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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. 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...

  6. Brominated Flame Retardants and Perfluorinated Chemicals

    EPA Science Inventory

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

  7. Biodegradation of brominated and organophosphorus flame retardants.

    PubMed

    Waaijers, Susanne L; Parsons, John R

    2016-04-01

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

  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. 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...

  10. 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...

  11. HEALTH ASPECTS OF BROMINATED FLAME RETARDANTS (BFRS)

    EPA Science Inventory

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

  12. Brominated flame retardants 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...

  13. Neurotoxicity of brominated flame retardants

    EPA Science Inventory

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

  14. 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

  15. 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.

  16. Occurrence of additive brominated flame retardants in aquatic organisms from Tai Lake and Yangtze River in Eastern China, 2009-2012.

    PubMed

    Su, Guanyong; Saunders, David; Yu, Yijun; Yu, Hongxia; Zhang, Xiaowei; Liu, Hongling; Giesy, John P

    2014-11-01

    Since the phase-out of PBDEs, reports regarding occurrences of these compounds in the environment have become less frequent. To characterize potential influences of the phase-out of PBDEs' on concentrations in the environment, trends in concentrations as a function of time were investigated for two additive brominated flame retardants, PBDEs and HBCDs. Three aquatic species, including shrimp, common carp, and yellow catfish, were collected from Meiliang Bay of Tai Lake, 2009-2012. The analysis of PBDEs in three aquatic organisms has shown a downward-trend in the first three years but a significant upward-trend in the final year. Concentrations of HBCDs have not shown temporal increases in the investigated environments. Concentrations of both PBDEs and HBCDs in the three studied organisms increased as a function of trophic level, which suggested that these additive flame retardants can be biomagnified through the food web of Tai Lake. In accordance with previous publications, PBDE-47 contributed the greatest proportion of ∑PBDEs and had a detection frequency of 100%. α-HBCD was the predominate isomer that contributed to ∑HBCDs. Both β-HBCD and γ-HBCD were likely detected at lesser concentrations than the α-isomer due to differences in bioavailability. Concentrations of ∑PBDEs in the three aquatic organisms from Tai Lake ranged from 1.13 to 97.59 ng g(-1) lipid. These concentrations were generally less than those in biota from other countries, but equal to those found at other locations in China. Specimens from the Yangtze River had greater concentrations of ∑HBCDs (169.6-316.5 ng g(-1) lipid) than those collected at Tai Lake, which were comparatively greater than many reported concentrations in freshwater organisms from other countries.

  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. PMID:24745557

  18. 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.

  19. 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.

  20. Environmental release and behavior of brominated flame retardants.

    PubMed

    Watanabe, Isao; Sakai, Shin-ichi

    2003-09-01

    Recently, environmental problems relating to brominated flame retardants (BFRs) have become a matter of greater concern than ever before, because of the recent marked increase in levels of polybrominated diphenyl ethers (PBDEs) found in human milk in Sweden and North America. The question that arises is whether environmental levels of PBDEs and other BFRs will continue to increase, causing toxic effects to humans. In an attempt to elucidate the current state of the science of BFRs, we review the consumer demand for BFRs (mainly in Japan), the characteristics of waste flame-retarded products, sources of emission, environmental behavior, routes of exposure of humans, temporal trends, and thermal-breakdown products of BFRs. At present, flame-retarded consumer products manufactured 10-20 years ago, when PBDEs were frequently used, are being dumped. The possible major sources of emission of BFRs into the environment are effluent and flue gases from BFR factories and other facilities processing BFRs. With respect to the environmental behavior of BFRs, the lower brominated compounds are, on the whole, predicted to be more volatile, more water soluble, and more bioaccumulative than the higher brominated compounds. The most probable route for exposure of the general human population to PBDEs, especially the lower brominated congeners, is through the diet. The release of BFRs from consumer products treated with these compounds could also lead to human exposure. Temporal trends in PBDE levels in the environment and in humans worldwide seem to vary considerably, depending on the regions or country, with possible reflections of the historic and current use of PBDEs. The environment and the general human population are also exposed to the thermal-breakdown products of PBDEs, such as polybrominated and mixed brominated/chlorinated dibenzo-p-dioxins and dibenzofurans (PBDDs/DFs and mixed PXDDs/DFs).

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

    PubMed

    Yecheskel, Yinon; Dror, Ishai; Berkowitz, Brian

    2013-09-01

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

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

    PubMed

    Ezechiáš, M; Covino, S; Cajthaml, T

    2014-12-01

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

  3. 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.

  4. Brominated flame retardants in Canadian chicken egg yolks

    PubMed Central

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

    2011-01-01

    Chicken eggs categorised as conventional, omega-3 enriched, free range and organic were collected at grading stations in three regions of Canada between 2005 and 2006. Free run eggs, which were only available for collection from two regions, were also sampled during this time frame. Egg yolks from each of these egg types (n = 162) were analysed to determine brominated flame retardant levels, specifically polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD). PBDEs were detected in 100% of the 162 samples tested, while HBCD was observed in 85% of the egg yolks. Total PBDE concentrations in egg yolks ranged from 0.018 to 20.9 ng g−1 lipid (median = 3.03 ng g−1 lipid), with PBDE 209 identified as being the major contributor to ΣPBDE concentrations. In addition to PBDE 209, PBDE 99, 47, 100, 183 and 153 were important contributors to ΣPBDE concentrations. Total HBCD concentrations ranged from below the limit of detection to a maximum concentration of 71.9 ng g−1 lipid (median = 0.053 ng g−1 lipid). The α-isomer was the dominant contributor to ΣHBCD levels in Canadian egg yolks and was the most frequently detected HBCD isomer. ΣPBDE levels exhibited large differences in variability between combinations of region and type. ΣHBCD concentrations were not significantly different among regions, although differences were observed between the different types of egg yolks analysed in the present study. PMID:21623506

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

    PubMed

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

    2016-02-01

    Hexabromocyclododecane (HBCDD) is a brominated flame retardant (BFR) and major additive to polystyrene foam thermal insulation that has recently been listed as a persistent organic pollutant by the Stockholm Convention. During a 2013/2014 field analytical survey, we measured HBCDD content ranging from 0.2 to 2.4% by weight in 98 polystyrene samples. Liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) analyses indicated that expandable (EPS) and extruded (XPS) polystyrene foams significantly differed in the α/γ HBCDD isomer ratio, with a majority of α and γ isomers in XPS and EPS, respectively. Interestingly, this technique indicated that some recent materials did not contain HBCDD, but demonstrated bromine content when analysed with X-ray fluorescence (XRF). Further investigation by Nuclear Magnetic Resonance (NMR) was able to discriminate between the BFRs present. In addition to confirming the absence or presence of HBCDD in polystyrene samples, high-field NMR spectroscopy provided evidence of the use of brominated butadiene styrene (BBS) as copolymer in the production of polystyrene. Use of this alternative flame retardant is expected to cause fewer health and environmental concerns. Our results highlight a trend towards the use of copolymerized BFRs as an alternative to HBCDD in polystyrene foam boards. In addition to providing a rapid NMR method to identify polymeric BFR, our analytical approach is a simple method to discriminate between flame-retardants in polystyrene foam insulating materials. PMID:26492426

  6. 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.

  7. 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).

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

    PubMed

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

    2015-01-01

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

  9. 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.

  10. 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

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

    PubMed

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

    2016-05-01

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

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

    PubMed

    Zhang, Mengmei; Buekens, Alfons; Li, Xiaodong

    2016-03-01

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

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

    PubMed

    Zhang, Mengmei; Buekens, Alfons; Li, Xiaodong

    2016-03-01

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

  14. 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) ...

  15. 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.

  16. 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

  17. 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.

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

    PubMed

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

    2015-01-01

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

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

    PubMed

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

    2009-03-01

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

  20. 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.

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

    PubMed

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

    2015-04-01

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

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

    PubMed

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

    2012-10-15

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

  3. Thermal Recycling of Brominated Flame Retardants with Fe2O3.

    PubMed

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

    2016-08-01

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

  4. Thermal Recycling of Brominated Flame Retardants with Fe2O3.

    PubMed

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

    2016-08-01

    Plastics containing brominated flame retardants (BFRs) constitute the major fraction of nonmetallic content in e-waste. Co-pyrolysis of BFRs with hematite (Fe2O3) represents a viable option for the thermal recycling of BFRs. Consensus of experimental findings confirms the excellent bromine fixation ability of Fe2O3 and the subsequent formation of iron bromides. This contribution provides a comprehensive mechanistic account of the primary reactions between a cluster model of Fe2O3 and major bromine-bearing products from the decomposition of tetrabromobisphenol A (TBBA), the most commonly deployed BFR. We estimate the thermo-kinetic parameters for interactions of Fe2O3 with HBr, brominated alkanes and alkenes, bromobenzene, and bromophenol. Dissociative addition of HBr at a Fe-O bond proceeds through a trivial barrier of 8.2 kcal/mol with fitted parameters in the Arrhenius equation of k(T) = 7.96 × 10(11) exp(-6400/RT) s(-1). The facile and irreversible nature for HBr addition to Fe2O3 accords with the experimentally reported 90% reduction in HBr emission when Fe2O3 interacts with TBBA pyrolysates. A detailed kinetic analysis indicates that, transformation of Fe2O3 into iron bromides and oxybromides occurs via successive addition of HBr to Fe(Br)-O(H) entities. Elimination of a water molecule proceeds through an intramolecular H transfer. A direct elimination one-step mechanism operates in the dehydrohalogenation of bromoethane into ethene over Fe2O3. Dissociative decomposition and direct elimination channels assume comparable reaction rates in formation of acetylene from vinyl bromide. Results from this study provide an atomic-based insight into a promising thermal recycling route of e-waste. PMID:27366936

  5. Distribution of brominated flame retardants in different dust fractions in air from an electronics recycling facility.

    PubMed

    Julander, Anneli; Westberg, Håkan; Engwall, Magnus; van Bavel, Bert

    2005-11-01

    Twelve air samples were collected from an electronic recycling facility in Sweden representing three different dust fractions; respirable, total and inhalable dust. Four samples were collected from each fraction. The highest concentration of polybrominated diphenyl ether (PBDE) #209 (ten bromine atoms) was found in the samples from the inhalable dust fraction (ID), which was 10 times higher than for the "total dust" fraction (TD). The concentration ranges were 157.6-208.6; 13.9-16.7; and 2.8-3.3 ng/m3 for inhalable, total and respirable fractions, respectively. The second most abundant PBDE congener was PBDE #183 (seven bromine atoms), followed by the second most abundant substance 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) in all samples. In addition, decabromodiphenyl ethane (DeBDethane) was tentatively identified in five of the samples. Because of the large differences in air concentrations between the three fractions in ID, TD and RD, it is suggested that the inhalable instead of "total dust" fraction should be used to assess air concentrations, in particular for the larger and higher brominated flame retardants (BFRs).

  6. 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.

  7. 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. PMID:27506419

  8. 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

  9. Versatile and fast gas chromatographic determination of frequently used brominated flame retardants in styrenic polymers.

    PubMed

    Pöhlein, Manfred; Bertran, Raquel Urpi; Wolf, Marion; van Eldik, Rudi

    2008-09-01

    Two versatile and fast methods to identify and quantify brominated flame retardants (BrFRs) in styrenic polymers were developed. Gas chromatography/mass spectrometry (GC/MS) as well as gas chromatography with electron-capture detection (GC/ECD), both following ultrasonic-supported dissolution and precipitation (USDP), were applied. The substance range includes poly-brominated biphenyls (PBBs) and diphenyl ethers (PBDEs), as well as other commonly used flame retardants (FRs), including two phosphate-based flame retardants. The methods were verified using congener standards and flame-retardant polymer samples. Good recoveries were found. Overall run time for the analysis, including sample preparation, is less than 60 min. PMID:18687441

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

    PubMed

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

    2015-01-01

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

  11. Vapor Pressure of Three Brominated Flame Retardants Determined via Knudsen Effusion Method

    PubMed Central

    Fu, Jinxia; Suuberg, Eric M.

    2012-01-01

    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 to 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. PMID:22213441

  12. Analysis of brominated flame retardants in house dust.

    PubMed

    Abb, Magdalena; Stahl, Beate; Lorenz, Wilhelm

    2011-12-01

    The main objective of this study was to create a robust analytical method to analyse the flame retardants decabromodiphenylether (BDE-209), hexabromocyclododecane (HBCD), and tetrabromobisphenol-A (TBBPA) in house dust in order to estimate the degree of contamination of indoor environment. A liquid chromatography method equipped with a UV-detector and electro spray-tandem mass spectrometry was used to achieve this result. Applying an external calibration for BDE-209, an internal calibration for TBBPA, and a standard addition method for HBCD low limits of quantification were obtained. The analytical procedure was carried out under exclusion of UV-light as the target compounds potentially degrade when being exposed to UV-light. Empirical data were obtained in addition to the dust samples to estimate potential influences of apartment characteristics. A weak correlation between the number of electric devices and TBBPA was found. PMID:21724229

  13. 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...

  14. Polybrominated diphenyl ethers vs alternate brominated flame retardants and Dechloranes from East Asia to the Arctic.

    PubMed

    Möller, Axel; Xie, Zhiyong; Cai, Minghong; Zhong, Guangcai; Huang, Peng; Cai, Minggang; Sturm, Renate; He, Jianfeng; Ebinghaus, Ralf

    2011-08-15

    Marine boundary layer air and seawater samples taken during a polar expedition cruise from East China Sea to the Arctic were analyzed in order to compare the occurrence, distribution, and fate of the banned polybrominated diphenyl ethers (PBDEs) with their brominated alternatives as well as the chlorinated Dechloranes. The sum of PBDEs (∑(10)PBDEs) in the atmosphere ranged from 0.07 to 8.1 pg m(-3) with BDE-209 being the dominating congener and from not detected (n.d.) to 0.6 pg L(-1) in seawater. Alternate brominated flame retardants (BFRs), especially hexabromobenzene (HBB), (2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), pentabromotoluene (PBT), 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EHTBB), bis-(2-ethylhexyl)-tetrabromophthalate (TBPH), were detected in higher concentrations than PBDEs, even in the high Arctic (0.6 to 15.4 pg m(-3) for sum of alternate BFRs), indicating the change of PBDEs toward alternate BFRs in the environmental predominance. In addition, Dechlorane Plus (DP) as well as Dechlorane 602, 603, and 604 were detected both in the atmosphere and in seawater. The highest concentrations as well as the highest compound variability were observed in East Asian samples suggesting the Asian continent as source of these compounds in the marine environment. The air-seawater exchange indicates strong deposition, especially of alternate BFRs, as well as dry particle-bound deposition of BDE-209 into the ocean. PMID:21751774

  15. 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

  16. Brominated and chlorinated dioxins, PCBs and brominated flame retardants in Scottish shellfish: methodology, occurrence and human dietary exposure.

