balloons, spanning latitudes from the equator to 75 deg N and altitudes up to 36.6 km. Analytical results are reported for 4 years of measurements and for laboratory simulations that determined the filter collection efficiencies for a number of brominated species. Mass mixing ratios for the collected bromine species in air average about 27 pptm in the stratosphere. Seasonal variability seems to be small.

  15. 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...

  16. Flame Imaging System

    NASA Technical Reports Server (NTRS)

    Barnes, Heidi L. (Inventor); Smith, Harvey S. (Inventor)

    1998-01-01

    A system for imaging a flame and the background scene is discussed. The flame imaging system consists of two charge-coupled-device (CCD) cameras. One camera uses a 800 nm long pass filter which during overcast conditions blocks sufficient background light so the hydrogen flame is brighter than the background light, and the second CCD camera uses a 1100 nm long pass filter, which blocks the solar background in full sunshine conditions such that the hydrogen flame is brighter than the solar background. Two electronic viewfinders convert the signal from the cameras into a visible image. The operator can select the appropriate filtered camera to use depending on the current light conditions. In addition, a narrow band pass filtered InGaAs sensor at 1360 nm triggers an audible alarm and a flashing LED if the sensor detects a flame, providing additional flame detection so the operator does not overlook a small flame.

  17. Analysis of Flame Retardancy in Polymer Blends by Synchrotron X-ray K-edge Tomography and Interferometric Phase Contrast Movies.

    PubMed

    Olatinwo, Mutairu B; Ham, Kyungmin; McCarney, Jonathan; Marathe, Shashidhara; Ge, Jinghua; Knapp, Gerry; Butler, Leslie G

    2016-03-10

    Underwriters Laboratories 94 test bars have been imaged with X-ray K-edge tomography between 12 and 32 keV to assess the bromine and antimony concentration gradient across char layers of partially burnt samples. Phase contrast tomography on partially burnt samples showed gas bubbles and dark-field scattering ascribed to residual blend inhomogeneity. In addition, single-shot grating interferometry was used to record X-ray movies of test samples during heating (IR and flame) intended to mimic the UL 94 plastics flammability test. The UL 94 test bars were formulated with varying concentrations of a brominated flame retardant, Saytex 8010, and a synergist, Sb2O3, blended into high-impact polystyrene (HIPS). Depending on the sample composition, samples will pass or fail the UL 94 plastics flammability test. Tomography and interferometry imaging show differences that correlate with UL 94 performance. Key features such as char layer, gas bubble formation, microcracks, and dissolution of the flame retardant in the char layer regions are used in understanding the efficiency of the flame retardant and synergist. The samples that pass the UL 94 test have a thick, highly visible char layer as well as an interior rich in gas bubbles. Growth of gas bubbles from flame-retardant thermal decomposition is noted in the X-ray phase contrast movies. Also noteworthy is an absence of bubbles near the burning surface of the polymer; dark-field images after burning suggest a microcrack structure between interior bubbles and the surface. The accepted mechanism for flame retardant activity includes free radical quenching in the flame by bromine and antimony species. The imaging supports this as well as provides a fast inspection of other parameters, such as viscosity and surface tension.

  18. Combustion and inorganic bromine emission of waste printed circuit boards in a high temperature furnace.

    PubMed

    Ni, Mingjiang; Xiao, Hanxi; Chi, Yong; Yan, Jianhua; Buekens, Alfons; Jin, Yuqi; Lu, Shengyong

    2012-03-01

    High temperature combustion experiments of waste printed circuit boards (PCBs) were conducted using a lab-scale system featuring a continuously-fed drop tube furnace. Combustion efficiency and the occurrence of inorganic bromine (HBr and Br(2)) were systematically studied by monitoring the main combustion products continuously. The influence of furnace temperature (T) was studied from 800 to 1400°C, the excess air factor (EAF) was varied from 1.2 to 1.9 and the residence time in the high temperature zone (RT(HT)) was set at 0.25, 0.5, or 0.75 s. Combustion efficiency depends on temperature, EAF and RT(HT); temperature has the most significant effect. Conversion of organic bromine from flame retardants into HBr and Br(2) depends on temperature and EAF. Temperature has crucial influence over the ratio of HBr to Br(2), whereas oxygen partial pressure plays a minor role. The two forms of inorganic bromine seem substantially to reach thermodynamic equilibrium within 0.25s. High temperature is required to improve the combustion performance: at 1200°C or higher, an EAF of 1.3 or more, and a RT(HT) exceeding 0.75 s, combustion is quite complete, the CO concentration in flue gas and remained carbon in ash are sufficiently low, and organobrominated compounds are successfully decomposed (more than 99.9%). According to these results, incineration of waste PCBs without preliminary separation and without additives would perform very well under certain conditions; the potential precursors for brominated dioxins formation could be destroyed efficiently. Increasing temperature could decrease the volume percentage ratio of Br(2)/HBr in flue gas greatly.

  19. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  20. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  1. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  2. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  3. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Bromide ion and residual bromine... Tolerances § 180.519 Bromide ion and residual bromine; tolerances for residues. (a) General. The food additives, bromide ion and residual bromine, may be present in water, potable in accordance with...

  4. Application of Shear Plate Interferometry to Jet Diffusion Flame Temperature Measurements

    NASA Technical Reports Server (NTRS)

    VanDerWege, Brad A.; OBrien, Chris J.; Hochgreb, Simone

    1997-01-01

    The recent ban on the production of bromotrifluoromethane (CF3Br) because of its high stratospheric ozone depletion potential has led to interest in finding alternative agents for fire extinguishing applications. Some of the promising alternatives are fluorinated hydrocarbons. A clear understanding of the effects of CF3Br and alternative chemical suppressants on diffusion flames is therefore necessary in the selection of alternative suppressants for use in normal and microgravity. The flame inhibition effects of halogen compounds have been studied extensively in premixed systems. The effect of addition of halocarbons (carbon-halogen compounds) to diffusion flames has been studied experimentally in coflow configurations and in counterflow gaseous and liquid-pool flames. Halogenated compounds are believed to inhibit combustion by scavenging hydrogen radicals to form the relatively unreactive compound HF, or through a catalytic recombination cycle involving HBr to form H2. Comparisons between halogens show that bromine inhibition is significantly more effective than chlorine or fluorine. Although fluorinated compounds are only slightly more effective inhibitors on a mass basis than nitrogen, they are more effective on a volume basis and are easily stored in liquid form. The objectives of this study are (a) to determine the stability limits of laminar jet diffusion flames with respect to inhibitor concentration in both normal and microgravity, and (b) to investigate the structure of halocarbon-inhibited flames. In the initial phase of this project, visual diagnostics were used to observe the structure and behavior of normal and microgravity flames. The initial observations showed significant changes in the structure of the flames with the addition of halocarbons to the surrounding environment, as discussed below. Furthermore, the study established that the flames are more stable relative to the addition of halocarbons in microgravity than in normal gravity. Visual

  5. Catalytic bromine recovery from HBr waste

    SciTech Connect

    Schubert, P.F.; Beatty, R.D.; Mahajan, S.

    1993-12-31

    Waste HBr is formed during the bromination of many organic molecules, such as flame retardants, pharmaceuticals, and agricultural chemicals. For over 50 years attempts to recover the bromine from waste HBr by catalytic oxidation have been unsuccessful due to low catalyst activity and stability. The discovery of a new high-activity catalysts with excellent long-term stability and life capable of high HBr conversion below 300{degrees}C has made catalytic oxidation of waste HBr commercially feasible. The oxidation of anhydrous HBr using oxygen is highly exothermic, giving an adiabatic temperature rise of 2000{degrees}C. Use of 48 wt% HBr in the oxidation reduces the adiabatic temperature rise to only 300{degrees}C. A multitubular heat exchanger type of reactor can then be used to manage the heat. A 5,000 kg/yr pilot plant was built to verify the performance of the catalyst, the suitability of the reactor materials of construction, and the multibular reactor concept. The pilot unit has a single full-scale reactor tube 4 m long and 2.54 cm in diameter with a hot oil jacket for heat management. Excellent catalyst stability was observed during a 600 h catalyst-life test. HBr conversion of 99% was maintained throughout the run, and over 360 kg of bromine was produced. The temperature at a localized hot spot near the reactor inlet was only 15-20{degrees}C above the reactor inlet temperature, indicating efficient heat management.

  6. Solid bromine complexers

    DOEpatents

    Grimes, Patrick G.

    1987-01-20

    The cell of the invention comprises a housing, a zinc or cadmium anode, a chemically non-reactive counterelectrode and cathodic halogen. The cathodic halogen is selected from chlorine and bromine, and preferably is bromine. The cell also is provided with an aqueous metal halide containing electrolyte in which the metal ions are of the same metal as the metal of the anode and halide anions are of the same halogen as the cathodic halogen material. Importantly, in the present invention, anion exchange resins provide a convenient means for storing the halogen generated during charging of the cell and providing a source of halogen to be used in the discharge of the cell.

  7. 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.

  8. Combustion and inorganic bromine emission of waste printed circuit boards in a high temperature furnace

    SciTech Connect

    Ni Mingjiang; Xiao Hanxi; Chi Yong; Yan Jianhua; Buekens, Alfons; Jin Yuqi; Lu Shengyong

    2012-03-15

    bromine from flame retardants into HBr and Br{sub 2} depends on temperature and EAF. Temperature has crucial influence over the ratio of HBr to Br{sub 2}, whereas oxygen partial pressure plays a minor role. The two forms of inorganic bromine seem substantially to reach thermodynamic equilibrium within 0.25 s. High temperature is required to improve the combustion performance: at 1200 Degree-Sign C or higher, an EAF of 1.3 or more, and a RT{sub HT} exceeding 0.75 s, combustion is quite complete, the CO concentration in flue gas and remained carbon in ash are sufficiently low, and organobrominated compounds are successfully decomposed (more than 99.9%). According to these results, incineration of waste PCBs without preliminary separation and without additives would perform very well under certain conditions; the potential precursors for brominated dioxins formation could be destroyed efficiently. Increasing temperature could decrease the volume percentage ratio of Br{sub 2}/HBr in flue gas greatly.

  9. A Substitute Foe "Bromine in Carbon Tetrachloride"

    ERIC Educational Resources Information Center

    Daley, Joshua M.; Landolt, Robert G.

    2005-01-01

    The addition of a dilute solution of bromine in carbon tetrachloride to a compound to test for carbon-carbon multiple bonds, which is one of the widely cited qualitative tests employed in organic chemistry is presented. Major advantages of this approach include the ease and rapidness of the procedure, the stability of the test solution over time,…

  10. Cool Flame Quenching

    NASA Technical Reports Server (NTRS)

    Pearlman, Howard; Chapek, Richard

    2001-01-01

    Cool flame quenching distances are generally presumed to be larger than those associated with hot flames, because the quenching distance scales with the inverse of the flame propagation speed, and cool flame propagation speeds are often times slower than those associated with hot flames. To date, this presumption has never been put to a rigorous test, because unstirred, non-isothermal cool flame studies on Earth are complicated by natural convection. Moreover, the critical Peclet number (Pe) for quenching of cool flames has never been established and may not be the same as that associated with wall quenching due to conduction heat loss in hot flames, Pe approx. = 40-60. The objectives of this ground-based study are to: (1) better understand the role of conduction heat loss and species diffusion on cool flame quenching (i.e., Lewis number effects), (2) determine cool flame quenching distances (i.e, critical Peclet number, Pe) for different experimental parameters and vessel surface pretreatments, and (3) understand the mechanisms that govern the quenching distances in premixtures that support cool flames as well as hot flames induced by spark-ignition. Objective (3) poses a unique fire safety hazard if conditions exist where cool flame quenching distances are smaller than those associated with hot flames. For example, a significant, yet unexplored risk, can occur if a multi-stage ignition (a cool flame that transitions to a hot flame) occurs in a vessel size that is smaller than that associated with the hot quenching distance. To accomplish the above objectives, a variety of hydrocarbon-air mixtures will be tested in a static reactor at elevated temperature in the laboratory (1g). In addition, reactions with chemical induction times that are sufficiently short will be tested aboard NASA's KC-135 microgravity (mu-g) aircraft. The mu-g results will be compared to a numerical model that includes species diffusion, heat conduction, and a skeletal kinetic mechanism

  11. ACUTE POSTNATAL EXPOSURE TO BROMINATED DIPHENYLETHER 47 DELAYS NEUROMOTOR ONTOGENY AND ALTERS MOTOR ACTIVITY IN MICE

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are widely used commercial flame retardants that are accumulating in the environment. 2,2’,4,4’-Brominated diphenyl ether (BDE 47) is a very stable congener of this group and has been shown to accumulate in humans. PBDEs may interfere with...

  12. Trophic transfer of naturally produced brominated aromatic compounds in a Baltic Sea food chain.

    PubMed

    Dahlgren, Elin; Lindqvist, Dennis; Dahlgren, Henrik; Asplund, Lillemor; Lehtilä, Kari

    2016-02-01

    Brominated aromatic compounds (BACs) are widely distributed in the marine environment. Some of these compounds are highly toxic, such as certain hydroxylated polybrominated diphenyl ethers (OH-PBDEs). In addition to anthropogenic emissions through use of BACs as e.g. flame retardants, BACs are natural products formed by marine organisms such as algae, sponges, and cyanobacteria. Little is known of the transfer of BACs from natural producers and further up in the trophic food chain. In this study it was observed that total sum of methoxylated polybrominated diphenyl ethers (MeO-PBDEs) and OH-PBDEs increased in concentration from the filamentous red alga Ceramium tenuicorne, via Gammarus sp. and three-spined stickleback (Gasterosteus aculeatus) to perch (Perca fluviatilis). The MeO-PBDEs, which were expected to bioaccumulate, increased in concentration accordingly up to perch, where the levels suddenly dropped dramatically. The opposite pattern was observed for OH-PBDEs, where the concentration exhibited a general trend of decline up the food web, but increased in perch, indicating metabolic demethylation of MeO-PBDEs. Debromination was also indicated to occur when progressing through the food chain resulting in high levels of tetra-brominated MeO-PBDE and OH-PBDE congeners in fish, while some penta- and hexa-brominated congeners were observed to be the dominant products in the alga. As it has been shown that OH-PBDEs are potent disruptors of oxidative phosphorylation and that mixtures of different congener may act synergistically in terms of this toxic mode of action, the high levels of OH-PBDEs detected in perch in this study warrants further investigation into potential effects of these compounds on Baltic wildlife, and monitoring of their levels.

  13. A study of tetrabromobisphenol A (TBBA) as a flame retardant additive for Li-ion battery electrolytes

    NASA Astrophysics Data System (ADS)

    Belov, Dmitry G.; Shieh, D. T.

    2014-02-01

    Electrochemical behavior and flammability of tetrabromobisphenol A (TBBA)-mixed electrolyte solutions are investigated using 1 mol L-1 LiPF6-EC:EMC (1:2 vol.%) with 0 wt.% (reference electrolyte) and 1-3 wt.% of TBBA. The cycling performance (at room and elevated temperature) and rate capability of the 18650 cell (LiMn2O4:Li(Ni1/3Co1/3Mn1/3)O2 (8:2)/Li4Ti5O12) cell containing TBBA-mixed electrolyte is similar to that of cell containing the reference electrolyte. A detailed analysis of the surface on both the anode and the cathode electrodes via X-ray photoelectron spectroscopy (XPS) indicated that the cathode electrode contains more Br components than the anode electrode. Within the first few cycles, on the positive electrode, we observe competing redox processes between the cathode material containing Mn and TBBA, which generate hydroxy radicals and other by-products. This process and the electrochemical reductive decomposition of TBBA to HBr, Br2 and bisphenole A are responsible for the increased flame retardant properties of the electrolyte containing TBBA. Safety tests were performed using an 18650 cell showed that even 1 wt.% of TBBA in the electrolyte significantly reduces cell flammability.

  14. Global Distribution of Organo-Bromine Gases.

    NASA Astrophysics Data System (ADS)

    Gunawardena, Rohith

    Both man-made and natural trace organo-bromine gases are present in the atmosphere in minute quantities --in the order of a few parts per trillion by volume. The man-made species CBrF_3 and CBrClF _2 are believed to be an important source of bromine to the stratosphere where they act as catalysts in the chlorofluorocarbon-ozone-depletion hypothesis. A high resolution capillary column EC-GC method with and O_2 doped detector was developed, System V, to measure these and related organo -bromine gases in the atmosphere. It was developed from a packed column EC-GC method, System I, that was used to measure CH_3I at sub pptv levels but could measure only one organo-bromine gas, CBrClF _2. The development work to improve upon System I involved testing and matching different types of columns, carrier gases, make-up gases to the detector and detector temperatures to obtain operating conditions with optimum resolution, very high sensitivity and sufficiently stable baseline to measure atmospheric organo-bromine gases. During this development work, nine organo-bromine gases were identified in clean background air. The precision of analysis of each system used was sufficient to determine the distributions and time course behavior of the species studied. During the course of this study, samples collected weekly at 11 remote stations around the world spanning latitudes from 82^circN down to 42^circS were analyzed for these organo-bromine gases. In addition, samples collected for 10 years at Cape Meares - Oregon, Cape Matatula - American Samoa, Cape Grim - Tasmania and at the South Pole during the austral summer months were analyzed for long term trends of CBrF_3 and CBrClF_2 . Significant altitudinal differences, interhemispheric gradients and seasonal cycles were observed for certain gases. Long-term trends were observed for CBrF _3 and CBrClF_2. CBrF _3 showed an exponential increase. From 1979 to 1987, its northern and southern hemispheric concentrations have increased at

  15. Development of Bromine-77 from the LAMPF facility

    SciTech Connect

    Mettler, F.A. Jr.

    1982-01-01

    The objective of the work is to conduct the necessary studies required to evaluate the efficacy, potential benefit and role of bromine-77 labelled steroids in the detection and evaluation of treatment for hormone-dependent tumors. The synthetic goals of the project are to prepose estradiol derivatives which are labelled with bromine-77 at specific positions in the steroid nucleus. In addition, animal studies imaging studies, and cooperative studies are being conducted. (KJD)

  16. Brominated flame retardant trends in aquatic birds from the Salish Sea region of the west coast of North America, including a mini-review of recent trends in marine and estuarine birds.

    PubMed

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

    2015-01-01

    Polybrominated diphenyl ethers (PBDEs) increased in many matrices during the 1990s and early 2000s. Since voluntary restrictions and regulations on PBDEs were implemented in North America circa early 2000s, decreases in PBDEs have occurred in many of these same matrices. To examine temporal trends in the North Pacific, we retrospectively analysed PBDEs and eight non-PBDE flame retardants (FR) in eggs of two aquatic bird species, great blue herons, Ardea herodias, and double-crested cormorants, Phalacrocorax auritus, collected along the British Columbia coast, Canada from 1979 to 2012. Increasing PBDE concentrations were observed in both species followed by significant decreases post-2000 for all dominant congeners and ΣPBDE. Non-PBDE FRs were generally undetected in cormorant eggs, or detected at very low levels in heron eggs, except for hexabromocyclododecane (HBCDD). HBCDD, currently unregulated in North America, was not detected in early sampling years; however low concentrations were observed in both species in recent sampling years (2003-2012). Dietary tracers (δ(13)C and δ(15)N) did not change significantly over time, indicating that temporal changes in PBDEs are likely caused by implemented regulations. A comparison with recently published temporal trends of ΣPBDE in marine birds from North America and Europe is given.

  17. DFT investigation of the mecahanism and stereochemistry of electrophilic transannular addition reaction of bromine to tricyclo[4.2.2.02,5]deca-3,7-diene.

    PubMed

    Abbasoglu, Rza; Misir, Miraç Nedim

    2012-03-01

    Full geometric optimization of tricyclo[4.2.2.02,5]deca-3,7-diene (TDD) has been done by DFT/B3LYP methods and the structure of the molecule was investigated. Cyclobuten double bond (I) of molecule is syn pyramidalized, and bicyclookten double bond (II) is also exo pyramidalized. The double bond (I) is more pyramidalized than the double bond (II) and it has higher reactivity. The TDD-Br2 system has been investigated by B3LYP/6-311++G(d,p) method and their stable configurations have been determined. The cationic intermediates and products obtained as a result of the addition reaction has been studied using B3LYP/6-311G(d,p) and B3LYP/6-311++G(d,p) methods. Bridged bromonium cation is more stable than U-type cation. Considering that the bridged cation does not isomerize to the less stable U-type cation, it is not possible for the U-type product to be obtained in the reaction. The bridged bromonium cation transformed into the more stable N-type cation and the N-type product was obtained via this cation. The thermodynamic stability of the anti, exo and anti, endo isomers of N-type dibromide molecule were almost identical. N-type product is 11.759 kcal mol more stable than U-type product.

  18. The Effect of CeO2 Addition on the Microstructure and Properties of Ni-Based Flame-Spray Coatings

    NASA Astrophysics Data System (ADS)

    Zhang, Zhenyu; Liang, Bunv; Guo, Hongjian

    2014-04-01

    Ni-based alloy with different amount of CeO2 powders were flame sprayed and melted onto 1045 carbon steel substrate. Microstructure and properties of the coatings were studied by XRD, field emission gun scanning electron microscope (FEGSEM) and SEM analyses. The wear behavior of the coatings was investigated under dry sliding wear conditions, and was compared with that of the coatings without CeO2, The results show that the microstructure of the coating with CeO2 differs widely from the coating without CeO2, the novel microstructure is beneficial for wear resistance. Abrasive wear tests without lubricant and analysis of the worn surfaces revealed that the Ni-based alloy coatings with the addition of 0.8% CeO2 exhibit higher wear resistance.

  19. Strain-induced extinction of hydrogen-air counterflow diffusion flames - Effects of steam, CO2, N2, and O2 additives to air

    NASA Technical Reports Server (NTRS)

    Pellett, G. L.; Northam, G. B.; Wilson, L. G.

    1992-01-01

    A fundamental study was performed using axisymmetric nozzle and tubular opposed jet burners to measure the effects of laminar plug flow and parabolic input velocity profiles on the extinction limits of H2-air counterflow diffusion flames. Extinction limits were quantified by 'flame strength', (average axial air jet velocity) at blowoff of the central flame. The effects of key air contaminants, on the extinction limits, are characterized and analyzed relative to utilization of combustion contaminated vitiated air in high enthalpy supersonic test facilities.

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

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  1. Triaxial Burke-Schumann Flames with Applications to Flame Synthesis

    NASA Technical Reports Server (NTRS)

    Chao, B. H.; Axelbaum, R. L.; Gokoglu, Suleyman (Technical Monitor)

    2000-01-01

    The problem of a flame generated by three coaxial flows is solved by extending the Burke-Schumann methodology to include a third stream. The solution is particularly relevant to flame synthesis wherein multiple tubes are often employed either to introduce inert as a diffusion barrier or to introduce more than two reactants. The general problem is solved where the inner and outer tubes contain reactants and the middle tube contains either an inert or a third reactant. Relevant examples are considered and the results show that the triaxial Burke-Schumann flame can be substantially more complicated than the traditional Burke-Schumann flame. When the middle flow is inert the flame temperature is no longer constant but increases axially, reaching a maximum at the flame centerline. At the exit the flame does not sit on the tube exit but instead resides between the inner and outer tubes, resulting in an effective barrier for particle build-up on the burner rim. For the case of a third reactant in the middle flow, synthesis chemistry where the inner reaction is endothermic and the outer reaction is exothermic is considered. In addition to showing the flame temperature and flame shape, the results identify conditions wherein reaction is not possible due to insufficient heat transfer from the outer flame to support the inner flame reaction.

  2. Changes of accumulation profiles from PBDEs to brominated and chlorinated alternatives in marine mammals from the South China Sea.

    PubMed

    Zhu, Bingqing; Lai, Nelson L S; Wai, Tak-Cheung; Chan, Leo L; Lam, James C W; Lam, Paul K S

    2014-05-01

    The present study investigated the composition profiles and levels of polybrominated diphenyl ethers (PBDEs) and five PBDE alternatives in the blubber of two species of marine mammals, Indo-Pacific humpback dolphins (Sousa chinensis) and finless porpoises (Neophocaena phocaenoides) from the South China Sea. Despite the fact that PBDEs were the most predominant brominated flame retardants in the samples analyzed, decabromodiphenyl ethane (DBDPE), 1,2-bis (2,4,6-tribromophenoxy) ethane (BTBPE), bis- (2-ethylhexyl) -tetrabromophthalate (TBPH), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB) and Dechlorane Plus (DP) were all detected in both cetacean species. In addition, significantly increasing temporal shifting trends of Deca-BDE to DBDPE, Octa-BDE to BTBPE, and Deca-BDE to DP were observed in porpoise samples between 2003 and 2012 and dolphin samples between 2003 and 2011. These patterns may be attributed to the replacement of PBDEs by alternative halogenated flame retardants (HFRs) and the increasing usage of these alternatives following the restriction/voluntary withdrawal of the production and use of PBDE commercial mixtures. Our findings suggest that the study region may be a source of contamination by PBDE alternative flame retardants due to the high detection frequencies and levels of these compounds in marine mammals.