    PubMed

    Fernandes, Alwyn; Dicks, Pamela; Mortimer, David; Gem, Martin; Smith, Frankie; Driffield, Malcolm; White, Shaun; Rose, Martin

    2008-02-01

    The most commonly consumed shellfish species produced in Scotland - mussels, oysters and scallops - were investigated for the occurrence of a range of brominated and chlorinated contaminants in order to establish current levels and estimate human dietary exposure. Flesh from individual sub-samples was representatively pooled and 35 composites were analysed for brominated and chlorinated dioxins (PBDD/Fs, PCDD/Fs), brominated and chlorinated biphenyls (PBBs, PCBs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs) and tetrabromobisphenol A (TBBPA). The analytical methodology used (13)C(12) labelled surrogates of the target compounds, with GC coupled to (usually) high resolution MS, and LC-MS/MS for HBCD and TBBPA analysis. Positive identifications were made in the majority of samples for most analytes with the exception of TBBPA and most PBDD congeners measured. None of the levels detected for PCDD/F and PCB were above the maximum permitted levels specified in European Union regulations. The levels of brominated furans predominated over brominated dioxins, reflecting the environmental distribution and source emission profiles of these contaminants, and relatively high levels of the tri-brominated congeners were observed. Levels of the flame retardant chemicals reflected current and legacy use, with appreciable concentrations of PBDEs and HBCDs (predominantly alpha-HBCD) but far lower levels of PBBs. TBBPA was not detected in any of the species. In general, mussels and oysters displayed relatively higher levels of contamination than scallops, although the gonad tissue of the latter showed significant levels of brominated dioxins. The estimated adult dietary intakes of PCDD/Fs and PCBs arising from the consumption of a typical portion of these foods in combination with an otherwise average UK diet were in the range 0.5-0.6 pg World Health Organisation (WHO)-toxic equivalent (TEQ)(2005)/kg bodyweight per day. These estimated dietary intakes are

  17. Playing with fire: the global threat presented by brominated flame retardants justifies urgent substitution.

    PubMed

    Santillo, David; Johnston, Paul

    2003-09-01

    Few would now deny that the use of organobromine compounds to achieve fire retardancy in a diverse array of products and materials has led to contamination of the ecosphere on a widespread scale. This environmental prevalence and persistence of the brominated flame retardants, coupled with growing evidence of their potential for harm, present all too familiar parallels with the previous generation of persistent organic pollutants. Indeed, given the intrinsic properties of these brominated chemicals, the nature and extent of the current problem could well have been predicted in advance. The question is then whether we are prepared to let history repeat itself once more or to take precautionary action now to switch to more sustainable alternatives. The choice facing society is not between brominated flame retardants and unsafe products, but between fire safety leading to global contamination or fire safety achieved in less polluting ways. If we look beyond options for simple chemical-for-chemical substitution to alternative materials and designs, many of the solutions are already available. The remainder could undoubtedly be developed given the incentives to do so. However, a strong and clear policy approach, backed by legislative phase-outs within specified (and challenging) timeframes, will be necessary to break our current dependency on organobromine chemistry. This paper presents the justification for such an approach, reviews those initiatives already underway to replace brominated flame retardants and identifies pathways to the use of more sustainable products in the service of society.

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

    PubMed

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

    2015-09-01

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

  20. 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.

  1. 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.

  2. 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.

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

    SciTech Connect

    Morita, Y.; Hagiwara, M.

    1982-09-01

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

  4. 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.

  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. 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.

  7. 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

  8. 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.

  9. Effects of Novel Brominated Flame Retardants on Steroidogenesis in Primary Porcine Testicular Cells.

    PubMed

    Mankidy, Rishikesh; Ranjan, Bibhuti; Honaramooz, Ali; Giesy, John P

    2013-10-24

    Brominated flame retardants are chemicals with fire quenching properties which are extensively used in manufacturing. Historically, less regulated use of legacy brominated flame retardants (BFRs) for a number of years has resulted in ubiquitous contamination of the environment. As a result, some of the more persistent BFRs have been phased out and are being replaced by a next generation of brominated compounds for which there is little toxicological data. The study investigated effects of 2-ethylhexyl tetrabromobenzoate (TBB), 1,2,5,6-tetrabromocyclooctane (TBCO), and bis-(2-ethylhexyl) tetrabromophthalate (TBPH) on steroidogenesis in a porcine primary testicular cell model. TBB did not affect sex-steroid production in this cell model; rather the data suggest a flux towards synthesis of aldosterone and cortisol via up-regulation of CYP21A2. At the greatest concentrations of TBCO and TBPH tested greater production of sex hormones testosterone (T) and estradiol (E2) was observed. Effects were mediated by regulation of multiple molecular targets in the steroidogenesis pathway; CYP11A in the case of TBPH and CYP17A1 in the case of TBCO. This investigation is the first of its kind to use a testicular mixed population cell model to investigate mechanism(s) of action of three chemically diverse compounds currently used in commercial fire retardants.

  10. Effects of novel brominated flame retardants on steroidogenesis in primary porcine testicular cells.

    PubMed

    Mankidy, Rishikesh; Ranjan, Bibhuti; Honaramooz, Ali; Giesy, John P

    2014-01-01

    Brominated flame retardants are chemicals with fire quenching properties which are extensively used in manufacturing. Historically, less regulated use of legacy brominated flame retardants (BFRs) for a number of years has resulted in ubiquitous contamination of the environment. As a result, some of the more persistent BFRs have been phased out and are being replaced by a next generation of brominated compounds for which there is little toxicological data. The study investigated effects of 2-ethylhexyl tetrabromobenzoate (TBB), 1,2,5,6-tetrabromocyclooctane (TBCO), and bis-(2-ethylhexyl) tetrabromophthalate (TBPH)on steroidogenesis in a porcine primary testicular cell model. TBB did not affect sex-steroid production in this cell model; rather the data suggest a flux towards synthesis of aldosterone and cortisol via up-regulation of CYP21A2. At the greatest concentrations of TBCO and TBPH tested greater production of sex hormones testosterone (T) and estradiol (E2) was observed. Effects were mediated by regulation of multiple molecular targets in the steroidogenesis pathway; CYP11A in the case of TBPH and CYP17A1 in the case of TBCO. This investigation is the first of its kind to use a testicular mixed population cell model to investigate mechanism(s) of action of three chemically diverse compounds currently used in commercial fire retardants.

  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. PMID:27183339

  12. 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.

  13. Degradation of brominated flame retardant in computer housing plastic by supercritical fluids.

    PubMed

    Wang, Yanmin; Zhang, Fu-Shen

    2012-02-29

    The degradation process of brominated flame retardant (BFR) and BFR-containing waste computer housing plastic in various supercritical fluids (water, methanol, isopropanol and acetone) was investigated. The results showed that the debromination and degradation efficiencies, final products were greatly affected by the solvent type. Among the four tested solvents, isopropanol was the most suitable solvent for the recovery of oil from BFR-containing plastic for its (1) excellent debromination effectiveness (debromination efficiency 95.7%), (2) high oil production (60.0%) and (3) mild temperature and pressure requirements. However, in this case, the removed bromine mostly existed in the oil. Introduction of KOH into the sc-isopropanol could capture almost all the inorganic bromine from the oil thus bromine-free oil could be obtained. Furthermore, KOH could enhance the depolymerization of the plastic. The obtained oil mainly consisted of single- and duplicate-ringed aromatic compounds in a carbon range of C9-C17, which had alkyl substituents or aliphatic bridges, such as butyl-benzene, (3-methylbutyl)-benzene, 1,1'-(1,3-propanediyl)bis benzene. Phenol, alkyl phenols and esters were the major oxygen-containing compounds in the oil. This study provides an efficient approach for debromination and simultaneous recovering valuable chemicals from BFR-containing plastic in e-waste.

  14. 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

  15. 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.

  16. Calorimetric evidence of interaction of brominated flame retardants with membrane model.

    PubMed

    Librando, Vito; Accolla, Maria Lorena; Minniti, Zelica; Pappalardo, Matteo; Castelli, Francesco; Cascio, Orazio; Sarpietro, Maria Grazia

    2015-05-01

    The presence of polybrominated flame retardants in the environment seems to be increasing in the past decade. Considering the toxic effects of these pollutants, it is important evaluating the potential interaction with biological membranes for a risk assessment. In this study low and high brominated biphenyls and biphenyl ethers were used to investigate their interaction with biological membrane models constituted by liposomes, using differential scanning calorimetry (DSC) technique. The medium influence on membrane absorption was also assessed. The findings indicate that membrane interaction is controlled by compound structural characteristics. The membrane absorption is allowed by lipophilic medium; instead hydrophilic medium prevents membrane permeation.

  17. 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.

  18. Emissions of organophosphate and brominated flame retardants from selected consumer products and building materials

    NASA Astrophysics Data System (ADS)

    Kemmlein, Sabine; Hahn, Oliver; Jann, Oliver

    The emissions of selected flame retardants were measured in 1- and 0.02-m 3 emission test chambers and 0.001-m 3 emission test cells. Four product groups were of interest: insulating materials, assembly foam, upholstery/mattresses, and electronics equipment. The experiments were performed under constant environmental conditions (23°C, 50% RH) using a fixed sample surface area and controlled air flow rates. Tris (2-chloro-isopropyl)phosphate (TCPP) was observed to be one of the most commonly emitted organophosphate flame retardants in polyurethane foam applications. Depending on the sample type, area-specific emission rates (SER a) of TCPP varied between 20 ng m -2 h -1 and 140 μg m -2 h -1. The emissions from electronic devices were measured at 60°C to simulate operating conditions. Under these conditions, unit specific emission rates (SER u) of organophosphates were determined to be 10-85 ng unit -1 h -1. Increasing the temperature increased the emission of several flame retardants by up to a factor of 500. The results presented in this paper indicate that emissions of several brominated and organophosphate flame retardants are measurable. Polybrominated diphenylethers exhibited an SER a of between 0.2 and 6.6 ng m -2 h -1 and an SER u of between 0.6 and 14.2 ng unit -1 h -1. Because of sink effects, i.e., sorption to chamber components, the emission test chambers and cells used in this study have limited utility for substances low vapour pressures, especially the highly brominated compounds; hexabromocyclododecane had an SER a of between 0.1 and 29 ng m -2 h -1 and decabromodiphenylether was not detectable at all.

  19. 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.

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

    PubMed

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

    2016-09-15

    Sample pretreatment is the critical section for residue monitoring of hazardous pollutants. In this paper, using the cellulose fabric as host matrix, three extraction sorbents such as poly (tetrahydrofuran) (PTHF), poly (ethylene glycol) (PEG) and poly (dimethyldiphenylsiloxane) (PDMDPS), were prepared on the surface of the cellulose fabric. Two practical extraction techniques including stir bar fabric phase sorptive extraction (stir bar-FPSE) and magnetic stir fabric phase sorptive extraction (magnetic stir-FPSE) have been designed, which allow stirring of fabric phase sorbent during the whole extraction process. In the meantime, three brominated flame retardants (BFRs) [tetrabromobisphenol A (TBBPA), tetrabromobisphenol A bisallylether (TBBPA-BAE), tetrabromobisphenol A bis(2,3-dibromopropyl)ether (TBBPA-BDBPE)] in the water sample were selected as model analytes for the practical evaluation of the proposed two techniques using high-performance liquid chromatography (HPLC). Moreover, various experimental conditions affecting extraction process such as the type of fabric phase, extraction time, the amount of salt and elution conditions were also investigated. Due to the large sorbent loading capacity and unique stirring performance, both techniques possessed high extraction capability and fast extraction equilibrium. Under the optimized conditions, high recoveries (90-99%) and low limits of detection (LODs) (0.01-0.05 μg L(-1)) were achieved. In addition, the reproducibility was obtained by evaluating the intraday and interday precisions with relative standard deviations (RSDs) less than 5.1% and 6.8%, respectively. The results indicated that two pretreatment techniques were promising and practical for monitoring of hazardous pollutants in the water sample. Due to low solvent consumption and high repeated use performance, proposed techniques also could meet green analytical criteria. PMID:27300591

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

    PubMed

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

    2015-10-15

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

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

    PubMed

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

    2015-10-15

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

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

    PubMed

    Aldrian, Alexia; Ledersteger, Alfred; Pomberger, Roland

    2015-02-01

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

  4. 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.

  5. 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.

  6. 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.

  7. Gender-specific proteomic responses in zebrafish liver following exposure to a selected mixture of brominated flame retardants.

    PubMed

    Kling, P; Norman, A; Andersson, P L; Norrgren, L; Förlin, L

    2008-10-01

    Proteomic effect screening in zebrafish liver was performed to generate hypotheses following exposure (21 days) to a structurally diverse mixture of brominated flame retardants (BFRs). Fish were exposed to two doses (10 and 100 nmol/g feed). Two-dimensional gel-electrophoresis, image analysis and MALDI-TOF mass-spectrometry revealed 13 and 19 significant responses in males and females, respectively. Effects on proteins related to cellular maintenance and stress were observed in both genders. Regulated proteins were gender-specific, but functionally indicated common protective responses (peroxiredoxin 6 and Zgc:92891 in males and transketolase in females) suggesting oxidative stress. Betaine homocysteine methyltransferase (BHMT) was induced in both genders. In addition a female-specific downregulation of ironhomeostatic proteins (iron-regulatory protein 1 and transferrin) were observed. Our proteomic approach revealed novel responses that suggest important gender-specific sensitivity to BFRs that should be considered when interpreting adverse effects of BFRs. PMID:18258299

  8. 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. PMID:24295083

  9. 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.

  10. 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.

  11. Brominated and chlorinated flame retardants in liver of Greenland shark (Somniosus microcephalus).

    PubMed

    Strid, Anna; Bruhn, Christoffer; Sverko, Ed; Svavarsson, Jörundur; Tomy, Gregg; Bergman, Åke

    2013-04-01

    Polybrominated diphenyl ethers (PBDEs) are known brominated flame retardants that have now been banned or phased out in many parts of the world. As a consequence, interest in the environmental occurrence of non-PBDE flame retardants has increased. In the present study several potential PBDE replacement products together with short chained chlorinated paraffins (SCCPs) were assessed in Greenland sharks accidentally caught in waters around Iceland between 2001 and 2003. Non-PBDE flame retardants detected were pentabromoethylbenzene (PBEB), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and 2,3,5,6-tetrabromo-p-xylene (TBX). The concentrations were lower than levels of BDE-47 but similar to other PBDE congeners previously reported in Greenland shark. The median concentrations of SCCPs was 430 ng g(-1) fat, similar to individual PCB congeners previously reported. This is the first report of SCCPs, BTBPE, PBEB and TBX in any shark species globally and confirms the usefulness of the Greenland shark as a screening species for environmental contamination in the Arctic and sub-Arctic environment. PMID:23360749

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

    PubMed

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

    2014-02-15

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

  13. 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.