  3. Bromination of hydrocarbons with CBr4, initiated by light-emitting diode irradiation

    PubMed Central

    Ohtani, Bunsho; Kikushima, Kotaro

    2013-01-01

    Summary The bromination of hydrocarbons with CBr4 as a bromine source, induced by light-emitting diode (LED) irradiation, has been developed. Monobromides were synthesized with high efficiency without the need for any additives, catalysts, heating, or inert conditions. Action and absorption spectra suggest that CBr4 absorbs light to give active species for the bromination. The generation of CHBr3 was confirmed by NMR spectroscopy and GC–MS spectrometry analysis, indicating that the present bromination involves the homolytic cleavage of a C–Br bond in CBr4 followed by radical abstraction of a hydrogen atom from a hydrocarbon. PMID:24062826

  4. Rapid methodology to screen flame retardants in upholstered furniture for compliance with new California labeling law (SB 1019).

    PubMed

    Petreas, Myrto; Gill, Ranjit; Takaku-Pugh, Sayaka; Lytle, Eric; Parry, Emily; Wang, Miaomiao; Quinn, John; Park, June-Soo

    2016-06-01

    In response to concerns regarding the widespread use of flame retardants, the California Legislature passed a law (SB1019) requiring labels on furniture products to indicate whether they do or do not contain flame retardants. To support the enforcement of the new law, our laboratory developed a step-wise, screening approach to test for brominated (BFR) and phosphorus-based flame retardants (OPFRs) in several types of furniture components (foam, fabric, batting, plumage, etc.). We used X-Ray Fluorescence (XRF) to screen for the presence of Br (and other elements) and Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES) to identify and measure the concentration of P (and other elements). The same samples were also extracted by dichloromethane using sonication and analyzed by a single injection into a Gas Chromatograph - Tandem Mass Spectrometer to obtain concentrations of specific BFRs and OPFRs. Our approach showed excellent screening potential for Br and Sb by XRF and for P by ICP-OES, with both tests having predictive values of a negative equal to 1. To explore and screen for flame retardants in products not included in our current list of target chemicals, we used Liquid Chromatography/Time-of-Flight Mass Spectrometry operated with electrospray ionization, to identify additional flame retardants to be incorporated in quantitative methods. We are making all our methodologies public to facilitate simple and low cost methods that can help manufacturers and suppliers have their products tested and correctly labeled, ultimately benefitting the consumer.

  5. Zinc-bromine battery development

    NASA Astrophysics Data System (ADS)

    Richards, Lew; Vanschalwijk, Walter; Albert, George; Tarjanyi, Mike; Leo, Anthony; Lott, Stephen

    1990-05-01

    This report describes development activities on the zinc-bromine battery system conducted by Energy Research Corporation (ERC). The project was a cost-shared program supported by the U.S. Department of Energy and managed through Sandia. The project began in September 1985 and ran through January 1990. The zinc-bromine battery has been identified as a promising alternative to conventional energy storage options for many applications. The low cost of the battery reactants and the potential for long life make the system an attractive candidate for bulk energy storage applications, such as utility load leveling. The battery stores energy by the electrolysis of an aqueous zinc bromide salt to zinc metal and dissolved bromine. Zinc is plated as a layer on the electrode surface while bromine is dissolved in the electrolyte and carried out of the stack. The bromine is then extracted from the electrolyte with an organic complexing agent in the positive electrolyte storage tank. On discharge the zinc and bromine are consumed, regenerating the zinc bromide salt.

  6. Flame Spectra.

    ERIC Educational Resources Information Center

    Cromer, Alan

    1983-01-01

    When salt (NaCl) is introduced into a colorless flame, a bright yellow light (characteristic of sodium) is produced. Why doesn't the chlorine produce a characteristic color of light? The answer to this question is provided, indicating that the flame does not excite the appropriate energy levels in chlorine. (JN)

  7. Autonomous space processor for orbital debris removal and flame augmentation additives in scramjets for the National Aerospace Plane

    NASA Technical Reports Server (NTRS)

    1988-01-01

    This is a brief description of the USRA-sponsored design project at the University of Arizona. Approximately eighty-percent of this effort was spent pursuing a novel engineering concept for the in-situ processing of orbital debris utilizing resources available in low Earth orbit (LEO); the other twenty-percent was devoted to discovering innovative additives for the anchoring of supersonic combustion zones that find direct use in the Aerospace Plane that is expected to use scramjets. The seriousness of the orbital debris problem is briefly described. Available 'solutions' are outlined from the literature. The engineering design is briefly mentioned, with an emphasis on the positive aspects of the space environment that should be used in an economical approach. The aspects of operating in microgravity, vacuum, and in utilizing solar energy are mentioned. A quantitative computer animation was developed to provide design data. Three specific dead spacecraft were identified for an initial cleanup mission. The design concept, which includes a solar processor, remote arm manipulators, and the gradual processing of the debris, is also described. This is followed by a description of hardware construction. Operation and actual processing of simulated debris parts (aluminum, for now) are demonstrated in the NASP task, construction of the new design for measuring the radiation from the key free radicals (as enhanced by the additives) is described. Immediate (1988) and long-range (through 1992) future plans are shown to clearly indicate the full engineering design strategy in the light of the national space program thrusts.

  8. Turbulent flame propagation in partially premixed flames

    NASA Technical Reports Server (NTRS)

    Poinsot, T.; Veynante, D.; Trouve, A.; Ruetsch, G.

    1996-01-01

    Turbulent premixed flame propagation is essential in many practical devices. In the past, fundamental and modeling studies of propagating flames have generally focused on turbulent flame propagation in mixtures of homogeneous composition, i.e. a mixture where the fuel-oxidizer mass ratio, or equivalence ratio, is uniform. This situation corresponds to the ideal case of perfect premixing between fuel and oxidizer. In practical situations, however, deviations from this ideal case occur frequently. In stratified reciprocating engines, fuel injection and large-scale flow motions are fine-tuned to create a mean gradient of equivalence ratio in the combustion chamber which provides additional control on combustion performance. In aircraft engines, combustion occurs with fuel and secondary air injected at various locations resulting in a nonuniform equivalence ratio. In both examples, mean values of the equivalence ratio can exhibit strong spatial and temporal variations. These variations in mixture composition are particularly significant in engines that use direct fuel injection into the combustion chamber. In this case, the liquid fuel does not always completely vaporize and mix before combustion occurs, resulting in persistent rich and lean pockets into which the turbulent flame propagates. From a practical point of view, there are several basic and important issues regarding partially premixed combustion that need to be resolved. Two such issues are how reactant composition inhomogeneities affect the laminar and turbulent flame speeds, and how the burnt gas temperature varies as a function of these inhomogeneities. Knowledge of the flame speed is critical in optimizing combustion performance, and the minimization of pollutant emissions relies heavily on the temperature in the burnt gases. Another application of partially premixed combustion is found in the field of active control of turbulent combustion. One possible technique of active control consists of pulsating

  9. Obtaining the Iodine Value of Various Oils via Bromination with Pyridinium Tribromide

    ERIC Educational Resources Information Center

    Simurdiak, Michael; Olukoga, Olushola; Hedberg, Kirk

    2016-01-01

    A laboratory exercise was devised that allows students to rapidly and fairly accurately determine the iodine value of oleic acid. This method utilizes the addition of elemental bromine to the unsaturated bonds in oleic acid, due to bromine's relatively fast reaction rate compared to that of the traditional Wijs solution method. This method also…

  10. New radiopaque acrylic bone cement. II. Acrylic bone cement with bromine-containing monomer.

    PubMed

    Rusu, M C; Ichim, I C; Popa, M; Rusu, M

    2008-07-01

    Bromine-containing methacrylate, 2-(2-bromopropionyloxy) ethyl methacrylate (BPEM), had been used in the formulation of acrylic radiopaque cements. The effect of this monomer incorporated into the liquid phase of acrylic bone cement, on the curing parameters, thermal properties, water absorption, density, compression tests and radiopacity was studied. A decrease of maximum temperature and an increase of the setting time were observed with the addition of the bromine-containing monomer in the radiolucent cement composition. Adding BPEM in radiolucent acrylic bone cements composition results in the decrease of glass transition temperature and increase of its thermal stability. Acrylic bone cements modified with bromine-containing comonomer are characterized by polymerization shrinkage lower than the radiolucent cement. Addition of bromine-containing comonomer in radiolucent acrylic bone cement composition determines the increase of compressive strength. Acrylic bone cements modified with bromine-containing comonomer proved to be radiopaque.

  11. Flame Detector

    NASA Technical Reports Server (NTRS)

    1990-01-01

    Scientific Instruments, Inc. has now developed a second generation, commercially available instrument to detect flames in hazardous environments, typically refineries, chemical plants and offshore drilling platforms. The Model 74000 detector incorporates a sensing circuit that detects UV radiation in a 100 degree conical field of view extending as far as 250 feet from the instrument. It operates in a bandwidth that makes it virtually 'blind' to solar radiation while affording extremely high sensitivity to ultraviolet flame detection. A 'windowing' technique accurately discriminates between background UV radiation and ultraviolet emitted from an actual flame, hence the user is assured of no false alarms. Model 7410CP is a combination controller and annunciator panel designed to monitor and control as many as 24 flame detectors. *Model 74000 is no longer being manufactured.

  12. Bayesian statistical modeling of disinfection byproduct (DBP) bromine incorporation in the ICR database.

    PubMed

    Francis, Royce A; Vanbriesen, Jeanne M; Small, Mitchell J

    2010-02-15

    Statistical models are developed for bromine incorporation in the trihalomethane (THM), trihaloacetic acids (THAA), dihaloacetic acid (DHAA), and dihaloacetonitrile (DHAN) subclasses of disinfection byproducts (DBPs) using distribution system samples from plants applying only free chlorine as a primary or residual disinfectant in the Information Collection Rule (ICR) database. The objective of this study is to characterize the effect of water quality conditions before, during, and post-treatment on distribution system bromine incorporation into DBP mixtures. Bayesian Markov Chain Monte Carlo (MCMC) methods are used to model individual DBP concentrations and estimate the coefficients of the linear models used to predict the bromine incorporation fraction for distribution system DBP mixtures in each of the four priority DBP classes. The bromine incorporation models achieve good agreement with the data. The most important predictors of bromine incorporation fraction across DBP classes are alkalinity, specific UV absorption (SUVA), and the bromide to total organic carbon ratio (Br:TOC) at the first point of chlorine addition. Free chlorine residual in the distribution system, distribution system residence time, distribution system pH, turbidity, and temperature only slightly influence bromine incorporation. The bromide to applied chlorine (Br:Cl) ratio is not a significant predictor of the bromine incorporation fraction (BIF) in any of the four classes studied. These results indicate that removal of natural organic matter and the location of chlorine addition are important treatment decisions that have substantial implications for bromine incorporation into disinfection byproduct in drinking waters.

  13. Determination of iodine and bromine in coal and atmospheric particles by inductively coupled plasma mass spectrometry.

    PubMed

    Sun, Mingxing; Gao, Yunchuan; Wei, Biwen; Wu, Xiaowei

    2010-04-15

    Bromine and iodine in atmospheric particles or coal can cause environmental problems such as destruction of ozone in the atmosphere; therefore, the presence of these compounds has recently received increased attention. Here, a rapid and reliable method for the simultaneous determination of total bromine and iodine using ICP-MS analysis is described. Samples were dissolved in mixtures of 5 mL of HNO(3) and 2 mL of H(2)O(2) in a high pressure microwave digester. The solution was then oxidized by per-sulfate (Na(2)S(2)O(8)) in addition to a small amount of silver nitrate, after which the total bromine and iodine were measured simultaneously by ICP-MS. The signal memory effects of bromine and iodine during analysis were effectively decreased by washing with a new mixture agent (2% alcohol acidic solution, pH 1-2 adjusted with HCl). The detection limits for bromine and iodine using this method were about 3.2 microg L(-1) and 1.1 microg L(-1), respectively. Additionally, the spike recoveries were between 78.7% and 121% for bromine and iodine analysis, while the relative standard deviations ranged from 4.3% to 9.7%, and from 1.5% to 3.4% for bromine and iodine, respectively. The results of this study indicate that the method described here is suitable for the analysis of micro-amounts of bromine and iodine in atmospheric particles and coal samples.

  14. 49 CFR 173.249 - Bromine.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 2 2013-10-01 2013-10-01 false Bromine. 173.249 Section 173.249 Transportation... PACKAGINGS Bulk Packaging for Hazardous Materials Other Than Class 1 and Class 7 § 173.249 Bromine. When... bromine service built prior to August 31, 1991, may continue in service under the requirements...

  15. 49 CFR 173.249 - Bromine.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 2 2014-10-01 2014-10-01 false Bromine. 173.249 Section 173.249 Transportation... PACKAGINGS Bulk Packaging for Hazardous Materials Other Than Class 1 and Class 7 § 173.249 Bromine. When... bromine service built prior to August 31, 1991, may continue in service under the requirements...

  16. 49 CFR 173.249 - Bromine.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 2 2011-10-01 2011-10-01 false Bromine. 173.249 Section 173.249 Transportation... PACKAGINGS Bulk Packaging for Hazardous Materials Other Than Class 1 and Class 7 § 173.249 Bromine. When... bromine service built prior to August 31, 1991, may continue in service under the requirements...

  17. 49 CFR 173.249 - Bromine.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 2 2012-10-01 2012-10-01 false Bromine. 173.249 Section 173.249 Transportation... PACKAGINGS Bulk Packaging for Hazardous Materials Other Than Class 1 and Class 7 § 173.249 Bromine. When... bromine service built prior to August 31, 1991, may continue in service under the requirements...

  18. Mineral Resource of the Month: Bromine

    USGS Publications Warehouse

    Schnebele, Emily

    2015-01-01

    Bromine, along with mercury, is one of only two elements that are liquid at room temperature. Bromine is a highly volatile and corrosive reddish-brown liquid that evaporates easily and converts to a metal at extreme pressures — above about 540,000 times atmospheric pressure. Bromine occurs in seawater, evaporitic (salt) lakes and underground brines associated with petroleum deposits. 

  19. Formation of brominated pollutants during the pyrolysis and combustion of tetrabromobisphenol A at different temperatures.

    PubMed

    Ortuño, Nuria; Moltó, Julia; Conesa, Juan A; Font, Rafael

    2014-08-01

    Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardant worldwide. A detailed examination of the degradation products emitted during thermal decomposition of TBBPA is presented in the study. Runs were performed in a laboratory furnace at different temperatures (650 and 800 °C) and in different atmospheres (nitrogen and air). More than one hundred semivolatile compounds have been identified by GC/MS, with special interest in brominated ones. Presence of HBr and brominated light hydrocarbons increased with temperature and in the presence of oxygen. Maximum formation of PAHs is observed at pyrolytic condition at the higher temperature. High levels of 2,4-, 2,6- and 2,4,6- bromophenols were found. The levels of polybrominated dibenzo-p-dioxins and furans have been detected in the ppm range. The most abundant isomers are 2,4,6,8-TeBDF in pyrolysis and 1,2,3,7,8-PeBDF in combustion. These results should be considered in the assessment of thermal treatment of materials containing brominated flame retardants.

  20. Advanced morphological - behavioral test platform reveals neurodevelopmental defects in embryonic zebrafish exposed to comprehensive suite of halogenated and organophosphate flame retardants.

    PubMed

    Noyes, Pamela D; Haggard, Derik E; Gonnerman, Greg D; Tanguay, Robert L

    2015-05-01

    The increased use of flammable plastics and electronic devices along with stricter fire safety standards has led to the heavy use of flame retardant chemicals in many consumer, commercial, and industrial products. Although flame retardant use has increased, a great deal of uncertainty surrounds their safety with some evidence showing toxicity and risk to human and environmental health. Recent efforts have focused on designing high-throughput biological platforms with nonmammalian models to evaluate and prioritize chemicals with limited hazard information. To complement these efforts, this study used a new morphological and behavioral testing platform with embryonic zebrafish to characterize the developmental toxicity of 44 halogenated and organophosphate flame retardants, including several of their known metabolites. Zebrafish were exposed to flame retardants from 6 to 120 h post fertilization (hpf) across concentrations spanning 4 orders of magnitude (eg, 6.4 nM to 64 µM). Flame retardant effects on survival and development were evaluated at 24 and 120 hpf, and neurobehavioral changes were measured using 2 photomotor response (PMR) assays. Compared to controls, 93% (41/44) of flame retardants studied elicited adverse effects among one or more of the bioassays and concentrations tested with the aryl phosphate ester (APE)-based mono-isopropylated triaryl phosphate and the brominated-bisphenol-A analog tetrabromobisphenol-A producing the greatest array of malformations. Hierarchical clustering showed that APE flame retardants with isopropyl, butyl, and cresyl substituents on phenyl rings clustered tightly and were particularly potent. Both PMR assays were highly predictive of morphological defects supporting their use as nonlethal means of evaluating teratogenicity that could allow for additional evaluations of long-term or delayed effects in older animals. Taken together, evidence presented here indicates that zebrafish neurodevelopment is highly sensitive to

  1. Advanced Morphological — Behavioral Test Platform Reveals Neurodevelopmental Defects in Embryonic Zebrafish Exposed to Comprehensive Suite of Halogenated and Organophosphate Flame Retardants

    PubMed Central

    Noyes, Pamela D.; Haggard, Derik E.; Gonnerman, Greg D.; Tanguay, Robert L.

    2015-01-01

    The increased use of flammable plastics and electronic devices along with stricter fire safety standards has led to the heavy use of flame retardant chemicals in many consumer, commercial, and industrial products. Although flame retardant use has increased, a great deal of uncertainty surrounds their safety with some evidence showing toxicity and risk to human and environmental health. Recent efforts have focused on designing high-throughput biological platforms with nonmammalian models to evaluate and prioritize chemicals with limited hazard information. To complement these efforts, this study used a new morphological and behavioral testing platform with embryonic zebrafish to characterize the developmental toxicity of 44 halogenated and organophosphate flame retardants, including several of their known metabolites. Zebrafish were exposed to flame retardants from 6 to 120 h post fertilization (hpf) across concentrations spanning 4 orders of magnitude (eg, 6.4 nM to 64 µM). Flame retardant effects on survival and development were evaluated at 24 and 120 hpf, and neurobehavioral changes were measured using 2 photomotor response (PMR) assays. Compared to controls, 93% (41/44) of flame retardants studied elicited adverse effects among one or more of the bioassays and concentrations tested with the aryl phosphate ester (APE)-based mono-isopropylated triaryl phosphate and the brominated-bisphenol-A analog tetrabromobisphenol-A producing the greatest array of malformations. Hierarchical clustering showed that APE flame retardants with isopropyl, butyl, and cresyl substituents on phenyl rings clustered tightly and were particularly potent. Both PMR assays were highly predictive of morphological defects supporting their use as nonlethal means of evaluating teratogenicity that could allow for additional evaluations of long-term or delayed effects in older animals. Taken together, evidence presented here indicates that zebrafish neurodevelopment is highly sensitive to

  2. 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.

  3. Effects of Flame Structure and Hydrodynamics on Soot Particle Inception and Flame Extinction in Diffusion Flames

    NASA Technical Reports Server (NTRS)

    Axelbaum, R. L.; Chen, R.; Sunderland, P. B.; Urban, D. L.; Liu, S.; Chao, B. H.

    2001-01-01

    This paper summarizes recent studies of the effects of stoichiometric mixture fraction (structure) and hydrodynamics on soot particle inception and flame extinction in diffusion flames. Microgravity experiments are uniquely suited for these studies because, unlike normal gravity experiments, they allow structural and hydrodynamic effects to be independently studied. As part of this recent flight definition program, microgravity studies have been performed in the 2.2 second drop tower. Normal gravity counterflow studies also have been employed and analytical and numerical models have been developed. A goal of this program is to develop sufficient understanding of the effects of flame structure that flames can be "designed" to specifications - consequently, the program name Flame Design. In other words, if a soot-free, strong, low temperature flame is required, can one produce such a flame by designing its structure? Certainly, as in any design, there will be constraints imposed by the properties of the available "materials." For hydrocarbon combustion, the base materials are fuel and air. Additives could be considered, but for this work only fuel, oxygen and nitrogen are considered. Also, the structure of these flames is "designed" by varying the stoichiometric mixture fraction. Following this line of reasoning, the studies described are aimed at developing the understanding of flame structure that is needed to allow for optimum design.

  4. Bromine and carbon isotope effects during photolysis of brominated phenols.

    PubMed

    Zakon, Yevgeni; Halicz, Ludwik; Gelman, Faina

    2013-12-17

    In the present study, carbon and bromine isotope effects during UV-photodegradation of bromophenols in aqueous and ethanolic solutions were determined. An anomalous relatively high inverse bromine isotope fractionation (εreactive position up to +5.1‰) along with normal carbon isotope effect (εreactive position of -12.6‰ to -23.4‰) observed in our study may be attributed to coexistence of both mass-dependent and mass-independent isotope fractionation of C-Br bond cleavage. Isotope effects of a similar scale were observed for all the studied reactions in ethanol, and for 4-bromophenol in aqueous solution. This may point out related radical mechanism for these processes. The lack of any carbon and bromine isotope effects during photodegradation of 2-bromophenol in aqueous solution possibly indicates that C-Br bond cleavage is not a rate-limiting step in the reaction. The bromine isotope fractionation, without any detectable carbon isotope effect, that was observed for 3-bromophenol photolysis in aqueous solution probably originates from mass-independent fractionation.

  5. Additives

    NASA Technical Reports Server (NTRS)

    Smalheer, C. V.

    1973-01-01

    The chemistry of lubricant additives is discussed to show what the additives are chemically and what functions they perform in the lubrication of various kinds of equipment. Current theories regarding the mode of action of lubricant additives are presented. The additive groups discussed include the following: (1) detergents and dispersants, (2) corrosion inhibitors, (3) antioxidants, (4) viscosity index improvers, (5) pour point depressants, and (6) antifouling agents.

  6. Electrolyte additive for improved battery performance

    DOEpatents

    Bellows, Richard J.; Kantner, Edward

    1989-04-04

    In one embodiment of the present invention, there is provided an electrochemical cell having a metal bromine couple. The cell includes an electrode structure on which to deposit the metal of the couple and a counterelectrode at which to generate bromine. A microporous membrane separates the electrode and counterelectrode. Importantly, the aqueous electrolyte comprises an aqueous metal bromide solution containing a water soluble bromine complexing agent capable of forming a water immiscible complex with bromine and an additive capable of decreasing the wettability of the microporous separators employed in such cells by such water immiscible bromine complexes.

  7. The toxicity of brominated and mixed-halogenated dibenzo-p-dioxins and dibenzofurans: An overview

    SciTech Connect

    Weber, L.W.D. |; Greim, H.

    1997-02-21

    Brominated dibenzo-p-dioxins and dibenzofurans can be formed under laboratory conditions by pyrolysis of flame retardants based on polybrominated biphenyls and biphenyl ethers. Their occurrence in the environment, however, is due to combustion processes such as municipal waste incineration and internal combustion engines. As these processes generally take place in the presence of an excess of chlorine, predominantly mixed brominated and chlorinated compounds have been identified so far in environmental samples. Brominated dibenzo-p-dioxins or dibenzofurans bind to the cytosolic Ah receptor about as avidly as their chlorinated congeners and induce hepatic microsomal enzymes with comparable potency. The same holds true for mixed brominated-chlorinated compounds. Gross pathologic symptoms-hypothyroidism, thymic atrophy, wasting of body mass, lethality-also occur at doses that, on a molar concentration basis, are virtually identical to those seen with the chlorinated compounds. Their potency to induce malformations in mice following prenatal exposure is equivalent to that of chlorinated dibenzo-p-dioxins and dibenzofurans. Possible activities as (co)carcinogens and endocrine disrupters have not been evaluated, but are likely to exist. Considering the overall similarity in action of chlorinated and brominated dibenzo-p-dioxins and dibenzofurans, environmental and health assessment should be based on molar body burdens without discrimination for the nature of the halogen. 107 refs., 1 fig., 7 tabs.

  8. Elucidating toxicological mechanisms of current flame retardants using a bacterial gene profiling assay.

    PubMed

    Krivoshiev, Boris V; Dardenne, Freddy; Blust, Ronny; Covaci, Adrian; Husson, Steven J

    2015-12-01

    Flame retardants are ubiquitously used chemicals that have been shown to contaminate environments. Toxicological data is largely limited, with little insight into their molecular modes of action that may give rise to their toxic phenotypes. Such insight would aid more effective risk assessments concerning these compounds, while also improving molecular design. We therefore used a bacterial stress-gene profiling assay to screen twelve currently-used flame retardants to obtain mechanistic insights of toxicity. Both brominated and organophosphate flame retardants were tested. All compounds showed statistically significant inductions of several stress genes when compared to control treatments. Triphenyl phosphate, tris(2-butoxyethyl) phosphate, tris(1,3-dichloro-2-propyl)phosphate, tris(butyl)phosphate, and tetrabromobisphenol A elicited (at least) two-fold inductions for any of the stress genes. When looking at absolute induction levels, the promoters induced are indicative of protein perturbation, DNA integrity and membrane integrity. However, normalising for the different induction potentials of the different stress genes and clustering using hierarchical and k-means algorithms indicated that in addition to protein and DNA damage, some compounds also resulted in growth arrest and oxidative damage. This research shows that this assay allows for the determination of toxicological modes-of-action while clustering and accounting for induction potentials of the different genes aids better risk assessment.

  9. Electronic properties of bromine-doped carbon nanotubes

    SciTech Connect

    Jhi, Seung-Hoon; Louie, Steven G.; Cohen, Marvin L.

    2002-07-15

    Intercalation of bromine molecules (Br2) into single-wall carbon nanotube (SWNT) ropes is studied using the ab initio pseudopotential density functional method. Electronic and vibrational properties of the SWNT and Br2 are studied for various bromine concentrations. A drastic change in the charge transfer, bromine stretching-mode, and bromine bond-length is observed when the bromine-bromine distance decreases. Calculated electronic structures show that, at high bromine concentrations, the bromine ppsigma level broadens due to the interbromine interaction. These states overlap with the electronic bands of the SWNT near the Fermi level which results in a substantial charge transfer from carbon to bromine.

  10. The chemistry of dimethacrylate-styrene networks, and, Development of flame retardant, halogen-free fiber reinforced vinyl ester composites

    NASA Astrophysics Data System (ADS)

    Rosario, Astrid Christa

    One of the major classes of polymer matrix resins under consideration for structural composite applications in the infrastructure and construction industries is vinyl ester resin. Vinyl ester resin is comprised of low molecular weight poly(hydroxyether) oligomers with methacrylate endgroups diluted with styrene monomer. The methacrylate endgroups cure with styrene via free radical copolymerization to yield thermoset networks. The copolymerization behavior of these networks was monitored by Fourier Transform Infrared Spectroscopy (FTIR) at various cure conditions. Reactions of the carbon-carbon double bonds of the methacrylate (943 cm-1) and styrene (910 cm-1 ) were followed independently. Oligomers possessing number average molecular weights of 700 g/mole were studied with systematically increasing levels of styrene. The Mortimer-Tidwell reactivity ratios indicated that at low conversion more styrene was incorporated into the network at lower cure temperatures. The experimental vinyl ester-styrene network compositions deviated significantly from those predicted by the Meyer-Lowry integrated copolymer equation at higher conversion, implying that the reactivity ratios for these networks may change with conversion. The kinetic data were used to provide additional insight into the physical and mechanical properties of these materials. In addition to establishing the copolymerization kinetics of these materials, the development of halogen free fiber reinforced vinyl ester composites exhibiting good flame properties was of interest. Flame retardant vinyl ester resins are used by many industries for applications requiring good thermal resistance. The current flame-retardant technology is dependent on brominated vinyl esters, which generate high levels of smoke and carbon monoxide. A series of halogen free binder systems has been developed and dispersed in the vinyl ester to improve flame retardance. The binder approach enables the vinyl ester resin to maintain its low

  11. Durability of polymeric materials used in zinc/bromine flow batteries

    NASA Astrophysics Data System (ADS)

    Arnold, C., Jr.

    The lifetimes of zinc/bromine flow batteries may be limited by the durability of components which are fabricated from thermoplastic materials and exposed to the bromine-containing electrolyte. Examples of such components are flowframes and carbon-filled plastic electrodes. In early versions of the zinc/bromine battery, flowframes and electrodes were made from polypropylene and copolymers of propylene and ethylene. In later versions of the zinc/bromine battery, polyvinyl chloride (PVC) was used as the material to fabricate flowframes and polyethylene was used as the material used to fabricate both flowframes and electrodes. We found that carbon-plastic electrodes made from polypropylene or polypropylene rich copolymers were swelled and chemically attacked by the bromine-containing electrolytes. As a result, warpage occurred and the battery failed. On the basis of accelerated aging studies we estimated the lifetimes of the electrode and its polypropylene based component to be 96 and 10 months, respectively. The enhanced stability of the electrode was attributed to the presence of carbon which is known to be an antioxidant for thermoxidation. In accelerated exposure tests, bromine-containing electrolytes were also found to attack and leach out the additives used in PVC flowframes. PVC itself was only slightly degraded by the electrolyte. A commercial fluorocarbon, Tefzel, which contains no additives, was determined to be stable in bromine-containing electrolytes and is recommended as a replacement for PVC. Currently, aging studies on carbon-filled polyethylene electrodes are in progress.

  12. Flames in vortices & tulip-flame inversion

    NASA Astrophysics Data System (ADS)

    Dold, J. W.

    This article summarises two areas of research regarding the propagation of flames in flows which involve significant fluid-dynamical motion [1]-[3]. The major difference between the two is that in the first study the fluid motion is present before the arrival of any flame and remains unaffected by the flame [1, 2] while, in the second study it is the flame that is responsible for all of the fluid dynamical effects [3]. It is currently very difficult to study flame-motion in which the medium is both highly disturbed before the arrival of a flame and is further influenced by the passage of the flame.

  13. Soot Formation in Purely-Curved Premixed Flames and Laminar Flame Speeds of Soot-Forming Flames

    NASA Technical Reports Server (NTRS)

    Buchanan, Thomas; Wang, Hai

    2005-01-01

    The research addressed here is a collaborative project between University of Delaware and Case Western Reserve University. There are two basic and related scientific objectives. First, we wish to demonstrate the suitability of spherical/cylindrical, laminar, premixed flames in the fundamental study of the chemical and physical processes of soot formation. Our reasoning is that the flame standoff distance in spherical/cylindrical flames under microgravity can be substantially larger than that in a flat burner-stabilized flame. Therefore the spherical/cylindrical flame is expected to give better spatial resolution to probe the soot inception and growth chemistry than flat flames. Second, we wish to examine the feasibility of determining the laminar flame speed of soot forming flames. Our basic assumption is that under the adiabatic condition (in the absence of conductive heat loss), the amount and dynamics of soot formed in the flame is unique for a given fuel/air mixture. The laminar flame speed can be rigorously defined as long as the radiative heat loss can be determined. This laminar flame speed characterizes the flame soot formation and dynamics in addition to the heat release rate. The research involves two integral parts: experiments of spherical and cylindrical sooting flames in microgravity (CWRU), and the computational counterpart (UD) that aims to simulate sooting laminar flames, and the sooting limits of near adiabatic flames. The computations work is described in this report, followed by a summary of the accomplishments achieved to date. Details of the microgra+ experiments will be discussed in a separate, final report prepared by the co-PI, Professor C-J. Sung of CWRU. Here only a brief discussion of these experiments will be given.

  14. Soot Formation in Laminar Premixed Flames

    NASA Technical Reports Server (NTRS)

    Xu, F.; Krishnan, S. S.; Faeth, G. M.

    1999-01-01

    Soot processes within hydrocarbon-fueled flames affect emissions of pollutant soot, thermal loads on combustors, hazards of unwanted fires and capabilities for computational combustion. In view of these observations, the present study is considering processes of soot formation in both burner-stabilized and freely-propagating laminar premixed flames. These flames are being studied in order to simplify the interpretation of measurements and to enhance computational tractability compared to the diffusion flame environments of greatest interest for soot processes. In addition, earlier studies of soot formation in laminar premixed flames used approximations of soot optical and structure properties that have not been effective during recent evaluations, as well as questionable estimates of flow residence times). The objective of present work was to exploit methods of avoiding these difficulties developed for laminar diffusion flames to study soot growth in laminar premixed flames. The following description of these studies is brief.

  15. Stability of Bromine Intercalated Graphite Fibers

    NASA Technical Reports Server (NTRS)

    Gaier, J. R.

    1984-01-01

    Previous evidence suggested that bromine intercalation compounds of crystalline graphite spontaneously deintercalate when the bromine atmosphere is removed. However, results show that bromine intercalated P-100 graphite fibers are stable for long periods of time. They are stable under vacuum conditions, high humidity, and current densities up to 24,000 A/sq cm. They are thermally stable to 200 C, and at temperatures as high as 400 C still retain 80 percent of the conductivity gained by intercalation. At temperatures greater than 300 C, there is significant oxidative degradation of the fibers. The environmental stability shown by the bromine compound makes it a promising candidate for practical applications in aerospace technology.

  16. Thyroid axis disruption in juvenile brown trout (Salmo trutta) exposed to the flame retardant β-tetrabromoethylcyclohexane (β-TBECH) via the diet.

    PubMed

    Park, Bradley J; Palace, Vince; Wautier, Kerry; Gemmill, Bonnie; Tomy, Gregg

    2011-09-15

    Tetrabromoethylcyclohexane (TBECH) is an additive brominated flame retardant used in domestic and industrial applications. It has been detected in wildlife, and there is early evidence that it is an endocrine disruptor. Whereas other brominated flame retardants with similar physicochemical properties have been shown to disrupt the thyroid axis, no such evaluation has been conducted for TBECH. To elucidate this, juvenile brown trout (Salmo trutta) were fed either a control diet or diets containing low, medium, or high doses of β-TBECH, the isomer most frequently detected in wildlife, for 56 days (uptake phase) followed by a control diet for an additional 77 days (depuration phase). Eight fish per treatment were lethally sampled on uptake days 7, 14, 21, 35, 49, and 56 and on depuration days 7, 21, 35, 49, and 77 to assess fish condition, circulating free and total triiodothyronine and thyroxine, and thyroid epithelial cell height. Although there was no effect on condition factor, there was a significant reduction in total plasma thyroxine in the high dose group and a significant increase in mean thyroid epithelial cell height in the low, medium, and high dose groups during the uptake phase, whereas there were no differences in the depuration phase. These results indicate that β-TBECH may modulate the thyroid axis in fish at environmentally relevant concentrations.

  17. 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.

  18. A method to remove intercalates from bromine and iodine intercalated carbon fibers

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh

    1993-01-01

    Upon exposure to room-temperature fluorine, intercalated carbon fibers (containing either bromine alone or iodine and bromine together) become heavier and less stable. For Amoco P-100 graphitized carbon fibers which were intercalated with 18 percent bromine by weight, 1 hr of fluorine exposure results in a large weight increase, but causes only a small decrease in thermal stability. More than l hr of fluorine exposure time results in small additional increases in fiber weight, but significant further decreases in fiber thermal stability. Such phenomena do not occur if the fluorine exposure is at 250 C. These observations suggest the mechanism that at room temperature, fluorine is absorbed quickly by the intercalated fibers and intercalated slowly into the fibers. Most of the original intercalates are replaced by fluorine in the process of fluorine intercalation. Under an inert environment, the bromine intercalated fibers are much more thermally stable. After 800 C vacuum heating for two weeks, the brominated fibers lost about 45 percent of their bromine, and their resistivity increased from 64 omega-cm to a range of 95 to 170 micro omega-cm. This is still much lower than the 300 micro omega-cm value for pristine P-100. For practical purposes, in order to preserve their thermal stability, brominated fibers need to be protected from exposure to fluorine at room temperature, or to any intercalate at a temperature where, upon direct contact to graphite, an intercalation compound can easily be formed.

  19. Conversion of bromine during thermal decomposition of printed circuit boards at high temperature.

    PubMed

    Jin, Yu-qi; Tao, Lin; Chi, Yong; Yan, Jian-hua

    2011-02-15

    The conversion of bromine during the thermal decomposition of printed circuit boards (PCBs) was investigated at isothermal temperatures ranging from 800°C to 1100°C by using a quartz tube furnace. The influence of temperature, oxygen concentrations (0%, 10% and 21% in the nitrogen-oxygen atmosphere) and content of steam on conversion of bromine was studied. With the increment of temperature, the conversion from organic bromine in the PCBs to inorganic bromine in the gaseous fraction increased from 69.0% to 96.4%. The bromine was mainly evolved as HBr and Br(2) in oxidizing condition and the Br(2)/HBr mass ratio increased at stronger oxidizing atmosphere. The experimental results also indicated that the existence of steam can reduce the formation of Br(2). Furthermore, co-combustion of PCBs with S and CaO, both as addition agents, was investigated, respectively. In the presence of SO(2), Br(2)/HBr mass ratio obviously decreased. Moreover, the utilization of calcium oxide can efficiently promote the conversion of organic bromine to inorganic bromine. According to the experimental results, incinerating PCBs at high temperature can efficiently destroy the organobrominated compounds that are considered to be possible precursors of polybrominated dibenzeo-p-dioxins and dibenzofurans (PBDD/Fs), but the Br(2) and HBr in flue gas should be efficiently controlled.

  20. DEVELOPMENTAL EVALUATIONS OF C57BL/6 MICE EXPOSED TO 2,2',4,4'-BROMINATED DIPHENYL ETHER (DE47) ON POSTNATAL DAY 10.

    EPA Science Inventory

    Polybrominated diphenyl ethers (PBDEs) are widely used commercial flame retardants that are accumulating in the environment. 2,2',4,4'-Brominated diphenyl ether (DE47) is the most stable congener of this group and is undergoing the most rapid accumulation in humans, despite the ...

  1. Bromination of olefins with HBr and DMSO.

    PubMed

    Karki, Megha; Magolan, Jakob

    2015-04-03

    A simple and inexpensive methodology is reported for the conversion of alkenes to 1,2-dibromo alkanes via oxidative bromination using HBr paired with dimethyl sulfoxide, which serves as the oxidant as well as cosolvent. The substrate scope includes 21 olefins brominated in good to excellent yields. Three of six styrene derivatives yielded bromohydrins under the reaction conditions.

  2. Brominated carbon black: An EDXD study

    SciTech Connect

    Carbone, Marilena; Gontrani, Lorenzo

    2014-06-19

    An energy dispersive X-Ray study of pure and brominated carbon black was carried out. The analysis of the diffraction patterns reveals that the low bromine load (ca.1% mol) is trapped into the structure, without significantly modifying it. This allows the application of the difference methods, widely tested for electrolyte solutions, inorganic matrices containing metals and isomorphic substitutions.

  3. Editor's Highlight: Comparative Toxicity of Organophosphate Flame Retardants and Polybrominated Diphenyl Ethers to Caenorhabditis elegans.

    PubMed

    Behl, Mamta; Rice, Julie R; Smith, Marjo V; Co, Caroll A; Bridge, Matthew F; Hsieh, Jui-Hua; Freedman, Jonathan H; Boyd, Windy A

    2016-12-01

    With the phasing-out of the polybrominated diphenyl ether (PBDE) flame retardants due to concerns regarding their potential developmental toxicity, the use of replacement compounds such as organophosphate flame retardants (OPFRs) has increased. Limited toxicity data are currently available to estimate the potential adverse health effects of the OPFRs. The toxicological effects of 4 brominated flame retardants, including 3 PBDEs and 3,3',5,5'-tetrabromobisphenol A, were compared with 6 aromatic OPFRs and 2 aliphatic OPFRs. The effects of these chemicals were determined using 3 biological endpoints in the nematode Caenorhabditis elegans (feeding, larval development, and reproduction). Because C. elegans development was previously reported to be sensitive to mitochondrial function, results were compared with those from an in vitro mitochondrial membrane permeabilization (MMP) assay. Overall 11 of the 12 flame retardants were active in 1 or more C. elegans biological endpoints, with only tris(2-chloroethyl) phosphate inactive across all endpoints including the in vitro MMP assay. For 2 of the C. elegans endpoints, at least 1 OPFR had similar toxicity to the PBDEs: triphenyl phosphate (TPHP) inhibited larval development at levels comparable to the 3 PBDEs; whereas TPHP and isopropylated phenol phosphate (IPP) affected C. elegans reproduction at levels similar to the PBDE commercial mixture, DE-71. The PBDEs reduced C. elegans feeding at lower concentrations than any OPFR. In addition, 9 of the 11 chemicals that inhibited C. elegans larval development also caused significant mitochondrial toxicity. These results suggest that some of the replacement aromatic OPFRs may have levels of toxicity comparable to PBDEs.

  4. Potent anti-inflammatory activity of novel microtubule-modulating brominated noscapine analogs.

    PubMed

    Zughaier, Susu; Karna, Prasanthi; Stephens, David; Aneja, Ritu

    2010-02-11

    Noscapine, a plant-derived, non-toxic, over-the-counter antitussive alkaloid has tubulin-binding properties. Based upon the structural resemblance of noscapine to colchicine, a tubulin-binding anti-inflammatory drug, noscapine and its semi-synthetic brominated analogs were examined for in vitro anti-inflammatory activity. Brominated noscapine analogs were found to inhibit cytokine and chemokine release from macrophage cell lines but did not affect cell viability. Brominated noscapine analogs demonstrated anti-inflammatory properties in both TLR- and non-TLR induced in vitro innate immune pathway inflammation models, mimicking septic and sterile infection respectively. In addition, electron microscopy and immunoblotting data indicated that these analogs induced robust autophagy in human macrophages. This study is the first report to identify brominated noscapines as innate immune pathway anti-inflammatory molecules.

  5. Electrical Aspects of Impinging Flames

    NASA Astrophysics Data System (ADS)

    Chien, Yu-Chien

    from the flame to the plate can be controlled using the electric field are the two main goals of this research. Multiple diagnostic techniques are employed such as OH chemiluminescence to identify the reaction zone, OH PLIF to characterize the location of this radical species, CO released from the flame, IR imaging and OH PLIF thermometry to understand the surface and gas temperature distribution, respectively. The principal finding is that carbon monoxide release from an impinging diffusion flame results from the escape of carbon monoxide created on the fuel side of the flame along the boundary layer near the surface where it avoids oxidation by OH, which sits to the air side of the reaction sheet interface. In addition, the plate proximity to the flame has a stronger influence on the emission of toxic carbon monoxide than does the electric field strength. There is, however, a narrow region of burner to surface distance where the electric field is most effective. The results also show that heat transfer can be spatially concentrated effectively using an electric field driven ion wind, particularly at some burner to surface distances.

  6. 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.

  7. Interaction of Two Micro-slot Flames: Heat Release Rate and Flame Shape

    NASA Astrophysics Data System (ADS)

    Kuwana, K.; Kato, S.; Kosugi, A.; Hirasawa, T.; Nakamura, Y.

    2014-11-01

    This paper studies the interaction between two identical micro-slot diffusion flames. Here, we define a micro-slot flame as a slot flame of which the slot width is less than about 1 mm. Because of its smallness, a micro-slot flame has a high heating density and can be used as a small heat source. However, the heat release rate of a single micro-slot flame is limited, and therefore, multiple micro-slot flames may be used to increase total heat release rate. As a first step, this paper considers a situation in which two micro-slot flames are used with certain burner spacing. When two diffusion flames are placed closely, flame shape changes from that of an isolated flame. Studying such flame shape change and resultant change in total heat release rate is the topic of this paper. Experiment is conducted and total heat release rate is measured by integrating CH* chemiluminescence recorded using a CCD camera and an optical filter of the wavelength of 430 nm. Two different burner materials, copper and glass, are tested to study the effect of heat loss to burners. An analytical model is applied to predict flame shape. In addition to the classical Burke-Schumann assumptions, two slot flames are modeled as line sources with zero width, enabling a simple analytical solution for the critical burner spacing at which two flames touch each other. The critical burner spacing is a key parameter that characterizes the interaction between two micro-slot flames. Computational fluid dynamics (CFD) simulations are then conducted to test the validity of the present theory. CFD results are favorably compared with the theoretical prediction.

  8. Sensitivity of Ozone to Bromine in the Lower Stratosphere

    NASA Technical Reports Server (NTRS)

    Salawitch, R. J.; Weisenstein, D. K.; Kovalenko, L. J.; Sioris, C. E.; Wennberg, P. O.; Chance, K.; Ko, M. K. W.; McLinden, C. A.

    2005-01-01

    Measurements of BrO suggest that inorganic bromine (Br(sub y)) at and above the tropopause is 4 to 8 ppt greater than assumed in models used in past ozone trend assessment studies. This additional bromine is likely carried to the stratosphere by short-lived biogenic compounds and their decomposition products, including tropospheric BrO. Including this additional bromine in an ozone trend simulation increases the computed ozone depletion over the past approx.25 years, leading to better agreement between measured and modeled ozone trends. This additional Br(sub y) (assumed constant over time) causes more ozone depletion because associated BrO provides a reaction partner for ClO, which increases due to anthropogenic sources. Enhanced Br(sub y) causes photochemical loss of ozone below approx.14 km to change from being controlled by HO(sub x) catalytic cycles (primarily HO2+O3) to a situation where loss by the BrO+HO2 cycle is also important.

  9. Laminar Diffusion Flame Studies (Ground- and Space-Based Studies)

    NASA Technical Reports Server (NTRS)

    Dai, Z.; El-Leathy, A. M.; Lin, K.-C.; Sunderland, P. B.; Xu, F.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

    2000-01-01

    Laminar diffusion flames are of interest because they provide model flame systems that are far more tractable for analysis and experiments than more practical turbulent diffusion flames. Certainly, understanding flame processes within laminar diffusion flames must precede understanding these processes in more complex turbulent diffusion flames. In addition, many properties of laminar diffusion flames are directly relevant to turbulent diffusion flames using laminar flamelet concepts. Laminar jet diffusion flame shapes (luminous flame boundaries) have been of particular interest since the classical study of Burke and Schumann because they are a simple nonintrusive measurement that is convenient for evaluating flame structure predictions. Thus, consideration of laminar flame shapes is undertaken in the following, emphasizing conditions where effects of gravity are small, due to the importance of such conditions to practical applications. Another class of interesting properties of laminar diffusion flames are their laminar soot and smoke point properties (i.e., the flame length, fuel flow rate, characteristic residence time, etc., at the onset of soot appearance in the flame (the soot point) and the onset of soot emissions from the flame (the smoke point)). These are useful observable soot properties of nonpremixed flames because they provide a convenient means to rate several aspects of flame sooting properties: the relative propensity of various fuels to produce soot in flames; the relative effects of fuel structure, fuel dilution, flame temperature and ambient pressure on the soot appearance and emission properties of flames; the relative levels of continuum radiation from soot in flames; and effects of the intrusion of gravity (or buoyant motion) on emissions of soot from flames. An important motivation to define conditions for soot emissions is that observations of laminar jet diffusion flames in critical environments, e.g., space shuttle and space station

  10. The crystal structure and superconducting properties of monatomic bromine.

    PubMed

    Duan, Defang; Meng, Xing; Tian, Fubo; Chen, Changbo; Wang, Liancheng; Ma, Yanming; Cui, Tian; Liu, Bingbing; He, Zhi; Zou, Guangtian

    2010-01-13

    The crystal structure and superconducting properties of monatomic bromine under high pressure have been studied by first-principles calculations. We have found the following phase transition sequence with increasing pressure: from body-centered orthorhombic (bco, phase II) to body-centered tetragonal structure (bct, phase III) at 126 GPa, then to face-centered cubic structure (fcc, phase IV) at 157 GPa, which is stable at least up to 300 GPa. The calculated superconducting critical temperature T(c) = 1.46 K at 100 GPa is consistent with the experimental value of 1.5 K. In addition, our results of T(c) decrease with increasing pressure in all the monatomic phases of bromine, similar to monatomic iodine. Further calculations show that the decrease of λ with pressure in phase IV is mainly attributed to the weakening of the 'soft' vibrational mode caused by pressure.