  14. 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.

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

    PubMed

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

    2016-10-01

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

  16. 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.

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

    PubMed

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

    2016-08-01

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

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

    PubMed

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

    2016-08-01

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

  19. Hair as an indicator of endogenous tissue levels of brominated flame retardants in mammals.

    PubMed

    D'Havé, Helga; Covaci, Adrian; Scheirs, Jan; Schepens, Paul; Verhagen, Ron; De Coen, Wim

    2005-08-15

    Few data are available on brominated flame retardants (BFRs) in terrestrial mammalian wildlife. Moreover, the use of hair in nondestructive monitoring of BFRs in mammals or humans has not been investigated. In the present study, concentrations of polybrominated diphenyl ethers (PBDEs) and brominated biphenyl 153 (BB 153) were analyzed in tissues of the European hedgehog Erinaceus europaeus. Road kills and carcasses from wildlife rescue centers were used to investigate relationships between concentrations of BFRs in hair and internal tissues, BFR tissue distribution (hair, liver, kidney, muscle, and adipose tissue), and PBDE congener tissue pattern dissimilarities. Liver concentrations of PBDEs and BB 153 were in the ranges 1-1178 and 0-2.5 ng/g of liver wet weight, respectively. PBDEs were predominant in adipose tissue and liver, while accumulation of BB 153 was tissue independent. The less persistent compound BDE 99 was more dominant in hair than in internal tissues. We observed positive relationships between BFR levels in hair and internal tissues for sum PBDEs and BDE 47 (0.37 < r < 0.78). The present study demonstrated that hair is a suitable indicator of PBDE exposure in terrestrial mammals which can be used in nondestructive monitoring schemes.

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

    PubMed

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

    2012-01-01

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

  1. Fingerprint analysis of brominated flame retardants and Dechloranes in North Sea sediments.

    PubMed

    Sühring, Roxana; Barber, Jonathan L; Wolschke, Hendrik; Kötke, Danijela; Ebinghaus, Ralf

    2015-07-01

    53 brominated and chlorinated flame retardants were investigated in sediment samples from the German rivers Elbe and Weser, the German Bight, Jadebusen, East Frisian Coast as well as the UK East coast. The aim of the presented study was to investigate the prevalence of different halogenated flame retardant groups as contaminants in North Sea sediments, identify determining factors for the distribution and levels as well as to identify area specific fingerprints that could help identify sources. In order to do that a fast and effective ASE extraction method with an on-line clean-up was developed as well as a GC-EI-MSMS and LC-ESI-MSMS method to analyse PBDEs, MeOBDEs, alternate BFRs, Dechloranes as well as TBBPA and HBCDD. A fingerprinting method was adopted to identify representative area-specific patterns based on detection frequency as well as concentrations of individual compounds. Concentrations in general were low, with<1 ng g(-1) dw for most compounds. Exceptions were the comparably high concentrations of BDE-209 with up to 7 ng g(-1) dw in selected samples and TBBPA in UK samples with 2.7±1.5 ng g(-1) dw. Apart from BDE-209 and TBBPA, alternate BFRs and Dechloranes were predominant in all analysed samples, displaying the increasing relevance of these compounds as environmental contaminants.

  2. 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.

  3. 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.

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

    PubMed

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

    2016-09-01

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

  5. Effects of tetrabromobisphenol A, brominated flame retardant, in ICR mice after prenatal and postnatal exposure.

    PubMed

    Tada, Y; Fujitani, T; Yano, N; Takahashi, H; Yuzawa, K; Ando, H; Kubo, Y; Nagasawa, A; Ogata, A; Kamimura, H

    2006-08-01

    Tetrabromobisphenol A (TBBPA), brominated flame retardant, is produced in the largest amounts globally for use in plastics or building materials. TBBPA has been detected in sediment, air at the dismantling plant or human serum samples. In the present study, we examined the effects of prenatal and postnatal exposure to TBBPA in mice. TBBPA (99.1% pure) in diet was administered to pregnant ICR mice at doses of 0% (control), 0.01%, 0.1% or 1.0% from gestational day 0 to weaning at postnatal day 27. The average daily food intake and body weight of dams showed no significant differences between the control and treated groups. There were no dose-related effects on reproductive data. Serum concentrations of total-cholesterol and liver weights of treated dams and offspring were higher than those of the control mice. Histological findings in treated dams or offspring showed the increase of focal necrosis of hepatocytes and inflammatory cell infiltration in the liver, and increase of dilation or atrophy of renal tubules and cyst in the kidney. TBBPA was developed as a new, safe class of flame retardant and was not highly toxic. However, the present data suggested that TBBPA caused a lipid metabolic disorder and hepatic or kidney lesion, under these conditions. PMID:16716481

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

    PubMed

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

    2013-02-15

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

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

    PubMed Central

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

    2013-01-01

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

  8. Analysis of flame retardant additives in polymer fractions of waste of electric and electronic equipment (WEEE) by means of HPLC-UV/MS and GPC-HPLC-UV.

    PubMed

    Schlummer, Martin; Brandl, Fritz; Mäurer, Andreas; van Eldik, Rudi

    2005-01-28

    An HPLC-UV/MS method has been developed to identify and quantify flame retardants in post-consumer plastics from waste of electric and electronic equipment (WEEE). Atmospheric pressure chemical ionisation spectra of 15 brominated and phosphate-based flame retardants were recorded and interpreted. The method was applied to detect flame retardant additives in polymer extracts obtained from pressurised liquid extraction of solid polymers. In addition, a screening method was developed for soluble styrene polymers to isolate a flame retardant fraction through the application of gel permeation chromatography (GPC). This fraction was transferred to an online-coupled HPLC column and detected by UV spectroscopy, which allowed a reliable qualitative and quantitative analysis of brominated flame retardants in the polymer solutions.

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

    PubMed

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

    2007-04-01

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

  10. 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.

  11. Leaching of brominated flame retardants from TV housing plastics in the presence of dissolved humic matter.

    PubMed

    Choi, Ki-In; Lee, Suk-Hui; Osako, Masahiro

    2009-01-01

    In this study, we investigated the contents of several brominated compounds in TV molding plastics, as well as their leaching characteristics in the presence of DHM. The PBDE content was about 3% of the sample weight, and deca-BDE was the most abundant homologue, accounting for over 80% of the total amount. TBBPA, PBPs and PBBs content was 8100, 4700 and 250 ng/g, respectively. Despite no detection of most of the lower brominated DEs in distilled water, most homologues could be detected in DHM solution, and their solubility increased according to the contact time; those of highly brominated compounds increased to 10 times their maximum solubility in distilled water. Especially, contrary to the relatively faster equilibrium in distilled water, BFR solubility in DHM solution was maintained even after 20 days. In addition, a modified first-order model adequately reflected rapid desorption for each compound in the initial period, but slow desorption afterwards. From an overall perspective, it is clear that hydrophobic BFRs can leach out to a great extent in the presence of DHM, which is a matter of great concern in E&E waste as the potential contaminant source of BFRs, especially in landfills and open dump sites that provide the perfect conditions for exposure of BFRs to abundant DHM. PMID:18977511

  12. Leaching of brominated flame retardants from TV housing plastics in the presence of dissolved humic matter.

    PubMed

    Choi, Ki-In; Lee, Suk-Hui; Osako, Masahiro

    2009-01-01

    In this study, we investigated the contents of several brominated compounds in TV molding plastics, as well as their leaching characteristics in the presence of DHM. The PBDE content was about 3% of the sample weight, and deca-BDE was the most abundant homologue, accounting for over 80% of the total amount. TBBPA, PBPs and PBBs content was 8100, 4700 and 250 ng/g, respectively. Despite no detection of most of the lower brominated DEs in distilled water, most homologues could be detected in DHM solution, and their solubility increased according to the contact time; those of highly brominated compounds increased to 10 times their maximum solubility in distilled water. Especially, contrary to the relatively faster equilibrium in distilled water, BFR solubility in DHM solution was maintained even after 20 days. In addition, a modified first-order model adequately reflected rapid desorption for each compound in the initial period, but slow desorption afterwards. From an overall perspective, it is clear that hydrophobic BFRs can leach out to a great extent in the presence of DHM, which is a matter of great concern in E&E waste as the potential contaminant source of BFRs, especially in landfills and open dump sites that provide the perfect conditions for exposure of BFRs to abundant DHM.

  13. Bioaccumulation and trophic transfer of some brominated flame retardants in a Lake Winnipeg (Canada) food web.

    PubMed

    Law, Kerri; Halldorson, Thor; Danell, Robert; Stern, Gary; Gewurtz, Sarah; Alaee, Mehran; Marvin, Chris; Whittle, Mike; Tomy, Gregg

    2006-08-01

    The extent of bioaccumulation and trophic transfer of brominated diphenyl ether (BDE) congeners, hexabromocyclododecane (HBCD) diastereoisomers (alpha, beta, and gamma), decabromodiphenylethane (DBDPE), and bis(2,4,6-tribromophenoxy)ethane (BTBPE) was examined in a Lake Winnipeg (Canada) food web. Six species of fish, zooplankton, mussels, sediment, and water from the south basin of the lake were selected for study. Significant positive correlations were found between concentrations of total (sigma) polybrominated diphenylethers (PBDEs; p < 0.005), sigmaHBCDs (p < 0.0001), BTBPE (p < 0.0001), and lipid content in fish. Strong positive linear relationships also were observed from individual plots of BDE 47, BDE 209, and DBDPE concentrations (lipid wt) and trophic level (based on delta15N), suggesting that these compounds biomagnify in the Lake Winnipeg food web. Biomagnification factors varied for the chemicals studied. Plots of log bioaccumulation factors for mussel and zooplankton versus log octanol-water partition coefficient (Kow) were similar and suggest that neither mussels nor zooplankton are in equilibrium with the water. Fifteen BDE congeners were consistently detected in water (dissolved phase, n = 3), with BDE 47 having the greatest concentration (17 pg/L). The rank order of compounds in water (arithmetic mean +/- standard error) were sigmaPBDEs (49 +/- 12 pg/ L) > alpha-HBCD (11 +/- 2 pg/L) > BTBPE (1.9 +/- 0.6 pg/L). Concentrations of DPDPE, BDE 209, and beta- and -gamma-HBCD isomers were below their respective method detection limits (MDLs) in water. Total PBDE concentrations in sediment (n = 4) were greater than any other brominated flame retardant examined in the present study and ranged from 1,160 to 1,610 ng/g (dry wt), with BDE 209 contributing roughly 50% of the total. The gamma-HBCD isomer was detected at concentrations of 50 +/- 20 pg/g (dry wt) in sediment, whereas BTBPE and DBDPE were consistently below their respective MDLs in sediment. PMID

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

    PubMed

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

    2009-06-01

    Brominated flame retardants (BFRs), including polybrominated diphenyl ethers (PBDEs), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), and polybrominated biphenyls (PBBs) were found in children's toys purchased from South China. The median BFR concentrations in the hard plastic toys were 53,000, 5540 ng/g, 101.1 ng/g, and 27.9 ng/g, fortotal PBDEs, DBDPE, BTBPE, and PBBs, respectively,which were notably higher than values in other toys. The PBDE concentrations were below the threshold limit (1000 ppm) required bythe European Commission's Restriction of Hazardous Substances (RoHS) and Waste Electrical and Electronic Equipment (WEEE) directives in all of the toys, except for one hard plastic toy with a total PBDE concentration of 5,344,000 ng/g. The BFR profiles in the toys were consistent with the patterns of their current production and consumption in China, where PBDEs, specifically decaBDE product, were the dominant BFR, followed by the emerging DBDPE. The relatively high concentrations of octa- and nonaBDEs in the foam toys and the results of principal component analysis (PCA) may suggest the decomposition of highly brominated BDEs during the manufacturing processes of the toys. Daily total PBDE exposures associated with toys via inhalation, mouthing, dermal contact, and oral ingestion ranged from 82.6 to 8992 pg/kg bw-day for children of 3 months to 14 years of age. Higher exposures, predominantly contributed through the mouthing pathway, were observed for infants and toddlers than for the other subgroups. In most cases, children's BFR exposure via the toys likely accounts for a small proportion of their daily BFR exposure, and the hazard quotients for noncancer risk evaluation were far below 1. To the author's knowledge, this is the first study to examine the concentrations of BFRs in toys, and the potential exposures to children. PMID:19569352

  15. 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...

  16. 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

  17. 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.

  18. Experimental and theoretical study of flame inhibition by bromine-containing compounds

    SciTech Connect

    Westbrook, C.K.; Beason, D.G.; Alvares, N.J.

    1981-01-20

    The present paper represents the first effort to date in which a combined experimental and theoretical approach has been used to study the effects of several inhibitors on hydrocarbon-air flames. This work is part of an attempt to build a consistent picture of chemical kinetic flame inhibition, beginning with a simple halogen molecule such as HBr and progressing sequentially towards more complex and more practical inhibitors such as CF/sub 3/Br. Inhibition efficiency can be defined as the rate of flame speed reduction, the amount of flame speed change per unit inhibitor added. Both the numerical model and the flame tube measurements found that the inhibition efficiency gradually decreases as the amount of inhibitor is increased. The present experimental and modeling results are shown, together with earlier data for CF/sub 3/Br-CH/sub 4/-air and CF/sub 3/Br-C/sub 3/H/sub 8/-air as well as HBr-CH/sub 4/-air, CH/sub 3/Br-CH/sub 4/-air and CF/sub 3/Br-CH/sub 4/-air. In the numerical study it was found that a stoichiometric methane-air mixture with up to 8% methyl bromide could support a flame, propagating at a speed of about 5 cm/sec, even though the addition of the first 1% of CH/sub 3/Br had reduced the flame speed from 38 cm/sec to about 26 cm/sec. Extensions of the model to include CF/sub 3/Br are currently under development. The available experimental data suggest that CF/sub 3/Br is somewhat more efficient as an inhibitor than HBr or CH/sub 3/Br.

  19. 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...

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

    PubMed

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

    2014-12-01

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

  1. 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...

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

    EPA Science Inventory

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

  3. 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

  4. Uptake and biotransformation of structurally diverse brominated flame retardants in zebrafish (Danio rerio) after dietary exposure.