  11. Novel brominated metabolites from Bryozoa: a functional analysis.

    PubMed

    Maltseva, Arina L; Kotenko, Olga N; Kutyumov, Vladimir A; Matvienko, Darya A; Shavarda, Alexey L; Winson, Michael K; Ostrovsky, Andrew N

    2016-11-29

    Marine invertebrates are a promising source of novel natural products with biological activities. The phylum Bryozoa is relatively under-investigated in this context, although a number of compounds with medical potential has been discovered in recent years. Here, we report on the novel group of brominated metabolites from the bryozoan Terminoflustra membranaceatruncata, including analysis of biological activities of the tribrominated terminoflustrindole A (Cm-1) and the structures of the related dibrominated variants terminoflustrindoles B and C. Terminoflustrindole A was previously shown to have fungicidal properties. Although they vary by just one bromine group in each case from terminoflustrindole A, in this study, we report that terminoflustrindoles B and C exhibit no antimicrobial activity in the same assays. In addition to displaying antifungal activity, Terminoflustrindole A was also found to exhibit potent cytotoxic activity when tested against tumour cell lines. The gradient distribution of this compound within the bryozoan colony was demonstrated using LC-MS-analysis.

  12. Effects of neonatal exposure to the flame retardant tetrabromobisphenol-A, aluminum diethylphosphinate or zinc stannate on long-term potentiation and synaptic protein levels in mice.

    PubMed

    Hendriks, Hester S; Koolen, Lucas A E; Dingemans, Milou M L; Viberg, Henrik; Lee, Iwa; Leonards, Pim E G; Ramakers, Geert M J; Westerink, Remco H S

    2015-12-01

    Brominated flame retardants such as tetrabromobisphenol-A (TBBPA) may exert (developmental) neurotoxic effects. However, data on (neuro)toxicity of halogen-free flame retardants (HFFRs) are scarce. Recent in vitro studies indicated a high neurotoxic potential for some HFFRs, e.g., zinc stannate (ZS), whereas the neurotoxic potential of other HFFRs, such as aluminum diethylphosphinate (Alpi), appears low. However, the in vivo (neuro)toxicity of these compounds is largely unknown. We therefore investigated effects of neonatal exposure to TBBPA, Alpi or ZS on synaptic plasticity in mouse hippocampus. Male C57bl/6 mice received a single oral dose of 211 µmol/kg bw TBBPA, Alpi or ZS on postnatal day (PND) 10. On PND 17-19, effects on hippocampal synaptic plasticity were investigated using ex vivo extracellular field recordings. Additionally, we measured levels of postsynaptic proteins involved in long-term potentiation (LTP) as well as flame retardant concentrations in brain, muscle and liver tissues. All three flame retardants induced minor, but insignificant, effects on LTP. Additionally, TBBPA induced a minor decrease in post-tetanic potentiation. Despite these minor effects, expression of selected synaptic proteins involved in LTP was not affected. The flame retardants could not be measured in significant amounts in the brains, suggesting low bioavailability and/or rapid elimination/metabolism. We therefore conclude that a single neonatal exposure on PND 10 to TBBPA, Alpi or ZS does affect neurodevelopment and synaptic plasticity only to a small extent in mice. Additional data, in particular on persistence, bioaccumulation and (in vivo) toxicity, following prolonged (developmental) exposure are required for further (human) risk assessment.

  13. Penetration of polar brominated DBPs through the activated carbon columns during total organic bromine analysis.

    PubMed

    Li, Yao; Zhang, Xiangru; Krasner, Stuart W; Shang, Chii; Zhai, Hongyan; Liu, Jiaqi; Yang, Mengting

    2011-10-01

    Total organic bromine (TOBr) is a collective parameter representing all the brominated organic disinfection byproducts (DBPs) in water samples. TOBr can be measured using the adsorption-pyrolysis method according to Standard Method 5320B. This method involves that brominated organic DBPs are separated from inorganic halides and concentrated from aqueous solution by adsorption onto the activated carbon (AC). Previous studies have reported that some commonly known brominated DBPs can partially penetrate through the AC during this adsorption step. In this work, the penetration of polar brominated DBPs through AC and ozone-modified AC was explored with two simulated drinking water samples and one chlorinated wastewater effluent sample. Polar brominated DBPs were selectively detected with a novel precursor ion scan method using electrospray ionization-triple quadrupole mass spectrometry. The results show that 3.4% and 10.4% of polar brominated DBPs (in terms of total ion intensity) in the chlorinated Suwannee River fulvic acid and humic acid samples, respectively, penetrated through the AC, and 19.6% of polar brominated DBPs in the chlorinated secondary wastewater effluent sample penetrated through the AC. The ozone-modification of AC minimized the penetration of polar brominated DBPs during the TOBr analysis.

  14. Systematic vibration thermodynamic properties of bromine

    NASA Astrophysics Data System (ADS)

    Liu, G. Y.; Sun, W. G.; Liao, B. T.

    2015-11-01

    Based on the analysis of the maturity and finiteness of vibrational levels of bromine molecule in ground state and evaluating the effect on statistical computation, according to the elementary principles of quantum statistical theorem, using the full set of bromine molecular vibrational levels determined with algebra method, the statistical contribution for bromine systematical macroscopic thermodynamic properties is discussed. Thermodynamic state functions Helmholtz free energy, entropy and observable vibration heat capacity are calculated. The results show that the determination of full set of vibrational levels and maximum vibrational quantum number is the key in the correct statistical analysis of bromine systematical thermodynamic property. Algebra method results are clearly different from data of simple harmonic oscillator and the related algebra method results are no longer analytical but numerical and are superior to simple harmonic oscillator results. Compared with simple harmonic oscillator's heat capacities, the algebra method's heat capacities are more consistent with the experimental data in the given temperature range of 600-2100 K.

  15. Room-Temperature Fluorine-Induced Decrease in the Stability of Bromine and Iodine Intercalated Carbon Fibers

    NASA Technical Reports Server (NTRS)

    Hung, Ching-Cheh

    1995-01-01

    Upon exposure to room-temperature fluorine, intercalated carbon fibers (containing either bromine alone or iodine and bromine together) become heavier and less stable. For Amoco P-100 graphitized carbon fibers, which were intercalated with 18 wt percent bromine, 1 hour of fluorine exposure resulted in a large weight increase but caused only a small decrease in thermal stability. An additional 89 hours of fluorine exposure time resulted in small additional increases in fiber weight, but significant further decreases in fiber thermal stability. Such phenomena of weight increase and stability decrease do not occur if the intercalated fibers are exposed to 250 C fluorine. These observations suggest that, at room temperature, fluorine is absorbed quickly by the intercalated fibers and is intercalated slowly into the fibers. Most of the original intercalates are replaced by fluorine in the process of fluorine intercalation. In an inert environment, the bromine intercalated fibers are much more thermally stable. After 800 C vacuum heating for 2 weeks, the brominated fibers lost about 45% of their bromine, and their resistivity increased from 64 mu(Omega)-cm to a range of 95-170 mu(Omega)-cm. This is still much lower than the value of 300 mu(Omega)-cm for pristine P-100. For practical purposes, to preserve their thermal stability, brominated fibers need to be protected from exposure to fluorine at room temperature or to any intercalate at a temperature where, upon direct contact with graphite, an intercalation compound can easily be formed.

  16. 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.

  17. The effect of bromination of carbon fibers on the coefficient of thermal expansion of graphite fiber-epoxy composites

    NASA Technical Reports Server (NTRS)

    Jaworske, D. A.; Maciag, C.

    1987-01-01

    To examine the effect of bromination of carbon fibers on the coefficient of thermal expansion (CTE) of carbon fiber epoxy composites, several pristine and brominated carbon fiber-epoxy composite samples were subjected to thermomechanical analysis. The CTE's of these samples were measured in the uniaxial and transverse directions. The CTE was dominated by the fibers in the uniaxial direction, while it was dominated by the matrix in the transverse directions. Bromination had no effect on the CTE of any of the composites. In addition, the CTE of fiber tow was measured in the absence of a polymer matrix, using an extension probe. The results from this technique were inconclusive.

  18. Manganese dioxide causes spurious gold values in flame atomic-absorption readings from HBr-Br2 digestions

    USGS Publications Warehouse

    Campbell, W.L.

    1981-01-01

    False readings, apparently caused by the presence of high concentrations of manganese dioxide, have been observed in our current flame atomic-absorption procedure for the determination of gold. After a hydrobromic acid (HBr)-bromine (Br2) leach, simply heating the sample to boiling to remove excess Br2 prior to extraction with methyl-isobutyl-ketone (MIBK) eliminates these false readings. ?? 1981.

  19. Toxicokinetics of the Sterioisomer Specific Flame Retardant Hexabromocyclododecane (HBCD) Gamma: Effect of Dose, Time, and Repeated Exposure

    EPA Science Inventory

    Hexabromocyclododecanes (HBCDs) are high production volume brominated aliphatic cyclic hydrocarbons used as flame-retardants in foams, plastics and textiles. Commercial HBCD is a mixture of three main stereoisomers, alpha (α), beta (β) and gamma (γ). A shift from the high percent...

  20. 75 FR 16104 - Bromine Registration Review Final Decision; Notice of Availability

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-03-31

    ... AGENCY Bromine Registration Review Final Decision; Notice of Availability AGENCY: Environmental... registration review decision for the pesticide Bromine, case 4015. Registration review is EPA's periodic review... registration review decision for bromine, case 4015. Bromine is a bromide releasing antimicrobial...

  1. Flame-in-gas-shield and miniature diffusion flame hydride atomizers for atomic fluorescence spectrometry: optimization and comparison

    NASA Astrophysics Data System (ADS)

    Marschner, Karel; Musil, Stanislav; Dědina, Jiří

    2015-07-01

    A detailed optimization of relevant experimental parameters of two hydride atomizers for atomic fluorescence spectrometry: flame-in-gas-shield atomizer with a two-channel shielding unit and a standard atomizer for atomic fluorescence spectrometry, miniature diffusion flame, was performed. Arsine, generated by the reaction with NaBH4 in a flow injection arrangement, was chosen as the model hydride. Analytical characteristics of both the atomizers (sensitivity, noise, limits of detection) were compared. Under optimum conditions sensitivity obtained with flame-in-gas-shield atomizer was approximately twice higher than with miniature diffusion flame. The additional advantage of flame-in-gas-shield atomizer is significantly lower flame emission resulting in a better signal to noise ratio. The resulting arsenic limits of detection for miniature diffusion flame and flame-in-gas-shield atomizer were 3.8 ng l- 1 and 1.0 ng l- 1, respectively.

  2. The Science of Flames.

    ERIC Educational Resources Information Center

    Cornia, Ray

    1991-01-01

    Describes an exercise using flames that allows students to explore the complexities of a seemingly simple phenomenon, the lighting of a candle. Contains a foldout that provides facts about natural gas flames and suggestions for classroom use. (ZWH)

  3. Electrochemical performance evaluations and safety investigations of pentafluoro(phenoxy)cyclotriphosphazene as a flame retardant electrolyte additive for application in lithium ion battery systems using a newly designed apparatus for improved self-extinguishing time measurements

    NASA Astrophysics Data System (ADS)

    Dagger, Tim; Lürenbaum, Constantin; Schappacher, Falko M.; Winter, Martin

    2017-02-01

    A modified self-extinguishing time (SET) device which enhances the reproducibility of the results is presented. Pentafluoro(phenoxy)cyclotriphosphazene (FPPN) is investigated as flame retardant electrolyte additive for lithium ion batteries (LIBs) in terms of thermal stability and electrochemical performance. SET measurements and adiabatic reaction calorimetry are applied to determine the flammability and the reactivity of a standard LIB electrolyte containing 5% FPPN. The results reveal that the additive-containing electrolyte is nonflammable for 10 s whereas the commercially available reference electrolyte inflames instantaneously after 1 s of ignition. The onset temperature of the safety enhanced electrolyte is delayed by ≈ 21 °C. Compatibility tests in half cells show that the electrolyte is reductively stable while the cyclic voltammogram indicates oxidative decomposition during the first cycle. Cycling experiments in full cells show improved cycling performance and rate capability, which can be attributed to cathode passivation during the first cycle. Post-mortem analysis of the electrolyte by gas chromatography-mass spectrometry confirms the presence of the additive in high amounts after 501 cycles which ensures enhanced safety of the electrolyte. The investigations present FPPN as stable electrolyte additive that improves the intrinsic safety of the electrolyte and its cycling performance at the same time.

  4. Bromine accumulation in acidic black colluvial soils

    NASA Astrophysics Data System (ADS)

    Cortizas, Antonio Martínez; Vázquez, Cruz Ferro; Kaal, Joeri; Biester, Harald; Casais, Manuela Costa; Rodríguez, Teresa Taboada; Lado, Luis Rodríguez

    2016-02-01

    Recent investigations showed that bromine is incorporated to soil organic matter (SOM), its content increasing with humification. But few research was done on its long-term accumulation and the role played by pedogenetic processes, as those involved in organic matter stabilization. We investigated bromine content and distribution in four deep, acidic, organic-rich, Holocene soils from an oceanic area of Western Europe. Bromine concentrations (93-778 μg g-1) in the silt + clay (<50 μm) fraction were on average 3-times higher than those (17-250 μg g-1) in the fine earth (<2 mm), the former containing almost all bromine (90 ± 5%). Inventories were between 148 and 314 g m-2, indicating a rather large variability in a small area, and total estimated retention was low (6-16%). The degree of SOM bromination, expressed as the Br/C molar ratio, varied between 0.03 and 1.20 mmol Br/mol C. The ratio was highly correlated (n = 23, r2 0.88, p < 0.01) with the age of the SOM for the last ∼12 ka. Partial least squares modeling indicates that bromine concentration depends on the amount of organic matter stabilized as aluminium-OM associations, and to a lesser extent on soil acidity (pH) and iron-OM associations. Thus, at scales of thousands of years, bromine accumulation in acidic soils is linked to the pool of metal-clay-stabilized organic matter.

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

    PubMed

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

    2016-03-01

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

  6. 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

  7. 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

  8. On the bromination of the dihydroazulene/vinylheptafulvene photo-/thermoswitch

    PubMed Central

    Mazzanti, Virginia; Cacciarini, Martina; Broman, Søren L; Parker, Christian R; Schau-Magnussen, Magnus; Bond, Andrew D

    2012-01-01

    Summary Background: The dihydroazulene (DHA)/vinylheptafulvene (VHF) system (with two cyano groups at C1) functions as a photo-/thermoswitch. Direct ionic bromination of DHA has previously furnished a regioselective route to a 7,8-dibromide, which by elimination was converted to a 7-bromo-substituted DHA. This compound has served as a central building block for functionalization of the DHA by palladium-catalyzed cross-coupling reactions. The current work explores another bromination protocol for achieving the isomeric 3-bromo-DHA and also explores the outcome of additional bromination of this compound as well as of the known 7-bromo-DHA. Results: Radical bromination on two different VHFs by using N-bromosuccinimide/benzoyl peroxide and light, followed by a ring-closure reaction generated the corresponding 3-bromo-DHAs, as confirmed in one case by X-ray crystallography. According to a 1H NMR spectroscopic study, the ring closure of the brominated VHF seemed to occur readily under the reaction conditions. A subsequent bromination–elimination protocol provided a 3,7-dibromo-DHA. In contrast, treating the known 7-bromo-DHA with bromine generated a very labile species that was converted to a new 3,7-dibromoazulene, i.e., the fully unsaturated species. Azulenes were also found to form from brominated compounds when left standing for a long time in the solid state. Kinetics measurements reveal that the 3-bromo substituent enhances the rate of the thermal conversion of the VHF to DHA, which is opposite to the effect exerted by a bromo substituent in the seven-membered ring. Conclusion: Two general procedures for functionalizing the DHA core with a bromo substituent (at positions 3 and 7, respectively) are now available with the DHA as starting material. PMID:23015846

  9. 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.

  10. Abiotic Bromination of Soil Organic Matter.

    PubMed

    Leri, Alessandra C; Ravel, Bruce

    2015-11-17

    Biogeochemical transformations of plant-derived soil organic matter (SOM) involve complex abiotic and microbially mediated reactions. One such reaction is halogenation, which occurs naturally in the soil environment and has been associated with enzymatic activity of decomposer organisms. Building on a recent finding that naturally produced organobromine is ubiquitous in SOM, we hypothesized that inorganic bromide could be subject to abiotic oxidations resulting in bromination of SOM. Through lab-based degradation treatments of plant material and soil humus, we have shown that abiotic bromination of particulate organic matter occurs in the presence of a range of inorganic oxidants, including hydrogen peroxide and assorted forms of ferric iron, producing both aliphatic and aromatic forms of organobromine. Bromination of oak and pine litter is limited primarily by bromide concentration. Fresh plant material is more susceptible to bromination than decayed litter and soil humus, due to a labile pool of mainly aliphatic compounds that break down during early stages of SOM formation. As the first evidence of abiotic bromination of particulate SOM, this study identifies a mechanistic source of the natural organobromine in humic substances and the soil organic horizon. Formation of organobromine through oxidative treatments of plant material also provides insights into the relative stability of aromatic and aliphatic components of SOM.

  11. The milling of pristine and brominated P-100 graphite fibers

    NASA Technical Reports Server (NTRS)

    Dillehay, M. E.; Gaier, J. R.

    1986-01-01

    Techniques were developed for the ball milling of pristine and brominated P-100 graphite fibers. Because of the lubrication properties of graphite, large ball loads (50 percent by volume) were required. Use of 2-propanol as a milling medium enhanced the efficiency of the process. Milled brominated P-100 fibers had resistivities which were indistinguishable from milled pristine P-100 fibers. Apparent loss of bromine from the brominated fibers suggests that bromine would not be the intercalate of choice in applications where milled fibers of this type are required. Other intercalates which do not degas may be more appropriate for a milled fiber application. These same results, however, do provide evidence that bromine molecules leave the fiber surface when removed from overpressure of bromine. While exploring possible solvent media for milling purposes, it was found that brominated fibers are stable in a wide variety of organic solvents.

  12. Flame structure and chemiluminescence in premixed flames

    NASA Astrophysics Data System (ADS)

    Grana-Otero, Jose; Mahmoudi, Siamak

    2016-11-01

    The quantitative use of chemiluminescence requires the knowledge of the relationship between the concentration of excited species with flame properties such as the equivalency ratio, the burning rate or the heat release rate. With the aim of rigorously finding from first principles these relations we have analyzed, numerically and analytically, the distribution of the excited species OH* and CH* in steady hydrogen and methane planar premixed flames. Their mass fractions turn out to be extremely small; thus, a kinetic mechanism describing their dynamics in the flame can be obtained by simply adding the kinetic mechanism describing the excitation and de-excitation to the mechanism of the base flame. Due also to their small concentrations, the excited species are in steady state, facilitating a simple analytical description. The analyses show that OH*, both in hydrogen and methane flames, can be found broadly distributed downstream the preheat region, in a three-layer structure that is analytically described. The distribution of CH* is much simpler, being always in equilibrium with CH, whose concentration is in turn proportional to that of CH4. As a result, CH* is confined to the methane consumption layer in lean flames, but broadly distributed in rich flames.

  13. 40 CFR 721.2925 - Brominated aromatic ester.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Brominated aromatic ester. 721.2925... Substances § 721.2925 Brominated aromatic ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a brominated aromatic ester (PMN...

  14. 40 CFR 721.3085 - Brominated phthalate ester.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Brominated phthalate ester. 721.3085... Substances § 721.3085 Brominated phthalate ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as brominated phthalate ester (PMN P-90-581)...

  15. 40 CFR 721.3085 - Brominated phthalate ester.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Brominated phthalate ester. 721.3085... Substances § 721.3085 Brominated phthalate ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as brominated phthalate ester (PMN P-90-581)...

  16. 40 CFR 721.2925 - Brominated aromatic ester.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Brominated aromatic ester. 721.2925... Substances § 721.2925 Brominated aromatic ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a brominated aromatic ester (PMN...

  17. 40 CFR 721.3085 - Brominated phthalate ester.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Brominated phthalate ester. 721.3085... Substances § 721.3085 Brominated phthalate ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as brominated phthalate ester (PMN P-90-581)...

  18. 40 CFR 721.3085 - Brominated phthalate ester.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Brominated phthalate ester. 721.3085... Substances § 721.3085 Brominated phthalate ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as brominated phthalate ester (PMN P-90-581)...

  19. 40 CFR 721.2925 - Brominated aromatic ester.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Brominated aromatic ester. 721.2925... Substances § 721.2925 Brominated aromatic ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a brominated aromatic ester (PMN...

  20. 40 CFR 721.2925 - Brominated aromatic ester.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Brominated aromatic ester. 721.2925... Substances § 721.2925 Brominated aromatic ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a brominated aromatic ester (PMN...

  1. 40 CFR 721.3085 - Brominated phthalate ester.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Brominated phthalate ester. 721.3085... Substances § 721.3085 Brominated phthalate ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as brominated phthalate ester (PMN P-90-581)...

  2. 40 CFR 721.2925 - Brominated aromatic ester.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Brominated aromatic ester. 721.2925... Substances § 721.2925 Brominated aromatic ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a brominated aromatic ester (PMN...

  3. Numerical simulation of bromine crossover behavior in flow battery

    NASA Astrophysics Data System (ADS)

    Jia, Yaobin; Cheng, Shijian; Chu, Dandan; Li, Xin

    2017-03-01

    Br2 and HBr has its own series of advantages as the positive electrolyte solution, so some batteries select the Br2/Br- as the positive electrolyte solution, such as sodium polysulfide/bromine flow battery, zinc/bromine flow battery, vanadium/ bromine flow batteries and hydrogen/bromine flow batteries. But the crossover benavior of bromine occurs in these batteries too, resulting in cross-contamination, capacity loss and affecting battery's performance. In this work, we build numerical models to study the influence of bromine crossover phenomenon on the three forms of bromine crossover, the concentration of electrolyte on the cathode side and the flow rate of the negative side in the quinone bromine flow battery, to find the main models affecting the bromine crossover and the impact of bromine crossover on battery performance. It was found that the three ways of crossover through the membranes was mainly by diffusion. By reducing the concentration of positive electrolyte solution, the bromine crossover can be reduced and Coulomb Efficiency can be improved. Rising the flow rate of the electrolyte solution on the negative side and reducing the differential between positive side's pressure and negative side's pressure can also reduce the amount of bromine crossover to improve Coulomb efficiency in the battery.

  4. 40 CFR 721.10124 - Brominated polyaromatic compound (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Brominated polyaromatic compound... Specific Chemical Substances § 721.10124 Brominated polyaromatic compound (generic). (a) Chemical substance... brominated polyaromatic compound (PMN P-06-617) is subject to reporting under this section for...

  5. 40 CFR 721.10124 - Brominated polyaromatic compound (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Brominated polyaromatic compound... Specific Chemical Substances § 721.10124 Brominated polyaromatic compound (generic). (a) Chemical substance... brominated polyaromatic compound (PMN P-06-617) is subject to reporting under this section for...

  6. 40 CFR 721.10124 - Brominated polyaromatic compound (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Brominated polyaromatic compound... Specific Chemical Substances § 721.10124 Brominated polyaromatic compound (generic). (a) Chemical substance... brominated polyaromatic compound (PMN P-06-617) is subject to reporting under this section for...

  7. 40 CFR 721.10124 - Brominated polyaromatic compound (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Brominated polyaromatic compound... Specific Chemical Substances § 721.10124 Brominated polyaromatic compound (generic). (a) Chemical substance... brominated polyaromatic compound (PMN P-06-617) is subject to reporting under this section for...

  8. Prediction of flame velocities of hydrocarbon flames

    NASA Technical Reports Server (NTRS)

    Dugger, Gordon L; Simon, Dorothy M

    1954-01-01

    The laminar-flame-velocity data previously reported by the Lewis Laboratory are surveyed with respect to the correspondence between experimental flame velocities and values predicted by semitheoretical and empirical methods. The combustible mixture variables covered are hydrocarbon structure (56 hydrocarbons), equivalence ratio of fuel-air mixture, mole fraction of oxygen in the primary oxygen-nitrogen mixture (0.17 to 0.50), and initial mixture temperature (200 degrees to 615 degrees k). The semitheoretical method of prediction considered are based on three approximate theoretical equations for flame velocity: the Semenov equation, the Tanford-Pease equation, and the Manson equation.

  9. The interaction of high-speed turbulence with flames: Turbulent flame speed

    SciTech Connect

    Poludnenko, A.Y.; Oran, E.S.

    2011-02-15

    substantially exceeds its laminar value, which results in a disproportionately large contribution of cusps to S{sub T} compared with the flame surface area in them. (7) A criterion is established for transition to the regime significantly influenced by cusp formation. In particular, at Karlovitz numbers Ka >or similar 20, flame collisions provide an important mechanism controlling S{sub T}, in addition to the increase of A{sub T} by large-scale motions and the potential enhancement of diffusive transport by small-scale turbulence. (author)

  10. Utilization of oxidation reactions for the spectrophotometric determination of captopril using brominating agents

    NASA Astrophysics Data System (ADS)

    El-Didamony, Akram M.; Erfan, Eman A. H.