    PubMed

    Nyholm, Jenny Rattfelt; Norman, Anna; Norrgren, Leif; Haglund, Peter; Andersson, Patrik L

    2009-05-01

    Zebrafish (Danio rerio) were fed a diet containing a mixture of 11 structurally diverse brominated flame retardants (BFRs) at nominal concentrations of either 1 or 100 nmol/g for up to 42 d, followed by an elimination period of 14 d. Uptake rates and elimination constants for five of the BFRs were calculated from measurements of their concentrations in the male fish during the exposure and elimination phases. Observed uptake efficiencies were highest for 2,4,4'-tribromodiphenyl ether (BDE 28) and 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) and were lowest for decabromodiphenyl ether (BDE 209). Estimated half-lives for TBECH and 2,4,6-tribromophenol were short (<2 d). Four BFR metabolites were identified in the fish: 2,2',3,4',5',6-Hexabromodiphenyl ether (BDE 149), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE 154), 2,4,6-tribromoanisole, and 1,2,4,5-hexabromobenzene. These metabolites were still present in the zebrafish after the 14-d elimination period. No relationship between the BFR concentrations in the zebrafish and their log octanol-water partition coefficient (Kow) values was found. Generally, low tendencies to bioaccumulate were observed for perbrominated and hydroxylated compounds. The observed accumulation of BFR metabolites in fish, however, shows that low concentration of a BFR does not provide, in isolation, a sound indication that the BFR poses low risks. PMID:19049262

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

    PubMed

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

    2016-05-01

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

  6. 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

    2015-01-01

    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.

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

    PubMed

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

    2016-05-01

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

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

    PubMed

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

    2016-05-01

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

  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. From Clothing to Laundry Water: Investigating the Fate of Phthalates, Brominated Flame Retardants, and Organophosphate Esters.

    PubMed

    Saini, Amandeep; Thaysen, Clara; Jantunen, Liisa; McQueen, Rachel H; Diamond, Miriam L

    2016-09-01

    The accumulation of phthalate esters, brominated flame retardants (BFRs) and organophosphate esters (OPEs) by clothing from indoor air and transfer via laundering to outdoors were investigated. Over 30 days cotton and polyester fabrics accumulated 3475 and 1950 ng/dm(2) ∑5phthalates, 65 and 78 ng/dm(2) ∑10BFRs, and 1200 and 310 ng/dm(2) ∑8OPEs, respectively. Planar surface area concentrations of OPEs and low molecular weight phthalates were significantly greater in cotton than polyester and similar for BFRs and high molecular weight phthalates. This difference was significantly and inversely correlated with KOW, suggesting greater sorption of polar compounds to polar cotton. Chemical release from cotton and polyester to laundry water was >80% of aliphatic OPEs (log KOW < 4), < 50% of OPEs with an aromatic structure, 50-100% of low molecular weight phthalates (log KOW 4-6), and < detection-35% of higher molecular weight phthalates (log KOW > 8) and BFRs (log KOW > 6). These results support the hypothesis that clothing acts an efficient conveyer of soluble semivolatile organic compounds (SVOCs) from indoors to outdoors through accumulation from air and then release during laundering. Clothes drying could as well contribute to the release of chemicals emitted by electric dryers. The results also have implications for dermal exposure. PMID:27507188

  12. Emerging brominated flame retardants in the sediment of the Great Lakes.

    PubMed

    Yang, Ruiqiang; Wei, Hua; Guo, Jiehong; Li, An

    2012-03-20

    The concentrations of 13 currently used brominated flame retardants (BFRs) were analyzed in 16 sediment cores collected from the North American Great Lakes. Among them, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromocyclododecane (HBCD), 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH), and hexachlorocyclopentadienyl dibromocyclooctane (HCDBCO) were more frequently detected than others. In general, these emerging BFRs have much lower concentrations than polybromodiphenyl ethers (PBDEs) and dechloranes. Inventories of the five BFRs named above, given on a logarithm basis, were found to decrease linearly with the increasing latitude of the sampling locations, but with weaker statistics than those previously reported for the dechloranes. Logarithm of surface fluxes, on the other hand, was found to be a better parameter in correlating with the longitude. With regard to time trends, the exponential increases in concentrations of these BFRs, particularly DBDPE and BTBPE, in recent years are particularly disturbing. The sediment concentration of DBDPE doubles every 3-5 years in Lake Michigan, and approximately every 7 years in Lake Ontario. The corresponding doubling times for BTBPE are about 5 and 7 years in Lakes Ontario and Michigan, respectively, although declines or leveling off were observed in the top sediment layers in Lake Ontario. In contrast to PCBs, PBDEs, and most dechloranes, the correlations between the surface concentration of emerging BFRs and the latitude or longitude of the sampling sites were not strengthened by normalization of the concentration based on the organic matter content of the sediment.

  13. 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. PMID:24999183

  14. From Clothing to Laundry Water: Investigating the Fate of Phthalates, Brominated Flame Retardants, and Organophosphate Esters.

    PubMed

    Saini, Amandeep; Thaysen, Clara; Jantunen, Liisa; McQueen, Rachel H; Diamond, Miriam L

    2016-09-01

    The accumulation of phthalate esters, brominated flame retardants (BFRs) and organophosphate esters (OPEs) by clothing from indoor air and transfer via laundering to outdoors were investigated. Over 30 days cotton and polyester fabrics accumulated 3475 and 1950 ng/dm(2) ∑5phthalates, 65 and 78 ng/dm(2) ∑10BFRs, and 1200 and 310 ng/dm(2) ∑8OPEs, respectively. Planar surface area concentrations of OPEs and low molecular weight phthalates were significantly greater in cotton than polyester and similar for BFRs and high molecular weight phthalates. This difference was significantly and inversely correlated with KOW, suggesting greater sorption of polar compounds to polar cotton. Chemical release from cotton and polyester to laundry water was >80% of aliphatic OPEs (log KOW < 4), < 50% of OPEs with an aromatic structure, 50-100% of low molecular weight phthalates (log KOW 4-6), and < detection-35% of higher molecular weight phthalates (log KOW > 8) and BFRs (log KOW > 6). These results support the hypothesis that clothing acts an efficient conveyer of soluble semivolatile organic compounds (SVOCs) from indoors to outdoors through accumulation from air and then release during laundering. Clothes drying could as well contribute to the release of chemicals emitted by electric dryers. The results also have implications for dermal exposure.

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

    PubMed

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

    2016-05-01

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

  16. Advances in enantioselective analysis of chiral brominated flame retardants. Current status, limitations and future perspectives.

    PubMed

    Badea, Silviu-Laurentiu; Niculescu, Violeta Carolina; Ionete, Roxana-Elena; Eljarrat, Ethel

    2016-10-01

    Enantioselective analysis is a powerful tool for the discrimination of biotic and abiotic transformation processes of chiral environmental contaminants because their environmental biodegradation is mostly stereospecific. However, it is challenging when applied to new contaminants since enantioselective analysis methods are currently available only for a limited number of compounds. The enantioselective analysis of chiral novel brominated flame retardants (NBFRs) either using gas chromatography (GC) or liquid chromatography (LC) with various chiral stationary phases (CSP) coupled with various mass spectrometric techniques was extensively discussed. The elution order of hexabromocyclododecane (HBCD) enantiomers in chiral LC was reviewed using the experimental LC data combined also with predictions from a multi-mode Hamiltonian dynamics simulation model based on interaction energies of HBCD enantiomers with β-permethylated cyclodextrin. The further development of analytical methodologies for new chiral BFRs using advanced hyphenated analytical techniques, but also the next generation mass spectrometer analyzers (i.e. GC-Qrbitrap MS-MS, LC-Qrbitrap MS-MS), will contribute to a better characterization of the transformation pathways of chiral BFRs.

  17. Leaching characteristics of heavy metals and brominated flame retardants from waste printed circuit boards.

    PubMed

    Zhou, Xiaoyu; Guo, Jie; Lin, Kuangfei; Huang, Kai; Deng, Jingjing

    2013-02-15

    Leaching assessment on five heavy metals (copper, zinc, lead, nickel and cadmium) and two brominated flame retardants (BFRs), polybrominated diphenyl ethers (PBDEs) and tetrabromobisphenol A (TBBPA), from waste printed circuit boards (WPCBs) were conducted using various leaching methods. The mean leaching concentrations of copper were the highest in both toxicity characteristic leaching procedures (TCLP) and synthetic precipitation leaching procedures (SPLP) tests at 8.6 mg/L and 1.1mg/L, while only lead (6.2mg/L) exceeded the TCLP criteria and Chinese EPA regulatory limit (both 5.0mg/L). However, PBDEs and TBBPA were not detected in TCLP and SPLP tests. Then the BFRs leaching trends and potential leachabilities were further investigated in actual landfill leachates using a modified method. Leaching characteristics that fast-leaching initially followed by slow-desorption over time were generally observed. In landfill leachate tests, the highest leaching concentrations of PBDEs and TBBPA were determined at 30.39 and 12.27 μg/L. Meanwhile, the highest leaching rates were estimated to reach 0.08% and 1.00%, respectively, which were significantly influenced by the dissolved organic carbon contents of extracts, the hydrophobicities of target BFRs and the specific surface areas of WPCBs materials. These results proved that leaching from WPCBs was a significant emission source of BFRs in landfill and electronic waste recycling dumpsite. PMID:23291335

  18. Advances in enantioselective analysis of chiral brominated flame retardants. Current status, limitations and future perspectives.

    PubMed

    Badea, Silviu-Laurentiu; Niculescu, Violeta Carolina; Ionete, Roxana-Elena; Eljarrat, Ethel

    2016-10-01

    Enantioselective analysis is a powerful tool for the discrimination of biotic and abiotic transformation processes of chiral environmental contaminants because their environmental biodegradation is mostly stereospecific. However, it is challenging when applied to new contaminants since enantioselective analysis methods are currently available only for a limited number of compounds. The enantioselective analysis of chiral novel brominated flame retardants (NBFRs) either using gas chromatography (GC) or liquid chromatography (LC) with various chiral stationary phases (CSP) coupled with various mass spectrometric techniques was extensively discussed. The elution order of hexabromocyclododecane (HBCD) enantiomers in chiral LC was reviewed using the experimental LC data combined also with predictions from a multi-mode Hamiltonian dynamics simulation model based on interaction energies of HBCD enantiomers with β-permethylated cyclodextrin. The further development of analytical methodologies for new chiral BFRs using advanced hyphenated analytical techniques, but also the next generation mass spectrometer analyzers (i.e. GC-Qrbitrap MS-MS, LC-Qrbitrap MS-MS), will contribute to a better characterization of the transformation pathways of chiral BFRs. PMID:27265736

  19. 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.

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

    PubMed

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

    2016-06-01

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

  1. Brominated flame retardants in the Arctic environment--trends and new candidates.

    PubMed

    de Wit, Cynthia A; Herzke, Dorte; Vorkamp, Katrin

    2010-07-01

    Polybrominated diphenyl ethers (PBDEs) containing two to 10 bromines are ubiquitous in the Arctic, in both abiotic and biotic samples. Hexabromocyclododecane (HBCD) is also ubiquitous in the Arctic, with the gamma-HBCD isomer predominating in air, the alpha-HBCD isomer predominating in biota and similar concentrations of alpha-, beta- and gamma-HBCD found in marine sediments. Other brominated flame retardants (BFRs) found in some Arctic samples are polybrominated biphenyls (PBBs), tetrabromobisphenol A (TBBPA), 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE), hexabromobenzene (HxBBz), pentabromoethylbenzene (PBEB), pentabromotoluene (PBT), and 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH). Temporal trends of tetra- to heptaBDEs and HBCD show increasing concentrations or a tendency to levelling off depending on the matrix (air, sediment, biota) and location, but no uniform picture for the Arctic emerges. BDE-209 concentrations are increasing in air. PBDEs and HBCD spatial trends in seabirds and marine mammals are similar to those seen previously for polychlorinated biphenyls (PCBs), with highest concentrations found in organisms from East Greenland and Svalbard. These trends indicate western Europe and eastern North America as important source regions of these compounds via long range atmospheric transport and ocean currents. Latitudinal trends showed lower concentrations and fluxes of PBDEs at higher latitudes. The tetra-hexaBDEs and alpha-HBCD biomagnify in Arctic food webs. Results for BDE-209 are more conflicting, showing either only low or no biomagnification potential. PBDE and HBCD concentrations are lower in terrestrial organisms and higher in marine top predators such as some killer whale populations in Alaska and glaucous gulls from the Barents Sea area. Higher concentrations are seen near populated areas indicating local sources. Findings of BTBPE, HxBBz, PBEB, PBT and TBECH in seabirds and/or marine mammals indicate that these compounds reach the

  2. 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

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

    PubMed

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

    2016-08-01

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

  4. 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.

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

    PubMed

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

    2016-08-01

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

  6. 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.

  7. Fate and metabolism of the brominated flame retardant tetrabromobisphenol A (TBBPA) in rice cell suspension culture.

    PubMed

    Wang, Songfeng; Cao, Siqi; Wang, Yongfeng; Jiang, Bingqi; Wang, Lianhong; Sun, Feifei; Ji, Rong

    2016-07-01

    Tetrabromobisphenol A (TBBPA) is the brominated flame retardant with the highest production volume and its bioaccumulation in environment has caused both human health and environmental concerns, however the fate and metabolism of TBBPA in plants is unknown. We studied the fate, metabolites, and transformation of (14)C-labeled TBBPA in rice cell suspension culture. During the incubation for 14 days, TBBPA degradation occurred continuously in the culture, accompanied by formation of one anisolic metabolite [2,6-dibromo-4-(2-(2-hydroxy)-propyl)-anisole] (DBHPA) (50% of the degraded TBBPA) and cellular debris-bound residues (46.4%) as well as mineralization (3.6%). The cells continuously accumulated TBBPA in the cytoplasm, while a small amount of DBHPA (2.1% of the initially applied TBBPA) was detectable inside the cells only at the end of incubation. The majority of the accumulated residues in the cells was attributed to the cellular debris-bound residues, accounting for 70-79% of the accumulation after the first incubation day. About 5.4% of the accumulation was associated with cell organelles, which contributed 7.5% to the cellular debris-bound residues. Based on the fate and metabolism of TBBPA in the rice cell suspension culture, a type II ipso-substitution pathway was proposed to describe the initial step for TBBPA degradation in the culture and balance the fate of TBBPA in the cells. To the best of our knowledge, our study provides for the first time the insights into the fate and metabolism of TBBPA in plants and points out the potential role of type II ipso-hydroxylation substitution in degradation of alkylphenols in plants. Further studies are required to reveal the mechanisms for the bound-residue formation (e.g., binding of residues to specific cell wall components), nature of the binding, and toxicological effects of the bound residues and DBHPA.