    2010-03-01

    Three simple, accurate and sensitive methods (A-C) for the spectrophotometric assay of captopril (CPL) in bulk drug, in dosage forms and in the presence of its oxidative degradates have been described. The methods are based on the bromination of captopril with a solution of excess brominating mixture in hydrochloric acid medium. After bromination, the excess brominating mixture is followed by the estimation of surplus bromine by three different reaction schemes. In the first method (A), the determination of the residual bromine is based on its ability to bleach the indigo carmine dye and measuring the absorbance at 610 nm. Method B, involves treating the unreacted bromine with a measured excess of iron(II) and the remaining iron(II) is complexed with 1,10-phenanthroline and the increase in absorbance is measured at 510 nm. In method (C), the surplus bromine is treated with excess of iron(II) and the resulting iron(III) is complexed with thiocyanate and the absorbance is measured at 478 nm. In all the methods, the amount of bromine reacted corresponds to the drug content. The different experimental parameters affecting the development and stability of the color are carefully studied and optimized. Beer's law is valid within a concentration range of 0.4-6.0, 0.4-2.8 and 1.2-4.8 μg mL -1 for methods A, B and C, respectively. The calculated apparent molar absorptivity was found to be 5.16 × 10 4, 9.95 × 10 4 and 1.74 × 10 5 L mol -1 cm -1, for methods A, B and C, respectively. Sandell's sensitivity, correlation coefficients, detection and quantification limits are also reported. No interference was observed from common additives found in pharmaceutical preparations. The proposed methods are successfully applied to the determination of CPL in the tablet formulations with mean recoveries of 99.94-100.11% and the results were statistically compared with those of a reference method by applying Student's t- and F-test.

  11. Ninth Spectrum of Bromine: Br IX

    NASA Astrophysics Data System (ADS)

    Joshi, Y. N.; van Kleef, Th A. M.

    1981-03-01

    The spectrum of bromine was photographed on a 6.60 m and a 10.7 m grazing incidence spectrograph in the region 300-90 Å. The source used was a triggered spark. The ninth spectrum of bromine was analysed on the basis of 3d9-3d84p transitions between 125-104 Å. Parametric level fitting calculations support the analysis. 44 lines are classified in this spectrum. Some Br VIII lines appearing in this region have been accurately measured.

  12. Bromine and Chlorine Go Separate Ways

    NASA Technical Reports Server (NTRS)

    2004-01-01

    This graph shows the relative concentrations of bromine and chlorine at various locations on Earth and Mars. Typically, bromine and chlorine stick together in a fixed ratio, as in martian meteorites and Earth seawater. But sometimes the elements split apart and their relative quantities diverge. This separation is usually caused by evaporation processes, as in the Dead Sea on Earth. On Mars, at Meridiani Planum and Gusev Crater, this split has been observed to an even greater degree than seen on Earth. This puzzling result is currently being further explored by Mars Exploration Rover scientists. Data for the Mars locations were taken by the rover's alpha particle X-ray spectrometer.

  13. Optically pumped molecular bromine laser. Master's thesis

    SciTech Connect

    Morrison, J.W.

    1990-12-01

    An optically pumped molecular bromine laser was studied to investigate the quenching kinetics state of Br2. This included characterization of the pressure dependence of the laser output power. The approach was to excite molecular bromine in a sealed cell with a Nd:YAG pumped dye laser. Unresolved side fluorescence and amplified stimulated emission (ASE) spectra were recorded. ASE offered the advantage of a simpler optical system with no externally induced wavelength dependencies. Stimulated emission as a signal monitor offered greater resolution than side fluorescence spectra and facilitated spectroscopic assignment. (JS)

  14. Improved charge carrier lifetime in planar perovskite solar cells by bromine doping

    NASA Astrophysics Data System (ADS)

    Kiermasch, David; Rieder, Philipp; Tvingstedt, Kristofer; Baumann, Andreas; Dyakonov, Vladimir

    2016-12-01

    The charge carrier lifetime is an important parameter in solar cells as it defines, together with the mobility, the diffusion length of the charge carriers, thus directly determining the optimal active layer thickness of a device. Herein, we report on charge carrier lifetime values in bromine doped planar methylammonium lead iodide (MAPbI3) solar cells determined by transient photovoltage. The corresponding charge carrier density has been derived from charge carrier extraction. We found increased lifetime values in solar cells incorporating bromine compared to pure MAPbI3 by a factor of ~2.75 at an illumination intensity corresponding to 1 sun. In the bromine containing solar cells we additionally observe an anomalously high value of extracted charge, which we deduce to originate from mobile ions.

  15. Improved charge carrier lifetime in planar perovskite solar cells by bromine doping

    PubMed Central

    Kiermasch, David; Rieder, Philipp; Tvingstedt, Kristofer; Baumann, Andreas; Dyakonov, Vladimir

    2016-01-01

    The charge carrier lifetime is an important parameter in solar cells as it defines, together with the mobility, the diffusion length of the charge carriers, thus directly determining the optimal active layer thickness of a device. Herein, we report on charge carrier lifetime values in bromine doped planar methylammonium lead iodide (MAPbI3) solar cells determined by transient photovoltage. The corresponding charge carrier density has been derived from charge carrier extraction. We found increased lifetime values in solar cells incorporating bromine compared to pure MAPbI3 by a factor of ~2.75 at an illumination intensity corresponding to 1 sun. In the bromine containing solar cells we additionally observe an anomalously high value of extracted charge, which we deduce to originate from mobile ions. PMID:27982095

  16. Improved charge carrier lifetime in planar perovskite solar cells by bromine doping.

    PubMed

    Kiermasch, David; Rieder, Philipp; Tvingstedt, Kristofer; Baumann, Andreas; Dyakonov, Vladimir

    2016-12-16

    The charge carrier lifetime is an important parameter in solar cells as it defines, together with the mobility, the diffusion length of the charge carriers, thus directly determining the optimal active layer thickness of a device. Herein, we report on charge carrier lifetime values in bromine doped planar methylammonium lead iodide (MAPbI3) solar cells determined by transient photovoltage. The corresponding charge carrier density has been derived from charge carrier extraction. We found increased lifetime values in solar cells incorporating bromine compared to pure MAPbI3 by a factor of ~2.75 at an illumination intensity corresponding to 1 sun. In the bromine containing solar cells we additionally observe an anomalously high value of extracted charge, which we deduce to originate from mobile ions.

  17. Chemistry of OClO in the Antarctic stratosphere - Implications for bromine

    NASA Technical Reports Server (NTRS)

    Salawitch, Ross J.; Wofsy, Steven C.; Mcelroy, Michael B.

    1988-01-01

    Previous observations of OClO over the Antarctic obtained in 1986 are used to constrain the stratospheric abundance of bromine. The observed diurnal variation is consistent with the production of OClO via the reaction of ClO with BrO if the branching ratio to the BrCl channel is between 3.5 and 14 percent. Otherwise, an additional source in twilight is indicated. The present results suggest a stratospheric bromine concentration of 16 + or - 4 pptv, a value which is consistent with independent measurements.

  18. Suppression of Low Strain Rate Nonpremixed Flames by an Agent

    NASA Technical Reports Server (NTRS)

    Hamins, A.; Bundy, M.; Puri, I. K.; McGrattan, K.; Park, W. C.

    2001-01-01

    The agent concentration required to achieve the suppression of low strain rate nonpremixed flames is an important consideration for fire protection in a microgravity environment such as a space platform. Currently, there is a lack of understanding of the structure and extinction of low strain rate (<20 s(exp -1)) nonpremixed flames. The exception to this statement is the study by Maruta et al., who reported measurements of low strain rate suppression of methane-air diffusion flames with N2 added to the fuel stream under microgravity conditions. They found that the nitrogen concentration required to achieve extinction increased as the strain rate decreased until a critical value was obtained. As the strain rate was further decreased, the required N2 concentration decreased. This phenomenon was termed "turning point" behavior and was attributed to radiation-induced nonpremixed flame extinction. In terms of fire safety, a critical agent concentration assuring suppression under all flow conditions represents a fundamental limit for nonpremixed flames. Counterflow flames are a convenient configuration for control of the flame strain rate. In high and moderately strained near-extinction nonpremixed flames, analysis of flame structure typically neglects radiant energy loss because the flames are nonluminous and the hot gas species are confined to a thin reaction zone. In counterflowing CH4-air flames, for example, radiative heat loss fractions ranging from 1 to 6 percent have been predicted and measured. The objective of this study is to investigate the impact of radiative emission, flame strain, agent addition, and buoyancy on the structure and extinction of low strain rate nonpremixed flames through measurements and comparison with flame simulations. The suppression effectiveness of a number of suppressants (N2, CO2, or CF3Br) was considered as they were added to either the fuel or oxidizer streams of low strain rate methane-air diffusion flames.

  19. Candle flames in microgravity

    NASA Technical Reports Server (NTRS)

    Dietrich, D. L.; Ross, H. D.; Tien, J. S.

    1995-01-01

    The candle flame in both normal and microgravity is non-propagating. In microgravity, however, the candle flame is also non-convective where (excepting Stefan flow) pure diffusion is the only transport mode. It also shares many characteristics with another classical problem, that of isolated droplet combustion. Given their qualitatively similar flame shapes and the required heat feedback to condensed-phase fuels, the gas-phase flow and temperature fields should be relatively similar for a droplet and a candle in reduced gravity. Unless the droplet diameter is maintained somehow through non-intrusive replenishment of fuel, the quasi-steady burning characteristics of a droplet can be maintained for only a few seconds. In contrast, the candle flame in microgravity may achieve a nearly steady state over a much longer time and is therefore ideal for examining a number of combustion-related phenomena. In this paper, we examine candle flame behavior in both short-duration and long-duration, quiescent, microgravity environments. Interest in this type of flame, especially 'candle flames in weightlessness', is demonstrated by very frequent public inquiries. The question is usually posed as 'will a candle flame burn in zero gravity', or, 'will a candle burn indefinitely (or steadily) in zero gravity in a large volume of quiescent air'. Intuitive speculation suggests to some that, in the absence of buoyancy, the accumulation of products in the vicinity of the flame will cause flame extinction. The classical theory for droplet combustion with its spherically-shaped diffusion flame, however, shows that steady combustion is possible in the absence of buoyancy if the chemical kinetics are fast enough. Previous experimental studies of candle flames in reduced and microgravity environments showed the flame could survive for at least 5 seconds, but did not reach a steady state in the available test time.

  20. Flame and flameless atomic-absorption determination of tellurium in geological materials

    USGS Publications Warehouse

    Chao, T.T.; Sanzolone, R.F.; Hubert, A.E.

    1978-01-01

    The sample is digested with a solution of hydrobromic acid and bromine and the excess of bromine is expelled. After dilution of the solution to approximately 3 M in hydrobromic acid, ascorbic acid is added to reduce iron(III) before extraction of tellurium into methyl isobutyl ketone (MIBK). An oxidizing air-acetylene flame is used to determine tellurium in the 0.1-20 ppm range. For samples containing 4-200 ppb of tellurium, a carbon-rod atomizer is used after the MIBK extract has been washed with 0.5 M hydrobromic acid to remove the residual iron. The flame procedure is useful for rapid preliminary monitoring, and the flameless procedure can determine tellurium at very low concentrations. ?? 1978.

  1. Determination of Zinc-Based Additives in Lubricating Oils by Flow-Injection Analysis with Flame-AAS Detection Exploiting Injection with a Computer-Controlled Syringe.

    PubMed

    Pignalosa, Gustavo; Knochen, Moisés; Cabrera, Noel

    2005-01-01

    A flow-injection system is proposed for the determination of metal-based additives in lubricating oils. The system, operating under computer control uses a motorised syringe for measuring and injecting the oil sample (200 muL) in a kerosene stream, where it is dispersed by means of a packed mixing reactor and carried to an atomic absorption spectrometer which is used as detector. Zinc was used as model analyte. Two different systems were evaluated, one for low concentrations (range 0-10 ppm) and the second capable of providing higher dilution rates for high concentrations (range 0.02%-0.2% w/w). The sampling frequency was about 30 samples/h. Calibration curves fitted a second-degree regression model (r(2) = 0.996). Commercial samples with high and low zinc levels were analysed by the proposed method and the results were compared with those obtained with the standard ASTM method. The t test for mean values showed no significant differences at the 95% confidence level. Precision (RSD%) was better than 5% (2% typical) for the high concentrations system. The carryover between successive injections was found to be negligible.

  2. Determination of Zinc-Based Additives in Lubricating Oils by Flow-Injection Analysis with Flame-AAS Detection Exploiting Injection with a Computer-Controlled Syringe

    PubMed Central

    Pignalosa, Gustavo; Cabrera, Noel

    2005-01-01

    A flow-injection system is proposed for the determination of metal-based additives in lubricating oils. The system, operating under computer control uses a motorised syringe for measuring and injecting the oil sample (200 μL) in a kerosene stream, where it is dispersed by means of a packed mixing reactor and carried to an atomic absorption spectrometer which is used as detector. Zinc was used as model analyte. Two different systems were evaluated, one for low concentrations (range 0–10 ppm) and the second capable of providing higher dilution rates for high concentrations (range 0.02%–0.2% w/w). The sampling frequency was about 30 samples/h. Calibration curves fitted a second-degree regression model (r 2 = 0.996). Commercial samples with high and low zinc levels were analysed by the proposed method and the results were compared with those obtained with the standard ASTM method. The t test for mean values showed no significant differences at the 95% confidence level. Precision (RSD%) was better than 5% (2% typical) for the high concentrations system. The carryover between successive injections was found to be negligible. PMID:18924720

  3. 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.

  4. Flame front geometry in premixed turbulent flames

    SciTech Connect

    Shepherd, I.G.; Ashurst, W.T.

    1991-12-01

    Experimental and numerical determinations of flame front curvature and orientation in premixed turbulent flames are presented. The experimental data is obtained from planar, cross sectional images of stagnation point flames at high Damkoehler number. A direct numerical simulation of a constant energy flow is combined with a zero-thickness, constant density flame model to provide the numerical results. The computational domain is a 32{sup 3} cube with periodic boundary conditions. The two-dimensional curvature distributions of the experiments and numerical simulations compare well at similar q{prime}/S{sub L} values with means close to zero and marked negative skewness. At higher turbulence levels the simulations show that the distributions become symmetric about zero. These features are also found in the three dimensional distributions of curvature. The simulations support assumptions which make it possible to determine the mean direction cosines from the experimental data. This leads to a reduction of 12% in the estimated flame surface area density in the middle of the flame brush. 18 refs.

  5. Suppression of Soot Formation and Shapes of Laminar Jet Diffusion Flames

    NASA Technical Reports Server (NTRS)

    Xu, F.; Dai, Z.; Faeth, G. M.

    2001-01-01

    Laminar nonpremixed (diffusion) flames are of interest because they provide model flame systems that are far more tractable for analysis and experiments than practical turbulent flames. In addition, many properties of laminar diffusion flames are directly relevant to turbulent diffusion flames using laminar flamelet concepts. Finally, laminar diffusion flame shapes have been of interest since the classical study of Burke and Schumann because they involve a simple nonintrusive measurement that is convenient for evaluating flame shape predictions. Motivated by these observations, the shapes of round hydrocarbon-fueled laminar jet diffusion flames were considered, emphasizing conditions where effects of buoyancy are small because most practical flames are not buoyant. Earlier studies of shapes of hydrocarbon-fueled nonbuoyant laminar jet diffusion flames considered combustion in still air and have shown that flames at the laminar smoke point are roughly twice as long as corresponding soot-free (blue) flames and have developed simple ways to estimate their shapes. Corresponding studies of hydrocarbon-fueled weakly-buoyant laminar jet diffusion flames in coflowing air have also been reported. These studies were limited to soot-containing flames at laminar smoke point conditions and also developed simple ways to estimate their shapes but the behavior of corresponding soot-free flames has not been addressed. This is unfortunate because ways of selecting flame flow properties to reduce soot concentrations are of great interest; in addition, soot-free flames are fundamentally important because they are much more computationally tractable than corresponding soot-containing flames. Thus, the objectives of the present investigation were to observe the shapes of weakly-buoyant laminar jet diffusion flames at both soot-free and smoke point conditions and to use the results to evaluate simplified flame shape models. The present discussion is brief.

  6. The Cool Flames Experiment

    NASA Technical Reports Server (NTRS)

    Pearlman, Howard; Chapek, Richard; Neville, Donna; Sheredy, William; Wu, Ming-Shin; Tornabene, Robert

    2001-01-01

    volume ratio, and (T(bar) - Tw ) is the spatially averaged temperature excess. This Newtonian form has been validated in spatially-uniform, well-stirred reactors, provided the effective heat transfer coefficient associated with the unsteady process is properly evaluated. Unfortunately, it is not a valid assumption for spatially-nonuniform temperature distributions induced by natural convection in unstirred reactors. "This is why the analysis of such a system is so difficult." Historically, the complexities associated with natural convection were perhaps recognized as early as 1938 when thermal ignition theory was first developed. In the 1955 text "Diffusion and Heat Exchange in Chemical Kinetics", Frank-Kamenetskii recognized that "the purely conductive theory can be applied at sufficiently low pressure and small dimensions of the vessel when the influence of natural convection can be disregarded." This was reiterated by Tyler in 1966 and further emphasized by Barnard and Harwood in 1974. Specifically, they state: "It is generally assumed that heat losses are purely conductive. While this may be valid for certain low pressure slow combustion regimes, it is unlikely to be true for the cool flame and ignition regimes." While this statement is true for terrestrial experiments, the purely conductive heat transport assumption is valid at microgravity (mu-g). Specifically, buoyant complexities are suppressed at mu-g and the reaction-diffusion structure associated with low temperature oxidation reactions, cool flames and auto-ignitions can be studied. Without natural convection, the system is simpler, does not require determination of the effective heat transfer coefficient, and is a testbed for analytic and numerical models that assume pure diffusive transport. In addition, mu-g experiments will provide baseline data that will improve our understanding of the effects of natural convection on Earth.

  7. Preparation of ionic membranes for zinc/bromine storage batteries

    NASA Astrophysics Data System (ADS)

    Assink, R. A.; Arnold, C., Jr.

    Zinc/bromine flow batteries are being developed for vehicular and utility load leveling applications. During charge, an aqueous zinc bromide salt is electrolyzed to zinc metal and molecular bromine. During discharge, the zinc and bromine react to again form the zinc bromide salt. One serious disadvantage of the microporous separators presently used in the zinc/bromine battery is that modest amounts of bromine and negatively charged bromine moieties permeate through these materials and react with the zinc anode. This results in partial self-discharge of the battery and low coulombic efficiencies. Our approach to this problem is to impregnate the microporous separators with a soluble cationic polyelectrolyte. In laboratory screening tests a sulfonated polysulfone resin and fully fluorinated sulfonic acid polymer substantially reduced bromine permeation with only modest increases in the area resistance.

  8. Graphite fiber intercalation: Dynamics of the bromine intercalation process

    NASA Technical Reports Server (NTRS)

    Jaworske, D. A.; Zinolabedini, R.

    1985-01-01

    The resistance of pitch-based graphite fibers was monitored, in situ, during a series of bromine intercalation experiments. The threshold pressure for the bromine intercalation of pitch-based fibers was estimated to be 102 torr. When the bromine atmosphere was removed from the reaction chamber, the resistivity of the intercalated graphite fibers increased consistently. This increase was attributed to loss of bromine from the perimeter of the fiber. The loss was confirmed by mapping the bromine concentration across the diameter of single intercalated fibers with either energy dispersive spectroscopy or scanning Auger microscopy. A statistical study comparing fibers intercalated in bromine vapor with fibers intercalated in bromine liquid showed that similar products were obtained with both methods of intercalation.

  9. Flame Holder System

    NASA Technical Reports Server (NTRS)

    Haskin, Henry H. (Inventor); Vasquez, Peter (Inventor)

    2013-01-01

    A flame holder system includes a modified torch body and a ceramic flame holder. Catch pin(s) are coupled to and extend radially out from the torch body. The ceramic flame holder has groove(s) formed in its inner wall that correspond in number and positioning to the catch pin(s). Each groove starts at one end of the flame holder and can be shaped to define at least two 90.degree.turns. Each groove is sized to receive one catch pin therein when the flame holder is fitted over the end of the torch body. The flame holder is then manipulated until the catch pin(s) butt up against the end of the groove(s).

  10. Bromination of selected pharmaceuticals in water matrices.

    PubMed

    Benitez, F Javier; Acero, Juan L; Real, Francisco J; Roldan, Gloria; Casas, Francisco

    2011-11-01

    The bromination of five selected pharmaceuticals (metoprolol, naproxen, amoxicillin, phenacetin, and hydrochlorothiazide) was studied with these compounds individually dissolved in ultra-pure water. The apparent rate constants for the bromination reaction were determined as a function of the pH, obtaining the sequence amoxicillin>naproxen>hydrochlorothiazide≈phenacetin≈metoprolol. A kinetic mechanism specifying the dissociation reactions and the species formed for each compound according to its pK(a) value and the pH allowed the intrinsic rate constants to be determined for each elementary reaction. There was fairly good agreement between the experimental and calculated values of the apparent rate constants, confirming the goodness of the proposed reaction mechanism. In a second stage, the bromination of the selected pharmaceuticals simultaneously dissolved in three water matrices (a groundwater, a surface water from a public reservoir, and a secondary effluent from a WWTP) was investigated. The pharmaceutical elimination trend agreed with the previously determined rate constants. The influence of the main operating conditions (pH, initial bromine dose, and characteristics of the water matrix) on the degradation of the pharmaceuticals was established. An elimination concentration profile for each pharmaceutical in the water matrices was proposed based on the use of the previously evaluated apparent rate constants, and the theoretical results agreed satisfactorily with experiment. Finally, chlorination experiments performed in the presence of bromide showed that low bromide concentrations slightly accelerate the oxidation of the selected pharmaceuticals during chlorine disinfection.

  11. Structure and functionality of bromine doped graphite.

    PubMed

    Hamdan, Rashid; Kemper, A F; Cao, Chao; Cheng, H P

    2013-04-28

    First-principles calculations are used to study the enhanced in-plane conductivity observed experimentally in Br-doped graphite, and to study the effect of external stress on the structure and functionality of such systems. The model used in the numerical calculations is that of stage two doped graphite. The band structure near the Fermi surface of the doped systems with different bromine concentrations is compared to that of pure graphite, and the charge transfer between carbon and bromine atoms is analyzed to understand the conductivity change along different high symmetry directions. Our calculations show that, for large interlayer separation between doped graphite layers, bromine is stable in the molecular form (Br2). However, with increased compression (decreased layer-layer separation) Br2 molecules tend to dissociate. While in both forms, bromine is an electron acceptor. The charge exchange between the graphite layers and Br atoms is higher than that with Br2 molecules. Electron transfer to the Br atoms increases the number of hole carriers in the graphite sheets, resulting in an increase of conductivity.

  12. Structure and functionality of bromine doped graphite

    SciTech Connect

    Hamdan, Rashid; Kemper, A. F.; Cao Chao; Cheng, H. P.

    2013-04-28

    First-principles calculations are used to study the enhanced in-plane conductivity observed experimentally in Br-doped graphite, and to study the effect of external stress on the structure and functionality of such systems. The model used in the numerical calculations is that of stage two doped graphite. The band structure near the Fermi surface of the doped systems with different bromine concentrations is compared to that of pure graphite, and the charge transfer between carbon and bromine atoms is analyzed to understand the conductivity change along different high symmetry directions. Our calculations show that, for large interlayer separation between doped graphite layers, bromine is stable in the molecular form (Br{sub 2}). However, with increased compression (decreased layer-layer separation) Br{sub 2} molecules tend to dissociate. While in both forms, bromine is an electron acceptor. The charge exchange between the graphite layers and Br atoms is higher than that with Br{sub 2} molecules. Electron transfer to the Br atoms increases the number of hole carriers in the graphite sheets, resulting in an increase of conductivity.

  13. 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

  14. Diffusion Flame Stabilization

    NASA Technical Reports Server (NTRS)

    Takahashi, Fumiaki; Katta, Viswanath R.