  8. 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

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

    PubMed

    Butt, Craig M; Stapleton, Heather M

    2013-11-18

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

  10. 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

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

    PubMed

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

    2012-09-01

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

  12. 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. PMID:12850097

  13. 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.

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

    PubMed

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

    2014-02-01

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

  15. The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer.

    PubMed

    Brebu, Mihai; Bhaskar, Thallada; Murai, Kazuya; Muto, Akinori; Sakata, Yusaku; Uddin, Md Azhar

    2004-08-01

    Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.

  16. 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

    2015-10-01

    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

  17. 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

    2015-10-01

    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

  18. A comparison of the in vitro cyto- and neurotoxicity of brominated and halogen-free flame retardants: prioritization in search for safe(r) alternatives.

    PubMed

    Hendriks, Hester S; Meijer, Marieke; Muilwijk, Mirthe; van den Berg, Martin; Westerink, Remco H S

    2014-04-01

    Brominated flame retardants (BFRs) are abundant persistent organic pollutants with well-studied toxicity. The toxicological and ecological concerns associated with BFRs argue for replacement by safe(r) alternatives. Though previous research identified the nervous system as a sensitive target organ for BFRs, the (neuro) toxic potential of alternative halogen-free flame retardants (HFFRs) is largely unknown. We therefore investigated the in vitro (neuro) toxicity of 13 HFFRs and three BFRs in dopaminergic pheochromocytoma (PC12) and neuroblastoma (B35) cells by assessing several cytotoxic and neurotoxic endpoints. Effects on cell viability and production of reactive oxygen species (ROS) were measured using a combined Alamar Blue and Neutral Red assay and a H2-DCFDA assay, respectively, whereas effects on calcium homeostasis were measured using single-cell fluorescent Ca(2+)-imaging. The majority of the tested flame retardants induced negligible cytotoxicity, except zinc hydroxystannate (ZHS) and zinc stannate (ZS). A considerable fraction of flame retardants affected ROS production (decabromodiphenyl ether (BDE-209), triphenylphosphate (TPP), aluminium trihydroxide (ATH), ammonium polyphosphate (APP), magnesium hydroxide (MHO), ZHS, ZS and melamine polyphosphate (MPP)). Interestingly, ATH, ZHS, ZS and montmorillonite (MMT) increased the basal intracellular calcium concentration ([Ca(2+)]i), whereas tetrabromobisphenol A (TBBPA), resorcinol bis (diphenylphosphate) (RDP), TPP, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), ATH, ZHS, ZS and MMT reduced depolarization-evoked increases in [Ca(2+)]i as a result of inhibition of voltage-gated calcium channels. These combined data on the in vitro (neuro) toxicity of HFFRs in comparison with BFRs are essential for prioritization of safe(r) flame retardants. Though additional data are required for a complete (toxic) risk assessment, our data demonstrate that several HFFRs could be suitable substitutes for

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

    PubMed

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

    2015-08-15

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

  20. 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

    2012-06-01

    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.

  1. Levels, distribution and human exposure of new non-BDE brominated flame retardants in the indoor dust of China.

    PubMed

    Qi, Hong; Li, Wen-Long; Liu, Li-Yan; Zhang, Zi-Feng; Zhu, Ning-Zheng; Song, Wei-Wei; Ma, Wan-Li; Li, Yi-Fan

    2014-12-01

    Indoor environment is an important source of human exposure to several toxicants, such as brominated flame retardants. This study presents the concentrations of 22 Non-BDE brominated flame retardants (NBFRs) in 81 indoor dust samples from 23 provinces across China in the winter of 2010. The concentrations of ΣNBFRs ranged from 6.3 to 20,000 ng/g, with a median concentration of 720 ng/g. DBDPE was the dominated compound, followed by HBCD and BEHTBP. Significant differences of concentrations were found between samples from rural and urban areas, and between family and public houses, indicating different applications of NBFRs. The geographical distribution of NBFRs highlighted several hotspots in North China, suggesting the influence of room temperature (heating). The exposure via dust ingestion of NBFRs was 3.8-14 times higher than that of dermal absorption. The toddlers demonstrated the highest exposure dose (9.6 ng/kg-bw/day) of NBFRs through indoor dust among all life stages.

  2. On-line detection of heavy metals and brominated flame retardants in technical polymers with laser-induced breakdown spectrometry.

    PubMed

    Stepputat, Michael; Noll, Reinhard

    2003-10-20

    The use of laser-induced breakdown spectrometry (LIBS) for the analysis of heavy metals and brominated flame retardants in end-of-life waste electric and electronic equipment (EOL-WEEE) pieces is investigated. Single- and double-pulse plasma excitation as well as the influence of detection parameters is studied to yield a parameter field with improved sensitivity and limits of detection. A LIBS analyzer was set up as an on-line measuring unit to detect heavy metals and brominated flame retardants in moving EOL-WEEE pieces in an automatic sorting line. An autofocusing unit with an adjustment range of 50 mm was incorporated to permit measurements of objects that pass by a LIBS analyzer with their surfaces at various distances from it. Tests with EOL-WEEE monitor housings on the conveyor belt of a pilot sorting system successfully demonstrated the capability of the LIBS analyzer to quantify the concentration of hazardous elements in real waste EOL-WEEE pieces. PMID:14594087

  3. On-line detection of heavy metals and brominated flame retardants in technical polymers with laser-induced breakdown spectrometry

    NASA Astrophysics Data System (ADS)

    Stepputat, Michael; Noll, Reinhard

    2003-10-01

    The use of laser-induced breakdown spectrometry (LIBS) for the analysis of heavy metals and brominated flame retardants in end-of-life waste electric and electronic equipment (EOL-WEEE) pieces is investigated. Single- and double-pulse plasma excitation as well as the influence of detection parameters is studied to yield a parameter field with improved sensitivity and limits of detection. A LIBS analyzer was set up as an on-line measuring unit to detect heavy metals and brominated flame retardants in moving EOL-WEEE pieces in an automatic sorting line. An autofocusing unit with an adjustment range of 50 mm was incorporated to permit measurements of objects that pass by a LIBS analyzer with their surfaces at various distances from it. Tests with EOL-WEEE monitor housings on the conveyor belt of a pilot sorting system successfully demonstrated the capability of the LIBS analyzer to quantify the concentration of hazardous elements in real waste EOL-WEEE pieces.

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

    PubMed

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

    2012-03-01

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

  5. Flame-retardant additives for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Hyung, Yoo E.; Vissers, Donald R.; Amine, Khalil

    To enhance the resistance of lithium-ion battery components to ignition and to reduce the flammability of the electrolyte with minimal effect on performance, we added flame-retardant additives to the electrolyte. The flame retardants were selected from a group of organic phosphate compounds, triphenylphosphate (TPP) and tributylphosphate (TBP), to provide superior thermal safety in lithium-ion cells at the fully charged state. The cycling characteristics of the lithium-ion cells containing flame-retardant additives were found to be similar or superior to the cells that contained no additives. Horizontal burning tests of electrolytes were carried out in a flame test chamber referenced by Underwriters Laboratories (UL) test standard 94 (UL 94) and ASTM D4986-98 to evaluate the electrolyes' flammability characteristics. The thermal stability characteristics of the electrodes and electrolytes with and without flame-retardant additives were investigated by accelerating rate calorimetry (ARC). Negative electrode samples with electrolytes containing flame-retardant additives revealed less heat generation and higher-onset decomposition temperatures. The results disclose that the thermal safety of lithium-ion cells can be improved by incorporating small amounts of suitable additives such as triphenylphosphate and tributylphosphate to the electrolyte.

  6. 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

    2014-06-01

    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.

  7. 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...

  8. 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...

  9. 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)

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

    PubMed

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

    2016-08-01

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

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

    PubMed

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

    2016-08-01

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

  12. 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.

  13. 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. PMID:26123348

  14. Flame retardant brominated styrene-based polymers. VII. Applications of dibromostyrene graft latices

    SciTech Connect

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

    1995-12-01

    The dibromostyrene graft lattices possessing desired physical properties combined with flame retardancy have passed five different flammability tests for the following applications: textile backcoating (MVSS-302 flammability test), contact adhesive (exposure to a 3 in blue methane Bunsen burner flame), latex binder (exposure to a 4 in high, 1950{degrees}F propane flame from a Fisher burner), latex sealant (the Butler chimney flammability test, AST4 D-3014) and latex paint (the limiting oxygen index test, ASTM D-2863).

  15. 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.

  16. 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.

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

    PubMed

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

    2012-03-01

    Polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE), polybrominated biphenyls (PBBs) and pentabromotoluene (PBT) were investigated in light-vented bulbul (LVB), long-tailed shrike (LTS) and oriental magpie-robin (OMR) collected from seven sampling sites in South China. ∑PBDEs, DBDPE, PBB 153, and PBT levels ranged from 35 to 15,000, no detected (nd)-130, nd-6800, and nd-6.8 ng/g lipid weight, respectively. Positive correlations were found between δ(15)N values and brominated flame retardant (BFR) concentrations. The BFR geographic pattern indicated that PBDEs were linked to e-waste recycling and local industry activities as well as urbanization; PBB 153 was derived from e-waste; DBDPE was mainly come from local industry activities; and no specific source was observed for PBT. PBDE congener profiles were found to be depended on bird species and sampling sites with relatively high abundances of lower brominated congeners in e-waste site and significantly higher abundance of BDE153 in LTS and OMR than in LVB. PMID:22243889

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

    PubMed

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

    2012-03-01

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

  19. 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

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

    PubMed

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

    2016-11-01

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

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

    PubMed

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

    2016-11-01

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

  2. 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.

  3. Brominated flame retardants (BFRs) in indoor and outdoor air in a community in Guangzhou, a megacity of southern China.

    PubMed

    Ding, Nan; Wang, Tao; Chen, She-Jun; Yu, Mei; Zhu, Zhi-Cheng; Tian, Mi; Luo, Xiao-Jun; Mai, Bi-Xian

    2016-05-01

    Indoor environments contribute a significant portion of human exposure to brominated flame retardants (BFRs) because of their extensive use in various household products. This study investigates the occurrence of a number of BFRs in the indoor and outdoor air in a megacity in southern China, in which little information on indoor BFRs contamination is available. The estimated total PBDE concentrations ranged from 1.43 to 57 pg/m(3) indoors and from 1.21 to 1522 pg/m(3) outdoors. The indoor concentrations of lower brominated PBDEs that are mainly derived from the technical penta- and octa-BDE mixtures were higher than or comparable to the outdoors, while the indoor levels of DecaBDEs and decabromodiphenyl ethane (DBDPE) were apparently lower than the outdoors. The seasonal variations of BFR concentrations indicated that evaporation from old indoor products is the primary source of Penta- and OctaBDEs in the air, whereas most DecaBDEs and DBDPE concentrations showing weak temperature-dependence are largely released from industrial activities. The PBDE congener profiles in the air were generally similar, which were dominated by BDE209, 28, and 47; whereas the appreciable indoor-outdoor differences in the compositions are possibly due to emission sources, photochemical degradation, or congener-specific transport of BFRs in the indoor and outdoor air. Significant correlations between the indoor and outdoor BFRs were observed suggesting the exchange of BFRs between the two compartments, which are more noticeable for PentaBDEs and DecaBDEs with strong indoor and outdoor emission sources, respectively. This study provides significant insights into the sources of BFRs in urban air in China.

  4. 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.

  5. Brominated flame retardants (BFRs) in indoor and outdoor air in a community in Guangzhou, a megacity of southern China.

    PubMed

    Ding, Nan; Wang, Tao; Chen, She-Jun; Yu, Mei; Zhu, Zhi-Cheng; Tian, Mi; Luo, Xiao-Jun; Mai, Bi-Xian

    2016-05-01

    Indoor environments contribute a significant portion of human exposure to brominated flame retardants (BFRs) because of their extensive use in various household products. This study investigates the occurrence of a number of BFRs in the indoor and outdoor air in a megacity in southern China, in which little information on indoor BFRs contamination is available. The estimated total PBDE concentrations ranged from 1.43 to 57 pg/m(3) indoors and from 1.21 to 1522 pg/m(3) outdoors. The indoor concentrations of lower brominated PBDEs that are mainly derived from the technical penta- and octa-BDE mixtures were higher than or comparable to the outdoors, while the indoor levels of DecaBDEs and decabromodiphenyl ethane (DBDPE) were apparently lower than the outdoors. The seasonal variations of BFR concentrations indicated that evaporation from old indoor products is the primary source of Penta- and OctaBDEs in the air, whereas most DecaBDEs and DBDPE concentrations showing weak temperature-dependence are largely released from industrial activities. The PBDE congener profiles in the air were generally similar, which were dominated by BDE209, 28, and 47; whereas the appreciable indoor-outdoor differences in the compositions are possibly due to emission sources, photochemical degradation, or congener-specific transport of BFRs in the indoor and outdoor air. Significant correlations between the indoor and outdoor BFRs were observed suggesting the exchange of BFRs between the two compartments, which are more noticeable for PentaBDEs and DecaBDEs with strong indoor and outdoor emission sources, respectively. This study provides significant insights into the sources of BFRs in urban air in China. PMID:26952274

  6. 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...

  7. 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.

  8. Occurrence and air-seawater exchange of brominated flame retardants and Dechlorane Plus in the North Sea

    NASA Astrophysics Data System (ADS)

    Möller, Axel; Xie, Zhiyong; Caba, Armando; Sturm, Renate; Ebinghaus, Ralf

    2012-01-01

    The occurrence, spatial and seasonal concentration variations in air and seawater and the air-seawater exchange of polybrominated diphenyl ethers (PBDEs), alternate brominated flame retardants (BFRs) and Dechlorane Plus (DP) were studied in the German part of the North Sea in 2010. BDE-209 and DP were found to be the dominating compounds, both in the atmosphere and in seawater. Sum PBDEs (∑ 10PBDEs) ranged from 0.31 to 10.7 pg m -3 in the atmosphere and from not detected (n.d.) to 10.5 pg L -1 in seawater, respectively. DP ranged from 0.13 to 22.3 pg m -3 and from 0.10 to 17.7 pg L -1 in air and seawater, respectively. Besides, four other BFRs including hexabromobenzene (HBB) and pentabromobenzene (PBBz) were detected. Elevated atmospheric concentrations were observed in continentally influenced air masses while highest seawater concentrations were observed at sampling stations close to the coast influenced by riverine discharge. The ratio of the two DP stereoisomers both in air and water was found to be close to the technical mixture at high concentrations but changed at lower concentrations giving first evidence for the alteration within the aquatic environment. Both dry air-seawater gas exchange and dry deposition are input pathways of BFRs and DP in the North Sea besides riverine discharge.