    2007-01-01

    Diffusion flames are commonly used for industrial burners in furnaces and flares. Oxygen/fuel burners are usually diffusion burners, primarily for safety reasons, to prevent flashback and explosion in a potentially dangerous system. Furthermore, in most fires, condensed materials pyrolyze, vaporize, and burn in air as diffusion flames. As a result of the interaction of a diffusion flame with burner or condensed-fuel surfaces, a quenched space is formed, thus leaving a diffusion flame edge, which plays an important role in flame holding in combustion systems and fire spread through condensed fuels. Despite a long history of jet diffusion flame studies, lifting/blowoff mechanisms have not yet been fully understood, compared to those of premixed flames. In this study, the structure and stability of diffusion flames of gaseous hydrocarbon fuels in coflowing air at normal earth gravity have been investigated experimentally and computationally. Measurements of the critical mean jet velocity (U(sub jc)) of methane, ethane, or propane at lifting or blowoff were made as a function of the coflowing air velocity (U(sub a)) using a tube burner (i.d.: 2.87 mm) (Fig. 1, left). By using a computational fluid dynamics code with 33 species and 112 elementary reaction steps, the internal chemical-kinetic structures of the stabilizing region of methane and propane flames were investigated (Fig. 1, right). A peak reactivity spot, i.e., reaction kernel, is formed in the flame stabilizing region due to back-diffusion of heat and radical species against an oxygen-rich incoming flow, thus holding the trailing diffusion flame. The simulated flame base moved downstream under flow conditions close to the measured stability limit.

  15. Diffusion Flame Stabilization

    NASA Technical Reports Server (NTRS)

    Takahashi, Fumiaki; Katta, V. R.

    2006-01-01

    Diffusion flames are commonly used for industrial burners in furnaces and flares. Oxygen/fuel burners are usually diffusion burners, primarily for safety reasons, to prevent flashback and explosion in a potentially dangerous system. Furthermore, in most fires, condensed materials pyrolyze, vaporize, and burn in air as diffusion flames. As a result of the interaction of a diffusion flame with burner or condensed-fuel surfaces, a quenched space is formed, thus leaving a diffusion flame edge, which plays an important role in flame holding in combustion systems and fire spread through condensed fuels. Despite a long history of jet diffusion flame studies, lifting/blowoff mechanisms have not yet been fully understood, compared to those of premixed flames. In this study, the structure and stability of diffusion flames of gaseous hydrocarbon fuels in coflowing air at normal earth gravity have been investigated experimentally and computationally. Measurements of the critical mean jet velocity (U(sub jc)) of methane, ethane, or propane at lifting or blowoff were made as a function of the coflowing air velocity (U(sub a)) using a tube burner (i.d.: 2.87 mm). By using a computational fluid dynamics code with 33 species and 112 elementary reaction steps, the internal chemical-kinetic structures of the stabilizing region of methane and propane flames were investigated. A peak reactivity spot, i.e., reaction kernel, is formed in the flame stabilizing region due to back-diffusion of heat and radical species against an oxygen-rich incoming flow, thus holding the trailing diffusion flame. The simulated flame base moved downstream under flow conditions close to the measured stability limit.

  16. (ELF) Enclosed Laminar Flames

    NASA Technical Reports Server (NTRS)

    1997-01-01

    The goal of the ELF investigation is to improve our fundamental understanding of the effects of the flow environment on flame stability. The flame's stability refers to the position of its base and ultimately its continued existence. Combustion research focuses on understanding the important hidden processes of ignitions, flame spreading, and flame extinction. Understanding these processes will directly affect the efficiency of combustion operations in converting chemical energy to heat and will create a more balanced ecology and healthy environment by reducing pollutants emitted during combustion.

  17. 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.

  18. Search for Possible Stratospheric Bromine Reservoir Species: Theoretical Study of the Photostability of Mono-, Tri-, and Pentacoordinated Bromine Compounds

    NASA Technical Reports Server (NTRS)

    Lee, TImothy J.; Mejia, Cesar N.; Beran, J. O.; Head-Gordon, Martin

    2004-01-01

    Previous work has shown that pentacoordinated bromine compounds have their lowest excited electronic states shifted to the blue relative to monocoordinated bromine molecules, and that this shift may be large enough to render them photostable in the lower stratosphere. Our earlier work has also shown that certain pentacoordinated bromine compounds are thermodynamically stable relative to their mono- or tricoordinated isomers, suggesting that if a bromine stratospheric reservoir species exists, then it is most likely a pentacoordinated compound. In this study we have examined the singlet excited electronic states of several bromine compounds in order to assess their photostability excited states in mono-, tri-, and pentacoordinated bromine molecules. Due to the strong spin-orbit mixing in bromine, we have also examined the lowest triplet excited state.

  19. Field Effects of Buoyancy on Lean Premixed Turbulent Flames

    NASA Technical Reports Server (NTRS)

    Cheng, R. K.; Johnson, M. R.; Greenberg, P. S.; Wernet, M. P.

    2003-01-01

    The study of field effects of buoyancy on premixed turbulent flames is directed towards the advancement of turbulent combustion theory and the development of cleaner combustion technologies. Turbulent combustion is considered the most important unsolved problem in combustion science and laboratory studies of turbulence flame processes are vital to theoretical development. Although buoyancy is dominant in laboratory flames, most combustion models are not yet capable to consider buoyancy effects. This inconsistency has impeded the validation of theories and numerical simulations with experiments. Conversely, the understanding of buoyancy effects is far too limited to help develop buoyant flame models. Our research is also relevant to combustion technology because lean premixed combustion is a proven method to reduce the formation of oxides of nitrogen (NOx). In industrial lean premixed combustion systems, their operating conditions make them susceptible to buoyancy thus affecting heat distribution, emissions, stability, flashback and blowoff. But little knowledge is available to guide combustion engineers as to how to avoid or overcome these problems. Our hypothesis is that through its influence on the mean pressure field, buoyancy has direct and indirect effects on local flame/turbulence interactions. Although buoyancy acts on the hot products in the farfield the effect is also felt in the nearfield region upstream of the flame. These changes also influence the generation and dissipation of turbulent kinetic energy inside the flame brush and throughout the flowfield. Moreover, the plume of an open flame is unstable and the periodic fluctuations make additional contributions to flame front dynamics in the farfield. Therefore, processes such as flame wrinkling, flow acceleration due to heat release and flame- generated vorticity are all affected. Other global flame properties (e.g. flame stabilization limits and flame speed) may all be coupled to buoyancy. This

  20. 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.

  1. In situ accumulation of HBCD, PBDEs, and several alternative flame-retardants in the bivalve (Corbicula fluminea) and gastropod (Elimia proxima).

    PubMed

    La Guardia, Mark J; Hale, Robert C; Harvey, Ellen; Mainor, T Matteson; Ciparis, Serena

    2012-06-05

    Alternative brominated flame-retardants (BFRs), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (TBB), 2-ethylhexyl 2,3,4,5-tetrabromophthalate (TBPH), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE) and decabromodiphenyl ethane (DBDPE), are now being detected in the environment. However, contaminant bioavailability is influenced by the organisms' ecology (i.e., route of uptake) and in situ environmental factors. We observed that the filter-feeding bivalve (Corbicula fluminea) and grazing gastropod (Elimia proxima), collected downstream from a textile manufacturing outfall, exhibited TBB, TBPH, and BTBPE concentrations from 152 to 2230 ng g(-1) lipid weight (lw). These species also contained additional BFRs. Maximum levels of total hexabromocyclododecane diastereomers (∑HBCDs) in these species were 363,000 and 151,000 ng g(-1) lw, and those of polybrominated diphenyl ethers (∑PBDEs) were 64,900 and 47,200 ng g(-1) lw, respectively. These concentrations are among the highest reported to date worldwide. While BDE-209 was once thought to be nonbioavailable and resistant to degradation, it was the dominant BFR present and likely debromination products were detected. Contributions of α- and β-HBCD were higher in tissues than sediments, consistent with γ-HBCD bioisomerization. Mollusk bioaccumulation factors were similar between HBCD and PBDEs with 4 to 6 bromines, but factors for TBB, TBPH, and BTBPE were lower. Despite different feeding strategies, the bivalves and gastropods exhibited similar BFR water and sediment accumulation factors.

  2. Distribution and speciation of bromine in mammalian tissue and fluids by X-ray fluorescence imaging and X-ray absorption spectroscopy.

    PubMed

    Ceko, Melanie J; Hummitzsch, Katja; Hatzirodos, Nicholas; Bonner, Wendy; James, Simon A; Kirby, Jason K; Rodgers, Raymond J; Harris, Hugh H

    2015-05-01

    Bromine is one of the most abundant and ubiquitous trace elements in the biosphere and until recently had not been shown to perform any essential biological function in animals. A recent study demonstrated that bromine is required as a cofactor for peroxidasin-catalysed formation of sulfilimine crosslinks in Drosophila. In addition, bromine dietary deficiency is lethal in Drosophila, whereas bromine replenishment restores viability. The aim of this study was to examine the distribution and speciation of bromine in mammalian tissues and fluids to provide further insights into the role and function of this element in biological systems. In this study we used X-ray fluorescence (XRF) imaging and inductively coupled plasma-mass spectrometry (ICP-MS) to examine the distribution of bromine in bovine ovarian tissue samples, follicular fluid and aortic serum, as well as human whole blood and serum and X-ray absorption spectroscopy (XAS) to identify the chemical species of bromine in a range of mammalian tissue (bovine, ovine, porcine and murine), whole blood and serum samples (bovine, ovine, porcine, murine and human), and marine samples (salmon (Salmo salar), kingfish (Seriola lalandi) and Scleractinian coral). Bromine was found to be widely distributed across all tissues and fluids examined. In the bovine ovary in particular it was more concentrated in the sub-endothelial regions of arterioles. Statistical comparison of the near-edge region of the X-ray absorption spectra with a library of bromine standards led to the conclusion that the major form of bromine in all samples analysed was bromide.

  3. 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.

  4. Effect of Intense Sound Waves on a Stationary Gas Flame

    NASA Technical Reports Server (NTRS)

    Hahnemann, H; Ehret, L

    1950-01-01

    Intense sound waves with a resonant frequency of 5000 cycles per second were imposed on a stationary propane-air flame issuing from a nozzle. In addition to a slight increase of the flame velocity, a fundamental change both in the shape of the burning zone and in the flow pattern could be observed. An attempt is made to explain the origin of the variations in the flame configuration on the basis of transition at the nozzle from jet flow to potential flow.

  5. The Flame Tree

    ERIC Educational Resources Information Center

    Lewis, Richard

    2004-01-01

    Lewis's own experiences living in Indonesia are fertile ground for telling "a ripping good story," one found in "The Flame Tree." He hopes people will enjoy the tale and appreciate the differences of an unfamiliar culture. The excerpt from "The Flame Tree" will reel readers in quickly.

  6. Candle Flames in Microgravity

    NASA Technical Reports Server (NTRS)

    Dietrich, D. L.; Ross, H. D.; Chang, P.; T'ien, J. S.

    2001-01-01

    The goal of this work is to study both experimentally and numerically the behavior of a candle flame burning in a microgravity environment. Two space experiments (Shuttle and Mir) have shown the candle flame in microgravity to be small (approximately 1.5 cm diameter), dim blue, and hemispherical. Near steady flames with very long flame lifetimes (up to 45 minutes in some tests) existed for many of the tests. Most of the flames spontaneously oscillated with a period of approximately 1 Hz just prior to extinction). In a previous model of candle flame in microgravity, a porous sphere wetted with liquid fuel simulated the evaporating wick. The sphere, with a temperature equal to the boiling temperature of the fuel, was at the end of an inert cone that had a prescribed temperature. This inert cone produces the quenching effect of the candle wax in the real configuration. Although the computed flame shape resembled that observed in the microgravity experiment, the model was not able to differentiate the effect of wick geometry, e.g., a long vs. a short wick. This paper presents recent developments in the numerical model of the candle flame. The primary focus has been to more realistically account for the actual shape of the candle.

  7. 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

  8. 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.

  9. 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.

  10. Kinetic bromine isotope effect: example from the microbial debromination of brominated phenols.

    PubMed

    Bernstein, Anat; Ronen, Zeev; Levin, Elena; Halicz, Ludwik; Gelman, Faina

    2013-03-01

    The increasing use of kinetic isotope effects for environmental studies has motivated the development of new compound-specific isotope analysis techniques for emerging pollutants. Recently, high-precision bromine isotope analysis in individual brominated organic compounds was proposed, by the coupling of gas chromatography to a multi-collector inductively coupled plasma mass spectrometer using strontium as an external spike for instrumental bias correction. The present study, for the first time, demonstrates an application of this technique for determining bromine kinetic isotope effects during biological reaction, focusing on the reductive debromination of brominated phenols under anaerobic conditions. Results show bromine isotope enrichment factors (ε) of -0.76 ± 0.08, -0.46 ± 0.19, and -0.20 ± 0.06 ‰ for the debromination of 4-bromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol, respectively. These values are rather low, yet still high enough to be obtained with satisfying certainty. This further implies that the analytical method may be also appropriate for future environmental applications.

  11. Membrane-less hydrogen bromine flow battery.

    PubMed

    Braff, William A; Bazant, Martin Z; Buie, Cullen R

    2013-01-01

    In order for the widely discussed benefits of flow batteries for electrochemical energy storage to be applied at large scale, the cost of the electrochemical stack must come down substantially. One promising avenue for reducing stack cost is to increase the system power density while maintaining efficiency, enabling smaller stacks. Here we report on a membrane-less hydrogen bromine laminar flow battery as a potential high-power density solution. The membrane-less design enables power densities of 0.795 W cm(-2) at room temperature and atmospheric pressure, with a round-trip voltage efficiency of 92% at 25% of peak power. Theoretical solutions are also presented to guide the design of future laminar flow batteries. The high-power density achieved by the hydrogen bromine laminar flow battery, along with the potential for rechargeable operation, will translate into smaller, inexpensive systems that could revolutionize the fields of large-scale energy storage and portable power systems.

  12. Marine bacterial degradation of brominated methanes

    USGS Publications Warehouse

    Goodwin, K.D.; Lidstrom, M.E.; Oremland, R.S.

    1997-01-01

    Brominated methanes are ozone-depleting compounds whose natural sources include marine algae such as kelp. Brominated methane degradation by bacteria was investigated to address whether bacterial processes might effect net emission of these compounds to the atmosphere. Bacteria in seawater collected from California kelp beds degraded CH2Br2 but not CHBr3. Specific inhibitors showed that methanotrophs and nitrifiers did not significantly contribute to CH2Br2 removal. A seawater enrichment culture oxidized 14CH2Br2 to 14CO2 as well as 14CH3Br to 14CO2. The rates of CH2Br2 degradation in laboratory experiments suggest that bacterial degradation of CH2Br2 in a kelp bed accounts for <1% of the CH2Br2 produced by the kelp. However, the half-life of CH2Br2 due to bacterial removal appears faster than hydrolysis and within an order of magnitude of volatilization to the atmosphere.Brominated methanes are ozone-depleting compounds whose natural sources include marine algae such as kelp. Brominated methane degradation by bacteria was investigated to address whether bacterial processes might effect net emission of these compounds to the atmosphere. Bacteria in seawater collected from California kelp beds degraded CH2Br2 but not CHBr3. Specific inhibitors showed that methanotrophs and nitrifiers did not significantly contribute to CH2Br2 removal. A seawater enrichment culture oxidized 14CH2Br2 to 14CO2 as well as 14CH3Br to 14CO2. The rates of CH2Br2 degradation in laboratory experiments suggest that bacterial degradation of CH2Br2 in a kelp bed accounts for <1% of the CH2Br2 produced by the kelp. However, the half-life of CH2Br2 due to bacterial removal appears faster than hydrolysis and within an order of magnitude of volatilization to the atmosphere.

  13. Accelerative propagation and explosion triggering by expanding turbulent premixed flames.

    PubMed

    Akkerman, V'yacheslav; Chaudhuri, Swetaprovo; Law, Chung K

    2013-02-01

    The dynamics and morphology of outwardly propagating, accelerating turbulent premixed flames and the effect of flame acceleration on explosion triggering are analyzed. Guided by recent theoretical results and substantiated by experiments, we find that an expanding flame front in an externally forced, near-isotropic turbulent environment exhibits accelerative propagation given by a well-defined power law based on the average global flame radius. In this context the limits of the power-law exponent and the effective turbulence intensity experienced by the flame are derived. The power-law exponent is found to be substantially larger than that for the hydrodynamically unstable cellular laminar flames, hence facilitating the possibility of detonation triggering in turbulent environments. For large length scales, hydrodynamic instability is expected to provide additional acceleration, thus further favoring the attainment of detonation triggering.

  14. 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.

  15. Flame Shapes of Nonbuoyant Laminar Jet Diffusion Flames

    NASA Technical Reports Server (NTRS)

    Xu, F.; Dai, Z.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z. G. (Technical Monitor)

    2001-01-01

    The shapes (flame-sheet and luminous-flame boundaries) of steady nonbuoyant round hydrocarbon-fueled laminar-jet diffusion flames in still and coflowing air were studied both experimentally and theoretically. Flame-sheet shapes were measured from photographs using a CH optical filter to distinguish flame-sheet boundaries in the presence of blue CO2 and OH emissions and yellow continuum radiation from soot. Present experimental conditions included acetylene-, methane-, propane-, and ethylene-fueled flames having initial reactant temperatures of 300 K, ambient pressures of 4-50 kPa, jet exit Reynolds number of 3-54, initial air/fuel velocity ratios of 0-9 and luminous flame lengths of 5-55 mm; earlier measurements for propylene- and 1,3-butadiene-fueled flames for similar conditions were considered as well. Nonbuoyant flames in still air were observed at micro-gravity conditions; essentially nonbuoyant flames in coflowing air were observed at small pressures to control effects of buoyancy. Predictions of luminous flame boundaries from soot luminosity were limited to laminar smokepoint conditions, whereas predictions of flame-sheet boundaries ranged from soot-free to smokepoint conditions. Flame-shape predictions were based on simplified analyses using the boundary layer approximations along with empirical parameters to distinguish flame-sheet and luminous flame (at the laminar smoke point) boundaries. The comparison between measurements and predictions was remarkably good and showed that both flame-sheet and luminous-flame lengths are primarily controlled by fuel flow rates with lengths in coflowing air approaching 2/3 lengths in still air as coflowing air velocities are increased. Finally, luminous flame lengths at laminar smoke-point conditions were roughly twice as long as flame-sheet lengths at comparable conditions due to the presence of luminous soot particles in the fuel-lean region of the flames.

  16. Flame Shapes of Nonbuoyant Laminar Jet Diffusion Flames. Appendix K

    NASA Technical Reports Server (NTRS)

    Xu, F.; Faeth, G. M.; Urban, D. L. (Technical Monitor); Yuan, Z.-G. (Technical Monitor)

    2000-01-01

    The shapes (flame-sheet and luminous-flame boundaries) of steady nonbuoyant round hydrocarbon-fueled laminar-jet diffusion flames in still and coflowing air were studied both experimentally and theoretically. Flame-sheet shapes were measured from photographs using a CH optical filter to distinguish flame-sheet boundaries in the presence of blue C02 and OH emissions and yellow continuum radiation from soot. Present experimental conditions included acetylene-, methane-, propane-, and ethylene-fueled flames having initial reactant temperatures of 300 K, ambient pressures of 4-50 kPa, jet exit Reynolds number of 3-54, initial air/fuel velocity ratios of 0-9 and luminous flame lengths of 5-55 mm; earlier measurements for propylene- and 1,3-butadiene-fueled flames for similar conditions were considered as well. Nonbuoyant flames in still air were observed at micro-gravity conditions; essentially nonbuoyant flames in coflowing air were observed at small pressures to control effects of buoyancy. Predictions of luminous flame boundaries from soot luminosity were limited to laminar smoke-point conditions, whereas predictions of flame-sheet boundaries ranged from soot-free to smoke-point conditions. Flame-shape predictions were based on simplified analyses using the boundary layer approximations along with empirical parameters to distinguish flame-sheet and luminous-flame (at the laminar smoke point) boundaries. The comparison between measurements and predictions was remarkably good and showed that both flame-sheet and luminous-flame lengths are primarily controlled by fuel flow rates with lengths in coflowing air approaching 2/3 lengths in still air as coflowing air velocities are increased. Finally, luminous flame lengths at laminar smoke-point conditions were roughly twice as long as flame-sheet lengths at comparable conditions due to the presence of luminous soot particles in the fuel-lean region of the flames.

  17. Non-premixed acoustically perturbed swirling flame dynamics

    SciTech Connect

    Idahosa, Uyi; Saha, Abhishek; Xu, Chengying; Basu, Saptarshi

    2010-09-15

    An investigation into the response of non-premixed swirling flames to acoustic perturbations at various frequencies (f{sub p}=0-315 Hz) and swirl intensities (S=0.09 and 0.34) is carried out. Perturbations are generated using a loudspeaker at the base of an atmospheric co-flow burner with resulting velocity oscillation amplitudes vertical stroke u'/U{sub avg} vertical stroke in the 0.03-0.30 range. The dependence of flame dynamics on the relative richness of the flame is investigated by studying various constant fuel flow rate flame configurations. Flame heat release rate is quantitatively measured using a photomultiplier with a 430 nm bandpass filter for observing CH* chemiluminescence which is simultaneously imaged with a phase-locked CCD camera. The flame response is observed to exhibit a low-pass filter characteristic with minimal flame response beyond pulsing frequencies of 200 Hz. Flames at lower fuel flow rates are observed to remain attached to the central fuel pipe at all acoustic pulsing frequencies. PIV imaging of the associated isothermal fields show the amplification in flame aspect ratio is caused by the narrowing of the inner recirculation zone (IRZ). Good correlation is observed between the estimated flame surface area and the heat release rate signature at higher swirl intensity flame configurations. A flame response index analogous to the Rayleigh criterion in non-forced flames is used to assess the potential for a strong flame response at specific perturbation configurations and is found to be a good predictor of highly responsive modes. Phase conditioned analysis of the flame dynamics yield additional criteria in highly responsive modes to include the effective amplitude of velocity oscillations induced by the acoustic pulsing. In addition, highly responsive modes were characterized by velocity to heat release rate phase differences in the {+-}{pi}/2 range. A final observed characteristic in highly responsive flames is a Strouhal number between

  18. Silver-Catalyzed Decarboxylative Bromination of Aliphatic Carboxylic Acids.

    PubMed

    Tan, Xinqiang; Song, Tao; Wang, Zhentao; Chen, He; Cui, Lei; Li, Chaozhong

    2017-03-13

    The silver-catalyzed Hunsdiecker bromination of aliphatic carboxylic acids is described. With Ag(Phen)2OTf as the catalyst and dibromoisocyanuric acid as the brominating agent, various aliphatic carboxylic acids underwent decarboxylative bromination to provide the corresponding alkyl bromides under mild conditions. This method not only is efficient and general but also enjoys wide functional group compatibility. An oxidative radical mechanism involving Ag(II) intermediates is proposed.

  19. Effects of buoyancy on gas jet diffusion flames

    NASA Technical Reports Server (NTRS)

    Bahadori, M. Yousef; Edelman, Raymond B.

    1993-01-01

    The objective of this effort was to gain a better understanding of the fundamental phenomena involved in laminar gas jet diffusion flames in the absence of buoyancy by studying the transient phenomena of ignition and flame development, (quasi-) steady-state flame characteristics, soot effects, radiation, and, if any, extinction phenomena. This involved measurements of flame size and development, as well as temperature and radiation. Additionally, flame behavior, color, and luminosity were observed and recorded. The tests quantified the effects of Reynolds number, nozzle size, fuel reactivity and type, oxygen concentration, and pressure on flame characteristics. Analytical and numerical modeling efforts were also performed. Methane and propane flames were studied in the 2.2 Second Drop Tower and the 5.18-Second Zero-Gravity Facility of NASA LeRC. In addition, a preliminary series of tests were conducted in the KC-135 research aircraft. Both micro-gravity and normal-gravity flames were studied in this program. The results have provided unique and new information on the behavior and characteristics of gas jet diffusion flames in micro-gravity environments.

  20. Flame Spread Across Liquids

    NASA Technical Reports Server (NTRS)

    Ross, Howard D.; Miller, Fletcher J.; Sirignano, William A.; Schiller, David

    1997-01-01

    The principal goal of our recent research on flame spread across liquid pools is the detailed identification of the mechanisms that control the rate and nature of flame spread when the liquid pool is initially at an isothermal bulk temperature that is below the fuel's flash point temperature. In our project, we specialize the subject to highlight the roles of buoyancy-related processes regarding the mechanisms of flame spread, an area of research cited recently by Linan and Williams as one that needs further attention and which microgravity (micro-g) experiments could help to resolve. Toward resolving the effects of buoyancy on this flame spread problem, comparisons - between 1-g and micro-g experimental observations, and between model predictions and experimental data at each of these gravitational levels - are extensively utilized. The present experimental and computational foundation is presented to support identification of the mechanisms that control flame spread in the pulsating flame spread regime for which long-duration, micro-g flame spread experiments have been conducted aboard a sounding rocket.