  9. 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 (

  10. 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.

  11. 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.

  12. Occurrence and Distribution Pattern of Alkylphenol Ethoxylates and Brominated Flame Retardants in Sediment Samples from Vaal River, South Africa.

    PubMed

    Chokwe, T B; Okonkwo, O J; Sibali, L L; Mporetji, S M

    2016-09-01

    High environmental concentrations for alkylphenol ethoxylates (APEs) and brominated flame retardants (BFRs) have been observed near cities than in rural environment. This is due, in part, to sewage systems receiving effluents from many industrial processes along with domestic wastewater. While these classes of compounds are being phased out in most developed countries, there is still widespread use in low to middle income countries. To better understand the extent of APEs and BFRs contamination in the environment, this study reports on the concentration and distribution of APEs and BFRs in sediments samples collected from Vaal River, South Africa. Measurable concentrations of these contaminants were obtained using GC-MS after heptafluorobutyric derivatization. The concentrations range (ng g(-1)) for these pollutants were as follows: nd-46, 20-127, 24-38, 3-5, 14-28, 16-54 for octylphenol penta ethoxylates, nonylphenol ethoxylates (mono- di), nonylphenol penta ethoxylates, PBB101, PBDEs, and HBCD; respectively. The distribution observed in this study indicated higher levels of sediment contamination by APEs relative to BFRs. These results underline the need to further investigate the burden and risks associated with chemical contamination in developing countries.

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

    PubMed

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

    2015-03-01

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

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

    PubMed

    Kuang, Jiangmeng; Ma, Yuning; Harrad, Stuart

    2016-04-01

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

  15. Occurrence and Distribution Pattern of Alkylphenol Ethoxylates and Brominated Flame Retardants in Sediment Samples from Vaal River, South Africa.

    PubMed

    Chokwe, T B; Okonkwo, O J; Sibali, L L; Mporetji, S M

    2016-09-01

    High environmental concentrations for alkylphenol ethoxylates (APEs) and brominated flame retardants (BFRs) have been observed near cities than in rural environment. This is due, in part, to sewage systems receiving effluents from many industrial processes along with domestic wastewater. While these classes of compounds are being phased out in most developed countries, there is still widespread use in low to middle income countries. To better understand the extent of APEs and BFRs contamination in the environment, this study reports on the concentration and distribution of APEs and BFRs in sediments samples collected from Vaal River, South Africa. Measurable concentrations of these contaminants were obtained using GC-MS after heptafluorobutyric derivatization. The concentrations range (ng g(-1)) for these pollutants were as follows: nd-46, 20-127, 24-38, 3-5, 14-28, 16-54 for octylphenol penta ethoxylates, nonylphenol ethoxylates (mono- di), nonylphenol penta ethoxylates, PBB101, PBDEs, and HBCD; respectively. The distribution observed in this study indicated higher levels of sediment contamination by APEs relative to BFRs. These results underline the need to further investigate the burden and risks associated with chemical contamination in developing countries. PMID:27443342

  16. 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.

  17. 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.

  18. 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 (

  19. Calibration of two passive air samplers for monitoring phthalates and brominated flame-retardants in indoor air.

    PubMed

    Saini, Amandeep; Okeme, Joseph O; Goosey, Emma; Diamond, Miriam L

    2015-10-01

    Two passive air samplers (PAS), polyurethane foam (PUF) disks and Sorbent Impregnated PUF (SIP) disks, were characterized for uptake of phthalates and brominated flame-retardants (BFRs) indoors using fully and partially sheltered housings. Based on calibration against an active low-volume air sampler for gas- and particle-phase compounds, we recommend generic sampling rates of 3.5±0.9 and 1.0±0.4 m(3)/day for partially and fully sheltered housing, respectively, which applies to gas-phase phthalates and BFRs as well as particle-phase DEHP (the later for the partially sheltered PAS). For phthalates, partially sheltered SIPs are recommended. Further, we recommend the use of partially sheltered PAS indoors and a deployment period of one month. The sampling rate for the partially sheltered PUF and SIP of 3.5±0.9 m(3)/day is indistinguishable from that reported for fully sheltered PAS deployed outdoors, indicating the role of the housing outdoors to minimize the effect of variable wind velocities on chemical uptake, versus the partially sheltered PAS deployed indoors to maximize chemical uptake where air flow rates are low.

  20. 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.

  1. 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.

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

    PubMed

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

    2005-08-01

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

  3. The brominated flame retardants TBP-AE and TBP-DBPE antagonize the chicken androgen receptor and act as potential endocrine disrupters in chicken LMH cells.

    PubMed

    Asnake, Solomon; Pradhan, Ajay; Kharlyngdoh, Joubert Banjop; Modig, Carina; Olsson, Per-Erik

    2015-12-01

    Increased exposure of birds to endocrine disrupting compounds has resulted in developmental and reproductive dysfunctions. We have recently identified the flame retardants, allyl-2,4,6-tribromophenyl ether (TBP-AE), 2-3-dibromopropyl-2,4,6-tribromophenyl ether (TBP-DBPE) and the TBP-DBPE metabolite 2-bromoallyl-2,4,6-tribromophenyl ether (TBP-BAE) as antagonists to both the human androgen receptor (AR) and the zebrafish AR. In the present study, we aimed at determining whether these compounds also interact with the chicken AR. In silico modeling studies showed that TBP-AE, TBP-BAE and TBP-DBPE were able to dock into to the chicken AR ligand-binding pocket. In vitro transfection assays revealed that all three brominated compounds acted as chicken AR antagonists, inhibiting testosterone induced AR activation. In addition, qRT-PCR studies confirmed that they act as AR antagonists and demonstrated that they also alter gene expression patterns of apoptotic, anti-apoptotic, drug metabolizing and amino acid transporter genes. These studies, using chicken LMH cells, suggest that TBP-AE, TBP-BAE and TBP-DBPE are potential endocrine disrupters in chicken.

  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 brominated flame retardants TBP-AE and TBP-DBPE antagonize the chicken androgen receptor and act as potential endocrine disrupters in chicken LMH cells.

    PubMed

    Asnake, Solomon; Pradhan, Ajay; Kharlyngdoh, Joubert Banjop; Modig, Carina; Olsson, Per-Erik

    2015-12-01

    Increased exposure of birds to endocrine disrupting compounds has resulted in developmental and reproductive dysfunctions. We have recently identified the flame retardants, allyl-2,4,6-tribromophenyl ether (TBP-AE), 2-3-dibromopropyl-2,4,6-tribromophenyl ether (TBP-DBPE) and the TBP-DBPE metabolite 2-bromoallyl-2,4,6-tribromophenyl ether (TBP-BAE) as antagonists to both the human androgen receptor (AR) and the zebrafish AR. In the present study, we aimed at determining whether these compounds also interact with the chicken AR. In silico modeling studies showed that TBP-AE, TBP-BAE and TBP-DBPE were able to dock into to the chicken AR ligand-binding pocket. In vitro transfection assays revealed that all three brominated compounds acted as chicken AR antagonists, inhibiting testosterone induced AR activation. In addition, qRT-PCR studies confirmed that they act as AR antagonists and demonstrated that they also alter gene expression patterns of apoptotic, anti-apoptotic, drug metabolizing and amino acid transporter genes. These studies, using chicken LMH cells, suggest that TBP-AE, TBP-BAE and TBP-DBPE are potential endocrine disrupters in chicken. PMID:26318274

  6. 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. PMID:24189551

  7. 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. PMID:27425757

  8. Brominated flame retardants in the European chemicals policy of REACH-Regulation and determination in materials.

    PubMed

    Kemmlein, Sabine; Herzke, Dorte; Law, Robin J

    2009-01-16

    The EU REACH legislation will require the registration of 30,000 currently marketed chemicals, including the main commercial BFRs in use (Deca-BDE, HBCD and TBBP-A). Much of the data needed for registration are already available, thanks to risk assessments of continued production and use already undertaken in the EU. Within the authorisation, substitution by less hazardous chemicals is encouraged. Both qualitative and quantitative methods for the analysis of flame-retarded polymers are needed in order that the identity and concentration of the BFRs can be established and compliance with regulations including the RoHS Directive demonstrated. These are reviewed.

  9. 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. PMID:26926265

  10. 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.

  11. 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. PMID:23948077

  12. 40 CFR 721.775 - Brominated aromatic com-pound (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    .... Requirements as specified in § 721.80 (j) (use as an additive flame retardant for plastics) and (q). (iv... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Brominated aromatic com-pound (generic... Specific Chemical Substances § 721.775 Brominated aromatic com-pound (generic name). (a)...

  13. 40 CFR 721.775 - Brominated aromatic com-pound (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    .... Requirements as specified in § 721.80 (j) (use as an additive flame retardant for plastics) and (q). (iv... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Brominated aromatic com-pound (generic... Specific Chemical Substances § 721.775 Brominated aromatic com-pound (generic name). (a)...

  14. 40 CFR 721.775 - Brominated aromatic com-pound (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    .... Requirements as specified in § 721.80 (j) (use as an additive flame retardant for plastics) and (q). (iv... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Brominated aromatic com-pound (generic... Specific Chemical Substances § 721.775 Brominated aromatic com-pound (generic name). (a)...

  15. 40 CFR 721.775 - Brominated aromatic com-pound (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    .... Requirements as specified in § 721.80 (j) (use as an additive flame retardant for plastics) and (q). (iv... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Brominated aromatic com-pound (generic... Specific Chemical Substances § 721.775 Brominated aromatic com-pound (generic name). (a)...

  16. Spatial and temporal changes of chlorinated pesticides, PCBs, dioxins (PCDDs/PCDFs) and brominated flame retardants in human breast milk from Northern Russia.

    PubMed

    Polder, A; Gabrielsen, G W; Odland, J Ø; Savinova, T N; Tkachev, A; Løken, K B; Skaare, J U

    2008-02-25

    This study presents for the first time temporal changes of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) in Russian human breast milk samples. Concentrations of OCPs and PCBs in samples from three locations in the North West of Russia in 2000-2002 (n=42), were compared to corresponding levels measured in 1993-1996 (n=58). In addition brominated flame retardants (BFRs), consisting of polybrominated diphenylethers (PBDEs) (including BDE-209) and hexabromocyclododecane (HBCD) were analysed in samples from 2000-2002 (n=37). The present levels of SigmaDDTs and SigmaHCHs were 5 and 10 times higher than corresponding levels in the neighbouring country Norway. Median concentrations of SigmaHCHs (196 microg/kg lw), SigmaCHBs (19.7 microg/kg lw) and SigmaPCBs(16) (316 microg/kg lw) were highest in Murmansk. The percentage of p,p'-DDT to SigmaDDTs and ratio DDE/DDT suggest possible ongoing use of DDT in Russia. Levels of PBDE were low and dominated by the congeners BDE-47 and BDE-153. The deca brominated BDE-209 was detected in all analysed samples (median concentration 0.19 microg/kg lipid). Levels of SigmaOCPs and SigmaPCBs decreased 56 and 30% in Murmansk and 36 and 43% in Arkhangelsk during the study period. The decline of SigmaOCPs was significant at both locations (p<0.05-p<0.0001). For SigmaPCBs, the decreasing trend was only significant in Arkhangelsk (p<0.0001). In addition, a decline of Sigmatotal TEQs (SigmaTEQs of PCDDs/PCDFs, non-ortho- and mono-ortho PCBs) was observed in Murmansk and Arkhangelsk during the study period. The exposure of infants by PCDDs/PCDFs and dioxin-like PCBs is still exceeding the daily tolerable intake (TDI) in North West Russia. However, the concentrations of PCDDs/PCDFs and dioxin-like PCBs seem to decline very rapidly.

  17. 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.

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

    PubMed

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

    2015-10-01

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

  19. 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.

  20. Alkylphenol ethoxylates and brominated flame retardants in water, fish (carp) and sediment samples from the Vaal River, South Africa.

    PubMed

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

    2015-08-01

    Alkylphenol ethoxylates (APEs) and brominated flame retardants (BFRs) are known to be bio-accumulative, persistent, and endocrine disruptors and can cause adverse health effects in animals and humans. In this study, environmental samples were collected from sites along the Vaal River, South Africa in order to determine the concentrations of APEs and BFRs in water, sediment, and fish samples. The highest concentrations of these pollutants were observed from discharge of the Rietspruit WWTW. Measurable levels of both APEs and BFRs were observed with APEs exhibiting higher concentrations than BFRs in all the matrices. The concentrations observed for APEs and BFRs were as follows: 1.00-3.85 μg/L APEs, 0.09-0.26 μg/L PBDEs, ND- 0.14 PBBs and 0.51-1.77 μg/L HBCD for water samples; 47-63 ng/g lipid APEs, 3.24-12.4 ng/g lipid PBB, 4.63-33 ng/g lipid PBDEs and 10-13 ng/g lipid HBCD for fish; and 40-184 ng/g (wet weight (ww)) APEs, 2.93-5.9 ng/g (ww) PBB, 10-24 ng/g (ww) PBDEs, and 15-52 ng/g (ww) HBCD for sediment samples. The concentrations of APEs and BFRs in water samples were found to be in the range with the results reported in the literature while the concentration in fish and sediment were lower than the concentrations reported in other studies.

  1. 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.

  2. The widely utilized brominated flame retardant tetrabromobisphenol A (TBBPA) is a potent inhibitor of the SERCA Ca2+ pump

    PubMed Central

    Ogunbayo, Oluseye A.; Michelangeli, Francesco

    2007-01-01

    TBBPA (tetrabromobisphenol A) is currently the most widely used type of BFR (brominated flame retardant) employed to reduce the combustibility of a large variety of electronic and other manufactured products. Recent studies have indicated that BFRs, including TBBPA, are bio-accumulating within animal and humans. BFRs including TBBPA have also been shown to be cytotoxic and potentially endocrine-disrupting to a variety of cells in culture. Furthermore, TBBPA has specifically been shown to cause disruption of Ca2+ homoeostasis within cells, which may be the underlying cause of its cytotoxicity. In this study, we have demonstrated that TBBPA is a potent non-isoform-specific inhibitor of the SERCA (sarcoplasmic/endoplasmic reticulum Ca2+-ATPase) (apparent Ki 0.46–2.3 μM), thus we propose that TBBPA inhibition of SERCA contributes in some degree to Ca2+ signalling disruption. TBBPA binds directly to the SERCA without the need to partition into the phospholipid bilayer. From activity results and Ca2+-induced conformational results, it appears that the major effect of TBBPA is to decrease the SERCA affinity for Ca2+ (increasing the Kd from approx. 1 μM to 30 μM in the presence of 10 μM TBBPA). Low concentrations of TBBPA can quench the tryptophan fluorescence of the SERCA and this quenching can be reversed by BHQ [2,5-di-(t-butyl)-1,4-hydroquinone] and 4-n-nonylphenol, but not thapsigargin, indicating that TBBPA and BHQ may be binding to similar regions in the SERCA. PMID:17784851

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

    PubMed

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

    2016-06-01

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

  4. Alkylphenol ethoxylates and brominated flame retardants in water, fish (carp) and sediment samples from the Vaal River, South Africa.

    PubMed

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

    2015-08-01

    Alkylphenol ethoxylates (APEs) and brominated flame retardants (BFRs) are known to be bio-accumulative, persistent, and endocrine disruptors and can cause adverse health effects in animals and humans. In this study, environmental samples were collected from sites along the Vaal River, South Africa in order to determine the concentrations of APEs and BFRs in water, sediment, and fish samples. The highest concentrations of these pollutants were observed from discharge of the Rietspruit WWTW. Measurable levels of both APEs and BFRs were observed with APEs exhibiting higher concentrations than BFRs in all the matrices. The concentrations observed for APEs and BFRs were as follows: 1.00-3.85 μg/L APEs, 0.09-0.26 μg/L PBDEs, ND- 0.14 PBBs and 0.51-1.77 μg/L HBCD for water samples; 47-63 ng/g lipid APEs, 3.24-12.4 ng/g lipid PBB, 4.63-33 ng/g lipid PBDEs and 10-13 ng/g lipid HBCD for fish; and 40-184 ng/g (wet weight (ww)) APEs, 2.93-5.9 ng/g (ww) PBB, 10-24 ng/g (ww) PBDEs, and 15-52 ng/g (ww) HBCD for sediment samples. The concentrations of APEs and BFRs in water samples were found to be in the range with the results reported in the literature while the concentration in fish and sediment were lower than the concentrations reported in other studies. PMID:25869432

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

    PubMed

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

    2015-05-01

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

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

    PubMed

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

    2014-12-01

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

  7. 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.

  8. 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.

  9. 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. PMID:27364485

  10. The widely utilized brominated flame retardant tetrabromobisphenol A (TBBPA) is a potent inhibitor of the SERCA Ca2+ pump.

    PubMed

    Ogunbayo, Oluseye A; Michelangeli, Francesco

    2007-12-15

    TBBPA (tetrabromobisphenol A) is currently the most widely used type of BFR (brominated flame retardant) employed to reduce the combustibility of a large variety of electronic and other manufactured products. Recent studies have indicated that BFRs, including TBBPA, are bio-accumulating within animal and humans. BFRs including TBBPA have also been shown to be cytotoxic and potentially endocrine-disrupting to a variety of cells in culture. Furthermore, TBBPA has specifically been shown to cause disruption of Ca2+ homoeostasis within cells, which may be the underlying cause of its cytotoxicity. In this study, we have demonstrated that TBBPA is a potent non-isoform-specific inhibitor of the SERCA (sarcoplasmic/endoplasmic reticulum Ca2+-ATPase) (apparent K(i) 0.46-2.3 microM), thus we propose that TBBPA inhibition of SERCA contributes in some degree to Ca2+ signalling disruption. TBBPA binds directly to the SERCA without the need to partition into the phospholipid bilayer. From activity results and Ca2+-induced conformational results, it appears that the major effect of TBBPA is to decrease the SERCA affinity for Ca2+ (increasing the K(d) from approx. 1 microM to 30 microM in the presence of 10 microM TBBPA). Low concentrations of TBBPA can quench the tryptophan fluorescence of the SERCA and this quenching can be reversed by BHQ [2,5-di-(t-butyl)-1,4-hydroquinone] and 4-n-nonylphenol, but not thapsigargin, indicating that TBBPA and BHQ may be binding to similar regions in the SERCA.

  11. Transient aberration of neuronal development in the hippocampal dentate gyrus after developmental exposure to brominated flame retardants in rats.

    PubMed

    Saegusa, Yukie; Fujimoto, Hitoshi; Woo, Gye-Hyeong; Ohishi, Takumi; Wang, Liyun; Mitsumori, Kunitoshi; Nishikawa, Akiyoshi; Shibutani, Makoto

    2012-09-01

    We immunohistochemically investigated the impact and reversibility of three brominated flame retardants (BFRs) known to be weak thyroid hormone disruptors on neuronal development in the hippocampal formation and apoptosis in the dentate subgranular zone. Pregnant Sprague-Dawley rats were exposed to 10, 100, or 1,000 ppm decabromodiphenyl ether (DBDE); 100, 1,000 or 10,000 ppm tetrabromobisphenol A (TBBPA) or 1,2,5,6,9,10-hexabromocyclododecane (HBCD) in the diet from gestational day 10 through to day 20 after delivery (weaning). On postnatal day (PND) 20, interneurons in the dentate hilus-expressing reelin increased with all chemicals, suggestive of aberration of neuronal migration. However, this increase had disappeared by PND 77. NeuN-positive mature neurons increased in the hilus on PND 77 with all chemicals. In the subgranular zone on PND 20, an increase in apoptotic bodies suggestive of impaired neurogenesis was observed after exposure to TBBPA or HBCD. The effects on neuronal development were detected at doses of ≥100 ppm DBDE; ≥1,000 ppm TBBPA; and at least at 10,000 ppm HBCD. On PND 20, the highest dose of DBDE and HBCD revealed mild fluctuations in the serum concentrations of thyroid-related hormones suggestive of weak developmental hypothyroidism, while TBBPA did not. Thus, DBDE and TBBPA may exert direct effect on neuronal development in the brain, but hypothyroidism may be operated for DBDE and HBCD at high doses. An excess of mature neurons in the hilus at later stages may be the signature of the developmental effects of BFRs. However, the effect itself was reversible.

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

    PubMed

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

    2016-07-01

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

  13. 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.

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

    PubMed

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

    2015-05-01

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

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

    PubMed

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

    2015-01-01

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

  16. 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.

  17. 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.

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

    PubMed

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

    2015-01-01

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

  19. 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

  20. 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...

  1. 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.

  2. 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.

  3. 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

  4. Determination of brominated flame retardants in electrical and electronic equipments with microwave-assisted extraction and gas chromatography-mass spectrometry.

    PubMed

    Li, Ying; Wang, Tianran; Hashi, Yuki; Li, Haifang; Lin, Jin-Ming

    2009-06-15

    Determination of brominated flame retardants in electrical and electronic equipments (EEE) was achieved through microwave-assisted extraction (MAE) and gas chromatography-mass spectrometry. Polybrominated biphenyls (PBBs) and polybrominated diphenyl ethers (PBDEs) including mono-brominated through deca-brominated congeners were qualified and quantified with good linearity (0.9963-0.9998) and repeatability (RSD, 1.1-8.1%). Multivariable orthogonal experimental design was used to optimize the MAE parameters. Extraction temperature and time were the most significant factors for extraction process. The extractants were cleaned up with SPE method after extraction. Recoveries of spiked blank samples ranged from 72.4% to 108.4% for most of the analytes. The method was applied to the determination of PBBs and PBDEs in several kinds of real EEE samples. It was found that no detectable level of PBBs was detected among them. Different contents of PBDEs were tested in the tested samples and the total contents ranged from 25.0 ng g(-1) to 194.0 ng g(-1). The proposed approach demonstrated an environmentally friendly and convenient alternative, which only consumed 10mL hexane to microwave extraction for 10min at 100 degrees C. PMID:19362212

  5. [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.

  6. 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

  7. 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

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

    SciTech Connect

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

    2010-04-15

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

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

    PubMed Central

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

    2015-01-01

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

  10. 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.

  11. 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

  12. 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.

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

    PubMed

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

    2009-04-15

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

  14. Levels and trends of organochlorines and brominated flame retardants in ivory gull eggs from the Canadian Arctic, 1976 to 2004.

    PubMed

    Braune, Birgit M; Mallory, Mark L; Grant Gilchrist, H; Letcher, Robert J; Drouillard, Ken G

    2007-06-01

    The ivory gull (Pagophila eburnea) is a circumpolar marine bird which has recently been listed as an endangered species in Canada. To determine whether contaminants may be playing a role in the population decline of this species, ivory gull eggs collected in 1976, 1987 and 2004 from Seymour Island in the Canadian Arctic were analyzed for organochlorines, polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs. This study also provides the first account of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs) and polybrominated biphenyls (PBBs) in ivory gulls. The most quantitatively abundant legacy organochlorines found in the ivory gull eggs were p,p'-DDE, SigmaPCB and oxychlordane. Concentrations of the organochlorines analyzed either decreased or showed little change between 1976 and 2004. Concentrations of SigmaPCDD in ivory gull eggs were greater than SigmaPCDF, and the non-ortho PCBs (primarily PCB-126) contributed the largest fraction to the total TEQ value in all years sampled. Concentrations of PCDDs, PCDFs and SigmaTEQ decreased from 1976 to 2004. In contrast, concentrations of the PBDEs steadily increased between 1976 and 2004 driven primarily by increases in BDE-47. Although concentrations of the persistent chlorinated compounds (i.e. organochlorine pesticides, PCBs, PCDDs, PCDFs) reported in this study were below published toxicological threshold values for eggs of wild birds, we cannot rule out the possibility of synergistic/additive, sublethal effects. Very few studies have been carried out to evaluate the exposure-effect relationship of the persistent brominated compounds in avian species. Given the scarcity of information on toxicity threshold levels for PBBs and PBDEs in avian species, coupled with the trend toward increasing concentrations in ivory gulls, continued monitoring and further toxicological studies of these compounds are warranted.

  15. Levels and trends of organochlorines and brominated flame retardants in ivory gull eggs from the Canadian Arctic, 1976 to 2004.

    PubMed

    Braune, Birgit M; Mallory, Mark L; Grant Gilchrist, H; Letcher, Robert J; Drouillard, Ken G

    2007-06-01

    The ivory gull (Pagophila eburnea) is a circumpolar marine bird which has recently been listed as an endangered species in Canada. To determine whether contaminants may be playing a role in the population decline of this species, ivory gull eggs collected in 1976, 1987 and 2004 from Seymour Island in the Canadian Arctic were analyzed for organochlorines, polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and non-ortho PCBs. This study also provides the first account of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs) and polybrominated biphenyls (PBBs) in ivory gulls. The most quantitatively abundant legacy organochlorines found in the ivory gull eggs were p,p'-DDE, SigmaPCB and oxychlordane. Concentrations of the organochlorines analyzed either decreased or showed little change between 1976 and 2004. Concentrations of SigmaPCDD in ivory gull eggs were greater than SigmaPCDF, and the non-ortho PCBs (primarily PCB-126) contributed the largest fraction to the total TEQ value in all years sampled. Concentrations of PCDDs, PCDFs and SigmaTEQ decreased from 1976 to 2004. In contrast, concentrations of the PBDEs steadily increased between 1976 and 2004 driven primarily by increases in BDE-47. Although concentrations of the persistent chlorinated compounds (i.e. organochlorine pesticides, PCBs, PCDDs, PCDFs) reported in this study were below published toxicological threshold values for eggs of wild birds, we cannot rule out the possibility of synergistic/additive, sublethal effects. Very few studies have been carried out to evaluate the exposure-effect relationship of the persistent brominated compounds in avian species. Given the scarcity of information on toxicity threshold levels for PBBs and PBDEs in avian species, coupled with the trend toward increasing concentrations in ivory gulls, continued monitoring and further toxicological studies of these compounds are warranted. PMID:17412396

  16. 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.

  17. 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.

  18. 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.

  19. 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. PMID:25797475

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

    PubMed

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

    2016-06-01

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

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

    PubMed

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

    2016-06-01

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

  2. 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. PMID:24040839

  3. Relevance of BFRs and thermal conditions on the formation pathways of brominated and brominated-chlorinated dibenzodioxins and dibenzofurans.

    PubMed

    Weber, Roland; Kuch, Bertram

    2003-09-01

    The widespread use of brominated flame-retarded products in the last two decades has resulted in an increasing presence of bromine in thermal processes such as waste combustion and accidental fires. Brominated and brominated-chlorinated dibenzodioxins and dibenzofurans (PBDDs/PBDFs, PXDDs/PXDFs) are micropollutants of concern arising from such processes. The present review aims to evaluate the relevance of these compound classes in actual thermal processes. Four categories of thermal processes are discussed in this respect according to their potential for PBDD/PBDF and PXDD/PXDF generation: thermal stress, pyrolysis/gasification, insufficient combustion conditions and controlled combustion conditions. Under thermal stress situations, as they may occur in production or recycling processes, PBDDs/PBDFs precursors like polybrominated diphenylethers (PBDE) can have a relevant potential for PBDD/PBDF formation via a simple elimination. Under insufficient combustion conditions as they are present in, e.g. accidental fires and uncontrolled burning as well as gasification/pyrolysis processes, considerable amounts of PBDDs/PBDFs can be formed from BFRs, preferably via the precursor pathway. In contrast, under controlled combustion conditions, BFRs and PBDDs/PBDFs can be destroyed with high efficiency. The relevance of de novo synthesis of PXDDs/PXDFs is discussed for this condition. Providing a basis for the understanding of PXDD/PXDF formation in actual thermal processes, the present paper also summarises the formation pathways of brominated and brominated-chlorinated PXDDs/PXDFs from brominated flame retardants (BFRs) investigated during laboratory thermolysis experiments. Relevant mechanistic steps for PBDD/PBDF formation from brominated precursors are discussed including elimination reactions, condensation steps and debromination/hydrogenation reactions. In addition, chlorination/bromination and halogen exchange reactions are briefly discussed with respect for their

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

    PubMed Central

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

    2015-01-01

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

  5. 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.

  6. 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.

  7. 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

    2014-11-01

    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.