  1. On Soot Inception in Nonpremixed Flames and the Effects of Flame Structure

    NASA Technical Reports Server (NTRS)

    Chao, B. H.; Liu, S.; Axelbaum, R. L.; Gokoglu, Suleyman (Technical Monitor)

    1998-01-01

    A simplified three-step model of soot inception has been employed with high activation energy asymptotics to study soot inception in nonpremixed counterflow systems with emphasis on understanding the effects of hydrodynamics and transport. The resulting scheme yields three zones: (1) a fuel oxidation zone wherein the fuel and oxidizer react to form product as well as a radical R, (e.g., H), (2) a soot/precursor formation zone where the radical R reacts with fuel to form "soot/precursor" S, and (3) a soot/precursor consumption zone where S reacts with the oxidizer to form product. The kinetic scheme, although greatly simplified, allows the coupling between soot inception and flame structure to be assessed. The results yield flame temperature, flame location, and a soot/precursor index S(sub I) as functions of Damkohler number for S formation. The soot/precursor index indicates the amount of S at the boundary of the formation region. The flame temperature indirectly indicates the total amount of S integrated over the formation region because as S is formed less heat release is available. The results show that unlike oxidation reactions, an extinction turning-point behavior does not exist for soot. Instead, the total amount of S slowly decreases with decreasing Damkohler number (increasing strain rate), which is consistent with counterflow flame experiments. When the Lewis number of the radical is decreased from unity, the total S reduces due to reduced residence time for the radical in the soot formation region. Similarly, when the Lewis number of the soot/precursor is increased from unity the amount of S increases for all Damkohler numbers. In addition to studying fuel-air (low stoichiometric mixture fraction) flames, the air-side nitrogen was substituted into the fuel, yielding diluted fuel-oxygen (high stoichiometric mixture fraction) flames with the same flame temperature as the fuel - air flames. The relative flame locations were different however, and

  2. Characteristics Of Turbulent Nonpremixed Jet-Flames And Jet-Flames In Crossflow In Normal- And Low-Gravity

    NASA Technical Reports Server (NTRS)

    Clemens, N. T.; Boxx, I. G.; Idicheria, C. A.

    2003-01-01

    It is well known that buoyancy has a major influence on the flow structure of turbulent nonpremixed jet flames. For example, previous studies have shown that transitional and turbulent jet flames exhibit flame lengths that are as much as a factor of two longer in microgravity than in normal gravity. The objective of this study is to extend these previous studies by investigating both mean and fluctuating characteristics of turbulent nonpremixed jet flames under three different gravity levels (1 g, 20 mg and 100 micrograms). This work is described in more detail elsewhere. In addition, we have recently initiated a new study into the effects of buoyancy on turbulent nonpremixed jet flames in cross-flow (JFICF). Buoyancy has been observed to play a key role in determining the centerline trajectories of such flames.6 The objective of this study is to use the low gravity environment to study the effects of buoyancy on the turbulent characteristics of JFICF.

  3. Structure of low-stretch methane nonpremixed flames

    SciTech Connect

    Han, Bai; Ibarreta, Alfonso F.; Sung, Chih-Jen; T'ien, James S.

    2007-04-15

    The present study experimentally and numerically investigates the structure associated with extremely low-stretch ({proportional_to}2 s{sup -1}) gaseous nonpremixed flames. The study of low-stretch flames aims to improve our fundamental understanding of the flame radiation effects on flame response and extinction limits. Low-stretch flames are also relevant to fire safety in reduced-gravity environments and to large buoyant fires, where localized areas of low stretch are attainable. In this work, ultra-low-stretch flames are established in normal gravity by bottom burning of a methane/nitrogen mixture discharged from a porous spherically symmetric burner of large radius of curvature. The large thickness of the resulting nonpremixed flame allows detailed mapping of the flame structure. Several advanced nonintrusive optical diagnostics are used to study the flame structure. Gas phase temperatures are measured by Raman scattering, while the burner surface temperatures are obtained by IR imaging. In addition, OH-PLIF and chemiluminescence imaging techniques are used to help characterize the extent of the flame reaction zone. These experimental results allow direct comparison with a quasi-one-dimensional numerical model including detailed chemistry, thermodynamic/transport properties, and radiation treatment. In addition, the radiative interactions between the flame and porous burner (modeled as a gray surface) are accounted for in the present model. The numerical modeling is demonstrated to be able to simulate the low-stretch flame structure. Using the current model, the extinction limits under different conditions are also examined. The computational results are consistent with experimental observations. (author)

  4. 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.

  5. Hydrogen-bromine fuel cell advance component development

    NASA Technical Reports Server (NTRS)

    Charleston, Joann; Reed, James

    1988-01-01

    Advanced cell component development is performed by NASA Lewis to achieve improved performance and longer life for the hydrogen-bromine fuel cells system. The state-of-the-art hydrogen-bromine system utilizes the solid polymer electrolyte (SPE) technology, similar to the SPE technology developed for the hydrogen-oxygen fuel cell system. These studies are directed at exploring the potential for this system by assessing and evaluating various types of materials for cell parts and electrode materials for Bromine-hydrogen bromine environment and fabricating experimental membrane/electrode-catalysts by chemical deposition.

  6. NMR investigation of non-brominated and brominated epoxy ester prepolymers

    NASA Astrophysics Data System (ADS)

    Žigon, M.; Osredkar, U.; Šebenik, A.

    1992-03-01

    1H, 13C and two-dimensional NMR spectroscopy has been used to investigate the structure of epoxy ester prepolymers, based on non-brominated DGEBA-type or brominated DGETBBA-type epoxy resins, and on an oligomeric carboxylic acid. In the presence of a quaternary phosphonium salt, besides diglycidylether of bisphenol A (DGEBA) or diglycidylether of tetrabromobisphenol A (DGETBBA) and their higher oligomers, monoesters with characteristic R-CH 2-CH(OH)-CH 2-OCOR' groups were detected in prevailing quantities. In dependence of the epoxy-carboxy ratio, isomeric monoesters with hydroxymethyl groups, diesters and diols might also be present.

  7. Premixed conical flame stabilization

    NASA Astrophysics Data System (ADS)

    Krikunova, A. I.; Son, E. E.; Saveliev, A. S.

    2016-11-01

    In the current work, stabilization of premixed laminar and lean turbulent flames for wide range of flow rates and equivalence ratios was performed. Methane-air mixture was ignited after passing through premixed chamber with beads and grids, and conical nozzle (Bunsen-type burner). On the edge of the nozzle a stabilized body-ring was mounted. Ring geometry was varied to get the widest stable flame parameters. This work was performed as part of the project on experimental investigation of premixed flames under microgravity conditions.

  8. Characterization of Three Tetrabromobisphenol-S Derivatives in Mollusks from Chinese Bohai Sea: A Strategy for Novel Brominated Contaminants Identification

    PubMed Central

    Liu, Ai-feng; Tian, Yong; Yin, Nuo-ya; Yu, Miao; Qu, Guang-bo; Shi, Jian-bo; Du, Yu-guo; Jiang, Gui-bin

    2015-01-01

    Identification of novel brominated contaminants in the environment, especially the derivatives and byproducts of brominated flame retardants (BFRs), has become a wide concern because of their adverse effects on human health. Herein, we qualitatively and quantitatively identified three byproducts of tetrabromobisphenol-S bis(2,3-dibromopropyl ether) (TBBPS-BDBPE), including TBBPS mono(allyl ether) (TBBPS-MAE), TBBPS mono(2-bromoallyl ether) (TBBPS-MBAE) and TBBPS mono(2,3-dibromopropyl ether) (TBBPS-MDBPE) as novel brominated contaminants. Meanwhile, the mass spectra and analytical method for determination of TBBPS-BDBPE byproducts were presented for the first time. The detectable concentrations (dry weight) of TBBPS-MAE, TBBPS-MBAE and TBBPS-MDBPE were in the ranges 28–394 μg/g in technical TBBPS-BDBPE and 0.1–4.1 ng/g in mollusks collected from the Chinese Bohai Sea. The detection frequencies in mollusk samples were 5%, 39%, 95% for TBBPS-MAE, TBBPS-MBAE and TBBPS-MDBPE, respectively, indicating their prevailing in the environment. The results showed that they could be co-produced and leaked into the environment with production process, and might be more bioaccumulative and toxic than TBBPS-BDBPE. Therefore, the production and use of TBBPS derivatives lead to unexpected contamination to the surrounding environment. This study also provided an effective approach for identification of novel contaminants in the environment with synthesized standards and Orbitrap high resolution mass spectrometry. PMID:26130450

  9. Modeling Candle Flame Behavior In Variable Gravity

    NASA Technical Reports Server (NTRS)

    Alsairafi, A.; Tien, J. S.; Lee, S. T.; Dietrich, D. L.; Ross, H. D.

    2003-01-01

    The burning of a candle, as typical non-propagating diffusion flame, has been used by a number of researchers to study the effects of electric fields on flame, spontaneous flame oscillation and flickering phenomena, and flame extinction. In normal gravity, the heat released from combustion creates buoyant convection that draws oxygen into the flame. The strength of the buoyant flow depends on the gravitational level and it is expected that the flame shape, size and candle burning rate will vary with gravity. Experimentally, there exist studies of candle burning in enhanced gravity (i.e. higher than normal earth gravity, g(sub e)), and in microgravity in drop towers and space-based facilities. There are, however, no reported experimental data on candle burning in partial gravity (g < g(sub e)). In a previous numerical model of the candle flame, buoyant forces were neglected. The treatment of momentum equation was simplified using a potential flow approximation. Although the predicted flame characteristics agreed well with the experimental results, the model cannot be extended to cases with buoyant flows. In addition, because of the use of potential flow, no-slip boundary condition is not satisfied on the wick surface. So there is some uncertainty on the accuracy of the predicted flow field. In the present modeling effort, the full Navier-Stokes momentum equations with body force term is included. This enables us to study the effect of gravity on candle flames (with zero gravity as the limiting case). In addition, we consider radiation effects in more detail by solving the radiation transfer equation. In the previous study, flame radiation is treated as a simple loss term in the energy equation. Emphasis of the present model is on the gas-phase processes. Therefore, the detailed heat and mass transfer phenomena inside the porous wick are not treated. Instead, it is assumed that a thin layer of liquid fuel coated the entire wick surface during the burning process

  10. 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.

  11. Flame spread across liquids

    NASA Technical Reports Server (NTRS)

    Ross, Howard D.; Miller, Fletcher; Schiller, David; Sirignano, William

    1995-01-01

    Recent reviews of our understanding of flame spread across liquids show that there are many unresolved issues regarding the phenomenology and causal mechanisms affecting ignition susceptibility, flame spread characteristics, and flame spread rates. One area of discrepancy is the effect of buoyancy in both the uniform and pulsating spread regimes. The approach we have taken to resolving the importance of buoyancy for these flames is: (1) normal gravity (1g) and microgravity (micro g) experiments; and (2) numerical modeling at different gravitational levels. Of special interest to this work, as discussed at the previous workshop, is the determination of whether, and under what conditions, pulsating spread occurs in micro g. Microgravity offers a unique ability to modify and control the gas-phase flow pattern by utilizing a forced air flow over the pool surface.

  12. Flame-resistant textiles

    NASA Technical Reports Server (NTRS)

    Fogg, L. C.; Stringham, R. S.; Toy, M. S.

    1980-01-01

    Flame resistance treatment for acid resistant polyamide fibers involving photoaddition of fluorocarbons to surface has been scaled up to treat 10 yards of commercial width (41 in.) fabric. Process may be applicable to other low cost polyamides, polyesters, and textiles.

  13. Enhancement of the carbon electrode capacitance by brominated hydroquinones

    NASA Astrophysics Data System (ADS)

    Gastol, Dominika; Walkowiak, Jedrzej; Fic, Krzysztof; Frackowiak, Elzbieta

    2016-09-01

    This paper presents supercapacitors utilizing new redox-active electrolytes with bromine species. Two sources of Br specimen were investigated, i.e. dibromodihydroxybenzene dissolved in KOH and potassium bromide dissolved in KOH with hydroxybenzene additive. KOH-activated carbon, exhibiting a well-developed porosity, was incorporated as an electrode material. The tested systems revealed a capacitance enhancement explained by Br- and partial BrO3- redox activity. The optimisation of the electrolyte concentration resulted in a capacitance value of 314 F g-1 achieved at 1.1 V voltage range. Good cyclability performance (11% capacitance loss) combined with a high capacitance value (244 F g-1) were obtained for the system operating in 0.2 mol L- 1 C6H4Br2O2 in 2 mol L-1 KOH electrolytic solution.

  14. Effects Of Electric Field On Hydrocarbon-Fueled Flames

    NASA Technical Reports Server (NTRS)

    Yuan, Z.-G.; Hegde, U.

    2003-01-01

    It has been observed that flames are susceptible to electric fields that are much weaker than the breakdown field strength of the flame gases. When an external electric field is imposed on a flame, the ions generated in the flame reaction zone drift in the direction of the electric forces exerted on them. The moving ions collide with the neutral species and change the velocity distribution in the affected region. This is often referred to as ionic wind effect. In addition, the removal of ions from the flame reaction zone can alter the chemical reaction pathway of the flame. On the other hand, the presence of space charges carried by moving ions affects the electric field distribution. As a result, the flame often changes its shape, location and color once an external electric field is applied. The interplay between the flame movement and the change of electric field makes it difficult to determine the flame location for a given configuration of electrodes and fuel source. In normal gravity, the buoyancy-induced flow often complicates the problem and hinders detailed study of the interaction between the flame and the electric field. In this work, the microgravity environment established at the 2.2 Second Drop Tower at the NASA Glenn Research Center is utilized to effectively remove the buoyant acceleration. The interaction between the flame and the electric field is studied in a one-dimensional domain. A specially designed electrode makes flame current measurements possible; thus, the mobility of ions, ion density, and ionic wind effect can be evaluated.

  15. Soot Formation in Hydrocarbon/Air Laminar Jet Diffusion Flames

    NASA Technical Reports Server (NTRS)

    Sunderland, P. B.; Faeth, G. M.

    1994-01-01

    Soot processes within hydrocarbon/air diffusion flames are important because they affect the durability and performance of propulsion systems, the hazards of unwanted fires, the pollutant and particulate emissions from combustion processes, and the potential for developing computational combustion. Motivated by these observations, this investigation involved an experimental study of the structure and soot properties of round laminar jet diffusion flames, seeking an improved understanding of soot formation (growth and nucleation) within diffusion flames. The present study extends earlier work in this laboratory concerning laminar smoke points (l) and soot formation in acetylene/air laminar jet diffusion flames (2), emphasizing soot formation in hydrocarbon/air laminar jet diffusion flames for fuels other than acetylene. In the flame system, acetylene is the dominant gas species in the soot formation region and both nucleation and growth were successfully attributed to first-order reactions of acetylene, with nucleation exhibiting an activation energy of 32 kcal/gmol while growth involved negligible activation energy and a collision efficiency of O.53%. In addition, soot growth in the acetylene diffusion flames was comparable to new soot in premixed flame (which also has been attributed to first-order acetylene reactions). In view of this status, a major issue is the nature of soot formation processes in diffusion flame involving hydrocarbon fuels other than acetylene. In particular, information is needed about th dominant gas species in the soot formation region and the impact of gas species other than acetylene on soot nucleation and growth.

  16. Active Control for Statistically Stationary Turbulent PremixedFlame Simulations

    SciTech Connect

    Bell, J.B.; Day, M.S.; Grcar, J.F.; Lijewski, M.J.

    2005-08-30

    The speed of propagation of a premixed turbulent flame correlates with the intensity of the turbulence encountered by the flame. One consequence of this property is that premixed flames in both laboratory experiments and practical combustors require some type of stabilization mechanism to prevent blow-off and flashback. The stabilization devices often introduce a level of geometric complexity that is prohibitive for detailed computational studies of turbulent flame dynamics. Furthermore, the stabilization introduces additional fluid mechanical complexity into the overall combustion process that can complicate the analysis of fundamental flame properties. To circumvent these difficulties we introduce a feedback control algorithm that allows us to computationally stabilize a turbulent premixed flame in a simple geometric configuration. For the simulations, we specify turbulent inflow conditions and dynamically adjust the integrated fueling rate to control the mean location of the flame in the domain. We outline the numerical procedure, and illustrate the behavior of the control algorithm on methane flames at various equivalence ratios in two dimensions. The simulation data are used to study the local variation in the speed of propagation due to flame surface curvature.

  17. Cellular Instabilities and Self-Acceleration of Expanding Spherical Flames

    NASA Technical Reports Server (NTRS)

    Law, C. K.; Kwon, O. C.

    2003-01-01

    In the present investigation we aim to provide experimental information on and thereby understanding of the generation and propagation of spark-ignited, outwardly propagating cellular flames, with three major focuses. The first is to unambiguously demonstrate the influence of the four most important parameters in inducing hydrodynamic and diffusional-thermal cellularities, namely thermal expansion, flame thickness, non-unity Lewis number, and global activation energy. The second is to investigate the critical state for the onset of cellularity for the stretch-affected, expanding flame. The third is to identify and consequently quantify the phenomena of self-acceleration and possibly auto-turbulization of cellular flames. Due to space limitation the effects of activation energy and the critical state for the onset of cellularity will not be discussed herein. Experiments were conducted using C3H8-air and H2-O2-N2 mixtures for their opposite influences of non-equidiffusivity. The additional system parameters varied were the chamber pressure (p) and the mixture composition including the equivalence ratio (phi). From a sequence of the flame images we can assess the propensity of cell formation, and determine the instantaneous flame radius (R), the flame propagation rate, the global stretch rate experienced by the flame, the critical flame radius at which cells start to grow, and the average cell size.

  18. Organophosphate Flame Retardants Act as Endocrine-Disrupting Chemicals in MA-10 Mouse Tumor Leydig Cells.

    PubMed

    Schang, Gauthier; Robaire, Bernard; Hales, Barbara F

    2016-04-01

    The organophosphate flame retardants (OPFRs) have emerged as alternatives to banned brominated flame retardants but little is known about their possible activity as endocrine disruptors. Our goal was to compare the effects of 7 commonly used OPFRsin vitroon MA-10 mouse Leydig tumor cells to those of a major brominated flame retardant, 2,2',4,4'-tetrabromodiphenyl ether (BDE-47). The effects of OPFRs and BDE-47 on mitochondrial activity, cell counts, oxidative stress, steroid secretion and gene expression were investigated. BDE-47 and all 7 OPFRs tested significantly reduced MA-10 cell mitochondrial activity (concentrations ≥50 μM) and cell number (concentrations ≥10 μM). All of the OPFRs significantly increased (10 μM, 1.7-4.4-fold) superoxide production whereas BDE-47 had no significant effect. Basal progesterone production was significantly increased (10 μM, 1.5 to 3-fold) by 2-ethylhexyl diphenyl phosphate, isodecyl diphenyl phosphate, isopropylated triphenyl phosphate, tert-butylphenyl diphenyl phosphate, and tricresyl phosphate, while BDE-47, triphenyl phosphate and tri-o-cresyl phosphate had no effect. Interestingly, isopropylated triphenyl phosphate enhanced dbcAMP-stimulated steroid production (∼2-fold), while tri-o-cresyl phosphate decreased (∼2/3) LH-stimulated steroid production. Several OPFRs affected the expression of genes involved in the biosynthesis of progesterone. In conclusion, all the OPFRs tested affected mitochondrial activity, cell survival, and superoxide production. Basal or stimulated steroid secretion was affected by all of the OPFRs except triphenyl phosphate; BDE-47 had no effect. Hence, the OPFRs currently used as alternatives affect Leydig cells to a greater extent than the brominated flame retardants that they have replaced.

  19. Triple flames in microgravity flame spread

    NASA Technical Reports Server (NTRS)

    Wichman, Indrek S.

    1995-01-01

    The purpose of this project is to examine in detail the influence of the triple flame structure on the flame spread problem. It is with an eye to the practical implications that this fundamental research project must be carried out. The microgravity configuration is preferable because buoyancy-induced stratification and vorticity generation are suppressed. A more convincing case can be made for comparing our predictions, which are zero-g, and any projected experiments. Our research into the basic aspects will employ two models. In one, flows of fuel and oxidizer from the lower wall are not considered. In the other, a convective flow is allowed. The non-flow model allows us to develop combined analytical and numerical solution methods that may be used in the more complicated convective-flow model.

  20. Potential hazards of brominated carbon sorbents for mercury emission control.

    PubMed

    Bisson, Teresa M; Xu, Zhenghe

    2015-02-17

    Mercury is a toxic air pollutant, emitted from the combustion of coal. Activated Carbon (AC) or other carbon sorbent (CS) injection into coal combustion flue gases can remove elemental mercury through an adsorption process. Recently, a brominated CS with biomass ash as the carbon source (Br-Ash) was developed as an alternative for costly AC-based sorbent for mercury capture. After mercury capture, these sorbents are disposed in landfill, and the stability of bromine and captured mercury is of paramount importance. The objective of this study is to determine the fate of mercury and bromine from Br-Ash and brominated AC after their service. Mercury and bromine leaching tests were conducted using the standard toxicity characteristic leaching procedure (TCLP). The mercury was found to be stable on both the Br-Ash and commercial brominated AC sorbents, while the bromine leached into the aqueous phase considerably. Mercury pulse injection tests on the sorbent material after leaching indicate that both sorbents retain significant mercury capture capability even after the majority of bromine was removed. Testing of the Br-Ash sorbent over a wider range of pH and liquid:solid ratios resulted in leaching of <5% of mercury adsorbed on the Br-Ash. XPS analysis indicated more organically bound Br and less metal-Br bonds after leaching.

  1. 40 CFR 721.10534 - Brominated aliphatic alcohol (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Brominated aliphatic alcohol (generic... Specific Chemical Substances § 721.10534 Brominated aliphatic alcohol (generic). (a) Chemical substance and... aliphatic alcohol (PMN P-12-260) is subject to reporting under this section for the significant new...

  2. 40 CFR 721.10534 - Brominated aliphatic alcohol (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Brominated aliphatic alcohol (generic... Specific Chemical Substances § 721.10534 Brominated aliphatic alcohol (generic). (a) Chemical substance and... aliphatic alcohol (PMN P-12-260) is subject to reporting under this section for the significant new...

  3. Species specific differences in the in vitro metabolism of the flame retardant mixture, Firemaster® BZ-54

    PubMed Central

    Bearr, Jonathan S.; Mitchelmore, Carys L.; Roberts, Simon C.; Stapleton, Heather M.

    2013-01-01

    Firemaster® BZ-54 is a flame retardant additive and consists of a brominated benzoate (2-ethylhexyl 2,3,4,5-tetrabromobenzoate; TBB) and a brominated phthalate (bis (2-ethylhexyl) 2,3,4,5-tetrabromophthalate; TBPH). Previous research has shown that fathead minnows exposed in vivo to Firemaster® BZ-54 accumulate TBB and TBPH. This study examined the in vitro biotransformation potential of TBB and TBPH in hepatic subcellular fractions (i.e., S9, microsomes and cytosol) in the fathead minnow, common carp, mouse and snapping turtle. Metabolism was evaluated by measuring the loss of the parent TBB or TBPH and identifying potential metabolites in the sample extracts. Metabolic loss of TBPH was measured for all species, while TBB loss was observed for all species except for the snapping turtle. Several metabolites were observed in all of the incubations except for snapping turtle. Metabolites observed appeared to be derived from TBB, given their structures and lack of appearance in the snapping turtle incubations. One of these metabolites, 2,3,4,5-tetrabromomethylbenzoate has been identified for the first time in a biological system. When metabolized, TBB and TBPH loss was found in each subcellular fraction suggesting that the enzyme(s) involved are present in both soluble and membrane-bound forms. It can be concluded that a broad range of species are capable of metabolizing TBB and TBPH to various metabolites and further research should be carried out to ascertain the specific products formed from metabolism of TBB and TBPH. PMID:22889877

  4. Species specific differences in the in vitro metabolism of the flame retardant mixture, Firemaster® BZ-54.

    PubMed

    Bearr, Jonathan S; Mitchelmore, Carys L; Roberts, Simon C; Stapleton, Heather M

    2012-11-15

    Firemaster(®) BZ-54 is a flame retardant additive and consists of a brominated benzoate (2-ethylhexyl 2,3,4,5-tetrabromobenzoate; TBB) and a brominated phthalate (bis (2-ethylhexyl) 2,3,4,5-tetrabromophthalate; TBPH). Previous research has shown that fathead minnows exposed in vivo to Firemaster(®) BZ-54 accumulate TBB and TBPH. This study examined the in vitro biotransformation potential of TBB and TBPH in hepatic subcellular fractions (i.e., S9, microsomes and cytosol) in the fathead minnow, common carp, mouse and snapping turtle. Metabolism was evaluated by measuring the loss of the parent TBB or TBPH and identifying potential metabolites in the sample extracts. Metabolic loss of TBPH was measured for all species, while TBB loss was observed for all species except for the snapping turtle. Several metabolites were observed in all of the incubations except for snapping turtle. Metabolites observed appeared to be derived from TBB, given their structures and lack of appearance in the snapping turtle incubations. One of these metabolites, 2,3,4,5-tetrabromomethylbenzoate has been identified for the first time in a biological system. When metabolized, TBB and TBPH loss was found in each subcellular fraction suggesting that the enzyme(s) involved are present in both soluble and membrane-bound forms. It can be concluded that a broad range of species are capable of metabolizing TBB and TBPH to various metabolites and further research should be carried out to ascertain the specific products formed from metabolism of TBB and TBPH.

  5. Effects of milling brominated P-100 graphite fibers

    NASA Technical Reports Server (NTRS)

    Gaier, James R.; Dillehay, Michael E.; Hambourger, Paul D.

    1987-01-01

    Preliminary procedures have been developed for the ball milling of pristine and brominated P-100 graphite fibers. Because of the lubricative properties of graphite, large ball loads (50 percent by volume) are required. Use of 2-propanol as a milling medium enhances the efficiency of the process. The fibers, when allowed to settle from the milling medium, tend to be preferentially aligned with rather few fibers standing up. Milled, brominated P-100 fibers have resistivities that are indistinguishable from their pristine counterparts, apparently because of loss of bromine. This suggests that bromine would not be the intercalate of choice in applications where milled fibers of this type are required. It was found that brominated graphite fibers are stable in a wide variety of organic solvents.

  6. Bromine oxidation in volcanic plumes

    NASA Astrophysics Data System (ADS)

    Bobrowski, N.; Vogel, L.; Kern, C.; Giuffrida, G. B.; Delgado-Granados, H.; Platt, U.

    2009-04-01

    Volcanoes are very strong sources of hydrogen, carbon, sulphur and halogen compounds, as well as of particles. Some gases only behave as passive tracers; others interact and affect the formation, growth or chemical characteristics of aerosol particles in a complex system. Recent measurements of halogen radicals in volcanic plumes showed that volcanic plumes are chemically very active. Kinetic considerations (Oppenheimer et al., 2006) and detailed calculations with an atmospheric chemistry model (Bobrowski et al., 2007) explain the halogen chemistry mainly with photochemical reactions involving both, the gas and particle phase. They reproduce the measured gas-phase concentrations quite well. However, temporal evolution of BrO in the early plume is not well described in the models. The understanding of chemical kinetics of BrO formation is still not complete. Recent measurement results (Vogel et al., 2008) do not fit with initial model calculation. The new data lead to the suggestion that the BrO formation could be much faster during the first few minutes after emission than initially suggested. Old and recent data sets will be confronted, compared and possible causes of their differences discussed. The measurements considered were taken at Mt. Etna (Italy), Villarica (Chile), and Popocatépetl (Mexico) volcanoes. Additionally, at Mt Etna the emission consists of up to four individual plumes from four summit craters. The differences between the individual plumes have been investigated during the last years and will be presented.

  7. Investigation of H2 Concentration and Combustion Instability Effects on the Kinetics of Strained Syngas Flames

    SciTech Connect

    Ahsan R. Choudhuri

    2006-08-07

    The flame extinction limits of syngas (H{sub 2}-CO) flames were measured using a twin-flame-counter-flow burner. Plots of Extinction limits vs. global stretch rates were generated at different mixture compositions and an extrapolation method was used to calculate the flame extinction limit corresponding to an experimentally unattainable zero-stretch condition. The zero-stretch extinction limit of H{sub 2}-CO mixtures decreases (from rich to lean) with the increase in H{sub 2} concentration in the mixture. The average difference between the measured flame extinction limit and the Le Chatelier's calculation is around {approx} 7%. The measured OH{sup -} chemiluminescent data indicates that regardless of mixture compositions the OH radical concentration reduces (within the experimental uncertainties) to an extinction value prior to the flame extinction. Flame extinction limits of H{sub 2}-CO mixtures measured in a flat-flame burner configuration also show a similar relation. Additionally, the measured laminar flame velocity close to the extinction indicates that regardless of fuel composition the premixed flame of hydrogen fuel blends extinguishes when the mixture laminar flame velocity falls below a critical value. The critical laminar flame velocity at extinction for H{sub 2}-CO premixed flames (measured in the flat flame burner configuration) is found to be 3.77({+-}0.38) cm/s. An externally perturbed H{sub 2}-CO twin flame was not experimentally achievable for the mixture conditions used in the present investigation. A slightest perturbation in the flow-field distorts the H{sub 2}-CO twin-flame. The flame becomes highly unstable with the introduction of an externally excited flow oscillation.

  8. DETAIL VIEW IN THE FLAME TRENCH LOOKING NORTH, FLAME DEFLECTOR ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    DETAIL VIEW IN THE FLAME TRENCH LOOKING NORTH, FLAME DEFLECTOR IN THE FOREGROUND, WATER PIPES AND VALVE ASSEMBLIES ON THE FOREGROUND. - Marshall Space Flight Center, Redstone Rocket (Missile) Test Stand, Dodd Road, Huntsville, Madison County, AL

  9. OMI observations of bromine monoxide emissions from salt lakes

    NASA Astrophysics Data System (ADS)

    Suleiman, R. M.; Chance, K.; Liu, X.; Gonzalez Abad, G.; Kurosu, T. P.

    2015-12-01

    In this study, we analyze bromine monoxide (BrO) data from the Ozone Monitoring Instrument (OMI) over various salt lakes. We used OMI data from 2005 to 2014 to investigate BrO signatures from salt lakes. The salt lakes regions we cover include Dead Sea; Salt Lake City, US; Salar de Uyuni, Bolivia; and Namtso, Tibet. Elevated signatures of BrO was found in July and August BrO monthly averages over the Dead Sea. Similar results were found in the BrO monthly averages for August 2006 for the Bolivian Salt Flats. We present a detailed description of the retrieval algorithm for the OMI operational bromine monoxide (BrO) product. The algorithm is based on direct fitting of radiances from 319.0-347.5 nm, within the UV-2 channel of OMI. Radiances are modeled from the solar irradiance, attenuated by contributions from the target gas and interfering gases, rotational Raman scattering, additive and multiplicative closure polynomials and a common mode spectrum. The common mode spectra (one per cross-track position, computed on-line) are the average of several hundred fitting residuals. They include any instrument effects that are unrelated to molecular scattering and absorption cross sections. The BrO retrieval uses albedo- and wavelength-dependent air mass factors (AMFs), which have been pre-computed using climatological BrO profiles. The wavelength-dependent AMF is applied pre-fit to the BrO cross-sections so that vertical column densities are retrieved directly. We validate OMI BrO with ground-based measurements from three stations (Harestua, Lauder, and Barrow) and with chemical transport model simulations. We analyze the global distribution and seasonal variation of BrO and investigate BrO emissions from volcanoes and salt lakes.

  10. 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.

  11. Aromatics oxidation and soot formation in flames

    SciTech Connect

    Howard, J.B.; Pope, C.J.; Shandross, R.A.; Yadav, T.

    1993-04-01

    This project is concerned with the kinetics and mechanisms of aromatics oxidation and soot and fullerenes formation in flames. The scope includes detailed measurements of profiles of stable and radical species concentrations in low-pressure one-dimensional premixed flames. Intermediate species identifications and mole fractions, fluxes, and net reaction rates calculated from the measured profiles are used to test postulated reaction mechanisms. Particular objectives are to identify, and to confirm or determine rate constants for, the main benzene oxidation reactions in flames, and to characterize soot and fullerenes and their formation mechanisms and kinetics. Stable and radical species profiles in the aromatics oxidation study are measured using molecular beam sampling with on-line mass spectrometry. The rate of soot formation measured by conventional optical techniques is found to support the hypotheses that particle inception occurs through reactive coagulation of high molecular weight PAH in competition with destruction by OHattack, and that the subsequent growth of the soot mass occurs through addition reactions of PAH and C[sub 2]H[sub 2] with the soot particles. During the first year of this reporting period, fullerenes C[sub 60] and C[sub 70] in substantial quantities were found in the flames being studied. The fullerenes were recovered, purified and spectroscopically identified. The yields of C[sub 60] and C[sub 70] were then determined over ranges of conditions in low-pressure premixed flames of benzene and oxygen.

  12. A model for bluff body flame stabilization

    SciTech Connect

    DeChamplain, J.A.; Bardon, M.F.

    1986-01-01

    Previous work on bluff body stabilization mechanisms is reviewed, and existing models are categorized in tabular form, showing the underlying assumptions and resulting equations. Lacunae in existing models are discussed, particularly their reliance on characteristics such as laminar flame speed which is difficult to predict for the conditions encountered in turbojet afterburners. A model for bluff body flame stabilization is proposed based on the stirred reactor approach. In addition to the effect of temperature, pressure and geometry, it includes chemical effects such as vitiation and fuel-air equivalence ratio. Blow off velocities predicted by the model are compared to experimental data for various conditions.

  13. New infrared spectroscopic database for bromine nitrate

    NASA Astrophysics Data System (ADS)

    Wagner, Georg; Birk, Manfred

    2016-08-01

    Fourier transform infrared measurements of bromine nitrate have been performed in the spectral region 675-1400 cm-1 at 0.014 cm-1 spectral resolution. Absorption cross sections were derived from 38 spectra covering the temperature range from 203 to 296 K and air pressure range from 0 to 190 mbar. For line-by-line analysis, further spectra were recorded at 0.00094 cm-1 spectral resolution at 223 and 293 K. The sample was synthesized from ClONO2 and Br2. Band strengths of the bands ν3 around 803 cm-1 and ν2 around 1286 cm-1 were determined from three pure BrONO2 measurements at different temperatures and pressures. Number densities in the absorption cell were derived from pressure measurements of the purified sample taking into account small amounts of impurities determined spectroscopically. Resulting band strengths are Sν3 = 2.872(52) × 10-17 cm2 molec-1 cm-1 and Sν2 = 3.63(15) × 10-17 cm2 molec-1 cm-1. Absorption cross sections of all measurements were scaled to these band strengths. Further data reduction was achieved with an interpolation scheme based on two-dimensional polynomials in ln(pressure) and temperature. The database is well-suited for remote-sensing application and should reduce the atmospheric bromine nitrate error budget substantially.

  14. A theoretical and experimental study of preferential-diffusion/stretch interactions of laminar premixed flames

    NASA Astrophysics Data System (ADS)

    Kwon, Oh Chae

    Recent work shows that preferential-diffusion/stretch interactions of laminar premixed flames are sufficiently robust to affect the stability of practical strongly-turbulent flames. In addition, past measurements of laminar burning velocities should be re-assessed because there generally was no attempt to control flame stretch. Finally, the sensitivity of laminar premixed flames to stretch (represented by the Markstein number) should be studied to better understand and model the properties of laminar premixed flames. Motivated by these considerations, an experimental and computational study of preferential-diffusion/stretch interactions for laminar premixed flames, for both alkane/alcohol-fuel-vapor-fueled flames (as practical fuels) and hydrogen-fueled flames (considering diluent-variation effects) was carried out during the present investigation. Considering outwardly-propagating spherical laminar premixed flames, laminar burning velocities of fuel-vapor/oxygen/nitrogen flames and hydrogen/oxygen/diluent (nitrogen, argon or helium) flames were measured for various values of stretch, fuel-equivalence ratios (0.6--4.5) and pressures (0.3--3 atm). The measurements were reduced to find fundamental unstretched laminar burning velocities and Markstein numbers. The measurements were also used to evaluate corresponding numerical simulations of the experimentally-observed flames, based on contemporary detailed H2/O2 reaction mechanisms. Both measured and predicted ratios of unstretched to stretched laminar burning velocities varied linearly with flame stretch (represented by the Karlovitz number), yielding a constant Markstein number for a particular reactant mixture. The present flames were very sensitive to flame stretch (i.e., they had large Markstein numbers with significant ratios of unstretched to stretched laminar burning velocities) for levels of flame stretch well below quenching conditions. Increasing flame temperatures tended to reduce flame sensitivity to

  15. Potential role of fire retardant-treated polyurethane foam as a source of brominated diphenyl ethers to the US environment.

    PubMed

    Hale, Robert C; La Guardia, Mark J; Harvey, Ellen; Mainor, T Matt

    2002-02-01

    Five tetra- to hexabrominated diphenyl ether (BDE) congeners (BDE-47, -99, -100, -153 and -154) are the most frequently reported in wildlife and humans. The commercial penta-BDE product, used predominantly to flame-retard polyurethane foam, consists primarily of these same congeners. In 1999, North American demand accounted for 98% of the total global penta-market of 8500 metric tons. Frogs, housed with flame retardant-treated polyurethane foam as a dry substrate, accumulated 10,100 microg/kg (wet weight) of the above BDEs. Crickets kept therein as food contained 14,400 microg/kg. The crickets are believed to have browsed directly on the foam and, in turn, were consumed by the frogs. BDE congener composition in all three matrices matched that of the penta-commercial product. Similar congeners were also observed in soil and stream sediments collected near a polyurethane foam manufacturing plant. Summed concentrations of BDE-47, -99 and -100, the dominant congeners observed in these samples, ranged from < 1 to 132 microg/kg (dry weight basis). Sunfish fillets obtained from a nearby, off-site pond contained a total of 624 microg/kg (lipid basis). Sewage treatment plant (STP) sludge exhibited these same congeners at 1370 microg/kg (dry weight). BDE-209, the fully brominated congener predominant in the commercial deca-BDE product, was also present at 1470 microg/kg. While no known polyurethane foam manufacturers discharged to this plant, the distribution pattern of the low brominated congeners in the sludge matched that of the penta-product. After four weeks of exposure to ambient outdoor conditions, the surface of flame-retarded polyurethane foam became brittle and began to disintegrate. Subsequent dispersal of these penta-containing foam fragments may be one mechanism by which these BDEs reach the environment.

  16. Aerodynamic and Kinetic Processes in Flames.

    DTIC Science & Technology

    1987-05-01

    effects of inert addition on soot formation In a counterflow diffusion flame," by R. L. Axelbaum, W. L. Flower , and C. K. Law, 1987 Western States SectIon...collaboration with Dr. W. L. Flower of Sandia, we have isolated the effect of fuel dilution by diluting the fuel stream with nitrogen while holding the maimum

  17. Bigger and Brighter Flame Tests.

    ERIC Educational Resources Information Center

    Dalby, David K.; Mosher, Melvyn M.

    1996-01-01

    Describes a method for flame test demonstrations that provides a way to set up quickly, clean up, and produce a large and very intense flame that can be seen easily in a 300-seat lecture auditorium. (JRH)

  18. Rubens Flame-Tube Demonstration.

    ERIC Educational Resources Information Center

    Ficken, George W.; Stephenson, Francis C.

    1979-01-01

    Investigates and explains the phenomenon associated with Rubens flame-tube demonstration, specifically the persistance of flames at regular intervals along the tube for few minutes after the gas is turned off. (GA)

  19. A Dramatic Flame Test Demonstration.

    ERIC Educational Resources Information Center

    Johnson, Kristin A.; Schreiner, Rodney

    2001-01-01

    Flame tests are used for demonstration of atomic structure. Describes a demonstration that uses spray bottles filled with methanol and a variety of salts to produce a brilliantly colored flame. (Contains 11 references.) (ASK)

  20. 40 CFR 415.290 - Applicability; description of the bromine production subcategory.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... bromine production subcategory. 415.290 Section 415.290 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Bromine Production Subcategory § 415.290 Applicability; description of the bromine production... bromine by the brine-mining process and by the Trona process....

  1. 40 CFR 415.290 - Applicability; description of the bromine production subcategory.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... bromine production subcategory. 415.290 Section 415.290 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Bromine Production Subcategory § 415.290 Applicability; description of the bromine production... bromine by the brine-mining process and by the Trona process....

  2. 40 CFR 415.290 - Applicability; description of the bromine production subcategory.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... bromine production subcategory. 415.290 Section 415.290 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Bromine Production Subcategory § 415.290 Applicability; description of the bromine production... bromine by the brine-mining process and by the Trona process....

  3. 40 CFR 415.290 - Applicability; description of the bromine production subcategory.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... bromine production subcategory. 415.290 Section 415.290 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Bromine Production Subcategory § 415.290 Applicability; description of the bromine production... bromine by the brine-mining process and by the Trona process....

  4. 40 CFR 415.290 - Applicability; description of the bromine production subcategory.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... bromine production subcategory. 415.290 Section 415.290 Protection of Environment ENVIRONMENTAL PROTECTION... CATEGORY Bromine Production Subcategory § 415.290 Applicability; description of the bromine production... bromine by the brine-mining process and by the Trona process....

  5. Investigations of two-phase flame propagation under microgravity conditions

    NASA Astrophysics Data System (ADS)

    Gokalp, Iskender

    2016-07-01

    Investigations of two-phase flame propagation under microgravity conditions R. Thimothée, C. Chauveau, F. Halter, I Gökalp Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), CNRS, 1C Avenue de la Recherche Scientifique, 45071 Orléans Cedex 2, France This paper presents and discusses recent results on two-phase flame propagation experiments we carried out with mono-sized ethanol droplet aerosols under microgravity conditions. Fundamental studies on the flame propagation in fuel droplet clouds or sprays are essential for a better understanding of the combustion processes in many practical applications including internal combustion engines for cars, modern aircraft and liquid rocket engines. Compared to homogeneous gas phase combustion, the presence of a liquid phase considerably complicates the physico-chemical processes that make up combustion phenomena by coupling liquid atomization, droplet vaporization, mixing and heterogeneous combustion processes giving rise to various combustion regimes where ignition problems and flame instabilities become crucial to understand and control. Almost all applications of spray combustion occur under high pressure conditions. When a high pressure two-phase flame propagation is investigated under normal gravity conditions, sedimentation effects and strong buoyancy flows complicate the picture by inducing additional phenomena and obscuring the proper effect of the presence of the liquid droplets on flame propagation compared to gas phase flame propagation. Conducting such experiments under reduced gravity conditions is therefore helpful for the fundamental understanding of two-phase combustion. We are considering spherically propagating two-phase flames where the fuel aerosol is generated from a gaseous air-fuel mixture using the condensation technique of expansion cooling, based on the Wilson cloud chamber principle. This technique is widely recognized to create well-defined mono-size droplets

  6. Use of Bromine and Bromo-Organic Compounds in Organic Synthesis.

    PubMed

    Saikia, Indranirekha; Borah, Arun Jyoti; Phukan, Prodeep

    2016-06-22

    Bromination is one of the most important transformations in organic synthesis and can be carried out using bromine and many other bromo compounds. Use of molecular bromine in organic synthesis is well-known. However, due to the hazardous nature of bromine, enormous growth has been witnessed in the past several decades for the development of solid bromine carriers. This review outlines the use of bromine and different bromo-organic compounds in organic synthesis. The applications of bromine, a total of 107 bromo-organic compounds, 11 other brominating agents, and a few natural bromine sources were incorporated. The scope of these reagents for various organic transformations such as bromination, cohalogenation, oxidation, cyclization, ring-opening reactions, substitution, rearrangement, hydrolysis, catalysis, etc. has been described briefly to highlight important aspects of the bromo-organic compounds in organic synthesis.

  7. Launch Pad Flame Trench Refractory Materials

    NASA Technical Reports Server (NTRS)

    Calle, Luz M.; Hintze, Paul E.; Parlier, Christopher R.; Bucherl, Cori; Sampson, Jeffrey W.; Curran, Jerome P.; Kolody, Mark; Perusich, Steve; Whitten, Mary

    2010-01-01

    The launch complexes at NASA's John F. Kennedy Space Center (KSC) are critical support facilities for the successful launch of space-based vehicles. These facilities include a flame trench that bisects the pad at ground level. This trench includes a flame deflector system that consists of an inverted, V-shaped steel structure covered with a high temperature concrete material five inches thick that extends across the center of the flame trench. One side of the "V11 receives and deflects the flames from the orbiter main engines; the opposite side deflects the flames from the solid rocket boosters. There are also two movable deflectors at the top of the trench to provide additional protection to shuttle hardware from the solid rocket booster flames. These facilities are over 40 years old and are experiencing constant deterioration from launch heat/blast effects and environmental exposure. The refractory material currently used in launch pad flame deflectors has become susceptible to failure, resulting in large sections of the material breaking away from the steel base structure and creating high-speed projectiles during launch. These projectiles jeopardize the safety of the launch complex, crew, and vehicle. Post launch inspections have revealed that the number and frequency of repairs, as well as the area and size of the damage, is increasing with the number of launches. The Space Shuttle Program has accepted the extensive ground processing costs for post launch repair of damaged areas and investigations of future launch related failures for the remainder of the program. There currently are no long term solutions available for Constellation Program ground operations to address the poor performance and subsequent failures of the refractory materials. Over the last three years, significant liberation of refractory material in the flame trench and fire bricks along the adjacent trench walls following Space Shuttle launches have resulted in extensive investigations of

  8. Field Effects of Buoyancy on Lean Premixed Turbulent Flames

    NASA Technical Reports Server (NTRS)

    Cheng, R. K.; Dimalanta, R.; Wernet, M. P.; Greenberg, P. S.

    2001-01-01

    Buoyancy affects the entire flowfield of steady turbulent flames and this aspect of flame buoyancy coupling is largely unexplored by experiments or by theory. Open flames and flames within large confinements are free to expand and interact with the surrounding environment. In addition to fluid and combustion conditions, their aerodynamic flowfields are determined by the flame brush orientation and geometry, wake of the stabilizer, enclosure size, and of course, the gravitational field. Because the flowfield consists mainly of cold reactants (mostly in the nearfield) and hot products (mostly in the farfield), buoyancy effects are manifested in the farfield region. In upward pointing flames, an obvious effect is a favorable axial pressure gradient that accelerates the products thereby increasing the axial aerodynamic stretch rate. Intrinsic to turbulent flows, changes in mean aerodynamic stretch also couple to the fluctuating pressure field. Consequently, buoyancy can influence the turbulence intensities upstream and downstream of the flame. Flame wrinkling process, and heat release rate are also directly affected. This backward coupling mechanism is the so-called elliptic problem. To resolve the field effects of buoyancy would require the solution of three-dimensional non-linear Navier Stokes equations with full specification of the upstream, wall and downstream boundary conditions.

  9. Flame extinction limit and particulates formation in fuel blends

    NASA Astrophysics Data System (ADS)

    Subramanya, Mahesh

    Many fuels used in material processing and power generation applications are generally a blend of various hydrocarbons. Although the combustion and aerosol formation dynamics of individual fuels is well understood, the flame dynamics of fuel blends are yet to be characterized. This research uses a twin flame counterflow burner to measure flame velocity, flame extinction, particulate formation and particulate morphology of hydrogen fuel blend flames at different H2 concentration, oscillation frequencies and stretch conditions. Phase resolved spectroscopic measurements (emission spectra) of OH, H, O and CH radical/atom concentrations is used to characterize the heat release processes of the flame. In addition flame generated particulates are collected using thermophoretic sample technique and are qualitative analyzed using Raman Spectroscopy and SEM. Such measurements are essential for the development of advanced computational tools capable of predicting fuel blend flame characteristics at realistic combustor conditions. The data generated through the measurements of this research are representative, and yet accurate, with unique well defined boundary conditions which can be reproduced in numerical computations for kinetic code validations.

  10. Flow/Soot-Formation Interactions in Nonbuoyant Laminar Diffusion Flames

    NASA Technical Reports Server (NTRS)

    Dai, Z.; Faeth, G. M.

    1999-01-01

    Nonpremixed (diffusion) flames are attractive for practical applications because they avoid the stability, autoignition, flashback, etc. problems of premixed flames. Unfortunately, soot formation in practical hydrocarbon-fueled diffusion flames reduces their attractiveness due to widely-recognized public health and combustor durability problems of soot emissions. For example, more deaths are attributed to the emission of soot (15,000-60,000 deaths annually in the U.S. alone) than any other combustion-generated pollutant. In addition, continuum radiation from soot-containing flames is the principle heat load to combustor components and is mainly responsible for engine durability problems of aircraft and gas turbine engines. As a result, there is considerable interest in controlling both soot concentrations within flames and soot emissions from flames. Thus, the objective of the present investigation is to study ways to control soot formation in diffusion flames by manipulating the mixing process between the fuel and oxidant streams. In order to prevent the intrusion of gravity from masking flow properties that reduce soot formation in practical flames (where effects of gravity are small), methods developed during past work will be exploited to minimize effects of buoyant motion.

  11. 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/