  8. 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

    2014-11-01

    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. PMID:25272197

  9. effect of hydrogen addition and burner diameter on the stability and structure of lean, premixed flames

    NASA Astrophysics Data System (ADS)

    Kaufman, Kelsey Leigh

    Low swirl burners (LSBs) have gained popularity in heating and gas power generation industries, in part due to their proven capacity for reducing the production of NOx, which in addition to reacting to form smog and acid rain, plays a central role in the formation of the tropospheric ozone layer. With lean operating conditions, LSBs are susceptible to combustion instability, which can result in flame extinction or equipment failure. Extensive work has been performed to understand the nature of LSB combustion, but scaling trends between laboratory- and industrial-sized burners have not been established. Using hydrogen addition as the primary method of flame stabilization, the current work presents results for a 2.54 cm LSB to investigate potential effects of burner outlet diameter on the nature of flame stability, with focus on flashback and lean blowout conditions. In the lean regime, the onset of instability and flame extinction have been shown to occur at similar equivalence ratios for both the 2.54 cm and a 3.81 cm LSB and depend on the resolution of equivalence ratios incremented. Investigations into flame structures are also performed. Discussion begins with a derivation for properties in a multicomponent gas mixture used to determine the Reynolds number (Re) to develop a condition for turbulent intensity similarity in differently-sized LSBs. Based on this requirement, operating conditions are chosen such that the global Reynolds number for the 2.54 cm LSB is within 2% of the Re for the 3.81 cm burner. With similarity obtained, flame structure investigations focus on flame front curvature and flame surface density (FSD). As flame structure results of the current 2.54 cm LSB work are compared to results for the 3.81 cm LSB, no apparent relationship is shown to exist between burner diameter and the distribution of flame surface density. However, burner diameter is shown to have a definite effect on the flame front curvature. In corresponding flow conditions, a

  10. FLame

    1995-03-03

    FLAME is data processing software explicitly written to support the ACAP software of DSP Technologies, Inc., of Fremont, CA. ACAP acquires and processes in-cylinder pressure data for reciprocating engines. However, it also has the capability to acquire data for two Sandia-developed technologies, ionization-probe instrumented head gaskets and fiber-optic instrumented spark plugs. FLAME post processes measurements of flame arrival from data files aquired with ACAP. Flame arrival time is determined from analog ionization-probe or visible-emission signals.more » The resulting data files are integrated with the standard ACAP files, providing a common data base for engine development.« less

  11. Estimation of physicochemical properties of 52 non-PBDE brominated flame retardants and evaluation of their overall persistence and long-range transport potential.

    PubMed

    Kuramochi, Hidetoshi; Takigami, Hidetaka; Scheringer, Martin; Sakai, Shin-Ichi

    2014-09-01

    Non-PBDE (polybromodiphenyl ether) brominated flame retardants (BFRs) used as alternatives to PBDEs should be evaluated in terms of their environmental contamination potential. We first used two well-known estimation tools, EPI Suite and SPARC, to estimate the physicochemical properties of 52 non-PBDE BFRs. We assessed the dependence of the properties on the molecular weight and chemical structure of the compounds. The accuracy of the estimates was evaluated by comparing results with previous experimental data. In the case of EPI Suite, we have recommended an appropriate calculation method for the air-water partition coefficient. Half-lives in each environmental medium were also estimated with EPI Suite. Based on the estimated properties and half-lives, the overall persistence (Pov) and long-range transport potential (LRTP) of the BFRs were calculated using the Organization for Economic Cooperation and Development Pov and LRTP Screening Tool. We selected some POP-like chemicals from among the non-PBDE BFRs on the basis of their Pov and LRTP. From a Monte Carlo analysis of the calculated results for the selected BFRs, we suggest physicochemical properties to be measured in the future. PMID:24802073

  12. Multi-year air monitoring of legacy and current-use brominated flame retardants in an urban center in northeastern China.

    PubMed

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

    2016-11-15

    The occurrence and temporal trends of polybrominated diphenyl ethers (PBDEs) and non-PBDE brominated flame retardants (NBFRs) were investigated in an urban atmosphere of Northeast China in consecutive six years (2008-2013). Among all chemicals, BDE-209, l,2,5,6,9,10-hexabromocyclododecane (HBCD), and decabromodiphenylethane (DBDPE) were the three most dominant compounds. During the period, the levels of pentabromodiphenyl ethers in the gas-phase and octabromodiphenyl ethers in the particle-phase significantly decreased, while the levels of BDE-209 and NBFRs increased in either the gas-phase or particle-phase. Ambient temperature was the most significant variable that influenced the gas-phase and particle-phase concentrations of BFRs, followed by wind speed and relative humidity. A stronger temperature dependence of the atmospheric concentrations was found for lower mass BFRs. Gas-particle partitioning studies suggested PBDEs in the urban atmosphere of Northeast China were at steady-state. Steady-state equation can also well describe the partitioning behavior for NBFRs, suggesting that the atmospheric partitioning behaviors of NBFRs were similar to those of PBDEs.

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

    PubMed

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

    2016-07-01

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

  14. 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.

  15. 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.

  16. 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

  17. 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. PMID:25820830

  18. 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.

  19. New priority substances of the European Water Framework Directive: biocides, pesticides and brominated flame retardants in the aquatic environment of Denmark.

    PubMed

    Vorkamp, Katrin; Bossi, Rossana; Bester, Kai; Bollmann, Ulla E; Boutrup, Susanne

    2014-02-01

    The biocides cybutryn (Irgarol) and terbutryn, the herbicides aclonifen and bifenox, the insecticides cypermethrin and heptachlor/heptachlor epoxide and the brominated flame retardant hexabromocyclododecane (HBCD) are new priority substances of the Water Framework Directive of the European Union. In order to gain knowledge about their presence in the aquatic environment in an off-season situation with regard to pesticide and biocide applications, these substances were analysed in freshwater, seawater and fish samples from Denmark. Aclonifen, bifenox, cypermethrin and heptachlor were below the limits of detection (LODs) in all samples. However, the LODs for cypermethrin and heptachlor exceeded the annual average environmental quality standards (AA-EQSs). Cybutryn, terbutryn, heptachlor epoxide and HBCD were detected in the majority of samples, with detection frequencies of 100% for heptachlor epoxide and HBCD in water and 90% in fish. No concentration was above maximum allowable concentration (MAC)-EQS values, but AA-EQS values were exceeded for all four compounds by several samples, including 100% of the water samples with regard to heptachlor epoxide. Methodological issues remain for cypermethrin, and to a certain extent for heptachlor/heptachlor epoxide, for which water LODs were above AA-EQSs although a water volume of 12L was combined with very sensitive high resolution mass spectrometry.

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

    PubMed

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

    2016-07-01

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

  1. Multi-year air monitoring of legacy and current-use brominated flame retardants in an urban center in northeastern China.

    PubMed

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

    2016-11-15

    The occurrence and temporal trends of polybrominated diphenyl ethers (PBDEs) and non-PBDE brominated flame retardants (NBFRs) were investigated in an urban atmosphere of Northeast China in consecutive six years (2008-2013). Among all chemicals, BDE-209, l,2,5,6,9,10-hexabromocyclododecane (HBCD), and decabromodiphenylethane (DBDPE) were the three most dominant compounds. During the period, the levels of pentabromodiphenyl ethers in the gas-phase and octabromodiphenyl ethers in the particle-phase significantly decreased, while the levels of BDE-209 and NBFRs increased in either the gas-phase or particle-phase. Ambient temperature was the most significant variable that influenced the gas-phase and particle-phase concentrations of BFRs, followed by wind speed and relative humidity. A stronger temperature dependence of the atmospheric concentrations was found for lower mass BFRs. Gas-particle partitioning studies suggested PBDEs in the urban atmosphere of Northeast China were at steady-state. Steady-state equation can also well describe the partitioning behavior for NBFRs, suggesting that the atmospheric partitioning behaviors of NBFRs were similar to those of PBDEs. PMID:27401280

  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. PMID:26889790

  3. Comparative antioxidant status in freshwater fish Carassius auratus exposed to six current-use brominated flame retardants: a combined experimental and theoretical study.

    PubMed

    Feng, Mingbao; Qu, Ruijuan; Wang, Chao; Wang, Liansheng; Wang, Zunyao

    2013-09-15

    Decabromodiphenyl ether (BDE-209) and several non-polybrominated diphenyl ether (PBDE) brominated flame retardants (BFRs), such as tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB) and pentabromotoluene (PBT), are persistent halogenated contaminants ubiquitously detected in aquatic systems. However, data on comparative toxicological effects of these BFRs are lacking for fish. In this study, a combined experimental and theoretical approach was used to compare and analyze the effects of these BFRs on biochemical biomarkers in liver of Carassius auratus injected intraperitoneally with different doses (10 and 100mg/kg) for 7, 14 and 30 days. Oxidative stress was evoked evidently for the prolonged exposure, represented by the significantly altered indices (superoxide dismutase, catalase, glutathione peroxidase, reduced glutathione, and malondialdehyde). The integrated biomarker response (IBR) index ranked biotoxicity as: PBT>HBB>HBCD>TBBPA>BDE-209>DBDPE. Quantum chemical calculations (electronic parameters, frontier molecular orbitals, and Wiberg bond order) were performed for theoretical analysis. Notably, some descriptors were correlated with the toxicity order, probably implying the existence of a potential structure-activity relationship when more BFRs were included. Besides, theoretical calculations also provided some valuable information regarding the molecular characteristics and metabolic pathways of these current-use BFRs, which may facilitate the understanding on their environmental behavior and fate. Overall, this study adopted a combined experimental and theoretical method for the toxicological determination and analysis of the BFRs, which may also be considered in future ecotoxicological studies. PMID:23880106

  4. Novel combined stir bar sorptive extraction coupled with ultrasonic assisted extraction for the determination of brominated flame retardants in environmental samples using high performance liquid chromatography.

    PubMed

    Yu, Chunhe; Hu, Bin

    2007-08-10

    A combined stir bar coated with poly (dimethysiloxane)-beta-cyclodextrin (PDMS-beta-CD) on single side has been prepared for the first time by sol-gel method and was coupled with ultrasonic assisted extraction (UAE) for the determination of some brominated flame-retardant compounds (BFRs) in soil and dust samples by high performance liquid chromatography (HPLC). Four different kinds of coatings including PDMS-beta-CD, PDMS, carbowax (CW)-PDMS-poly (vinyl alcohol) (PVA) and PDMS-PVA were evaluated for stir bar sorptive extraction of BFRs by orthogonal experiment design. The experimental results reveal that the PDMS-beta-CD combined stir bar exhibited the best extraction efficiency for the target analytes. The reproducibility for the preparation of PDMS-beta-CD combined stir bar ranged from 1.3% to 15.7% in one batch, and 7.2% to 15.1% among batches. Extraction time, desorption solvent, concentration of methanol and NaCl in the matrix, pH, temperature and stirring speed were optimized. The combined stir bar can avoid direct friction of the coating with the bottom of the vessel, and could be used for more than 100 times. Linearity (>0.993), repeatability (<10.5%), reproducibility (<16.5%), recovery (56-118%) and detection limits (2.9-4.2 microg L(-1)) were proper to determine the seven BFRs. The developed method was applied to the determination of BFRs in soil and dust with satisfactory results. PMID:17561025

  5. 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.

  6. 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 (

  7. Effect of Brazilian Propolis on Exacerbation of Respiratory Syncytial Virus Infection in Mice Exposed to Tetrabromobisphenol A, a Brominated Flame Retardant

    PubMed Central

    Takeshita, Tomomi; Toyama, Satomi; Hayashi, Yuya; Honda, Shiori; Sakamoto, Shuichi; Matsuoka, Sayuri; Hidaka, Muneaki; Tsutsumi, Shigetoshi; Yasukawa, Ken; Park, Yong Kun

    2013-01-01

    Tetrabromobisphenol A (TBBPA), a brominated flame retardant, has been found to exacerbate pneumonia in respiratory syncytial virus- (RSV-) infected mice. We examined the effect of Brazilian propolis (AF-08) on the exacerbation of RSV infection by TBBPA exposure in mice. Mice were fed a powdered diet mixed with 1% TBBPA alone, 0.02% AF-08 alone, or 1% TBBPA and 0.02% AF-08 for four weeks and then intranasally infected with RSV. TBBPA exposure increased the pulmonary virus titer and level of IFN-γ, a representative marker of pneumonia due to RSV infection, in the lungs of infected mice without toxicity. AF-08 was significantly effective in reducing the virus titers and IFN-γ level increased by TBBPA exposure. Also, AF-08 significantly reduced proinflammatory cytokine (TNF-α and IL-6) levels in the lungs of RSV-infected mice with TBBPA exposure, but Th2 cytokine (IL-4 and IL-10) levels were not evidently increased. Neither TBBPA exposure nor AF-08 treatment affected the anti-RSV antibody production in RSV-infected mice. In flow cytometry analysis, AF-08 seemed to be effective in reducing the ratio of pulmonary CD8a+ cells in RSV-infected mice with TBBPA exposure. TBBPA and AF-08 did not exhibit anti-RSV activity in vitro. Thus, AF-08 probably ameliorated pneumonia exacerbated by TBBPA exposure in RSV-infected mice by limiting excess cellular immune responses. PMID:24250719

  8. 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.

  9. 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

  10. 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

  11. The effects of ferrocene addition on soot particle inception and growth in premixed ethylene flames

    SciTech Connect

    Ritrievi, K.E.; Longwell, J.P.; Sarofim, A.F.

    1987-10-01

    The effects of the addition of dicyclopentadienyl iron, ferrocene, on soot particle inception and growth were studied in atmospheric pressure, premixed ethylene flames with C/O = 0.71-0.83 at 0.015-0.46% ferrocene by weight of the fuel. The rate of surface growth of soot in undoped and doped flames was measured using laser light scattering and light extinction techniques to determine the particle size and number density as a function of residence time in the flame. The final soot yields in the ferrocene doped flames were enhanced by factors of 13.5-1.2 over the range of flame C/O ratios studied. This enhancement decreased with increasing C/O ratio for the same concentration of iron in the flames. The spatial distribution of the elements iron and carbon in the particles was determined with Auger spectroscopy. The iron was found to be concentrated in the cores of the particles. The results of a steady-state one-dimensional nucleation model which indicated that the iron oxide particles would nucleate well in advance of the soot inception time were consistent with this elemental stratification and the observation of the onset of carbon deposition in doped flames at earlier residence times than in undoped flames of the same C/O ratio. The iron oxide particle sizes and number densities predicted from the model indicated that these particles were both numerous and small enough to be seed particles on which carbon deposition could take place. The importance of the activity of the surfaces of the solid in determining the rate of surface growth of soot was investigated.

  12. 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.

  13. Investigation of fuel-additive effects on sooting flames. Annual report

    SciTech Connect

    Bonczyk, P.A.

    1987-06-30

    The objective of this research is to clarify the mechanisms responsible for the suppression of soot in flames by fuel additives. Measurements are limited to well-defined hydrocarbon/air prevaporized liquid- and gaseous-fueled flames. Emphasis is given to ferrocene in a diffusion flame fueled by prevaporized iso-octane. Nonperturbing laser/optical diagnostic techniques are used to relate changes in soot particulate size, number density, and volume fraction to additive concentration. Ferrocene is observed to suppress a visible soot plume completely and, in general, to intervene at a late combustion stage. Suppression is due to both size and number density reduction, which suggests that ferrocene enhances the oxidative burn-out of soot. In contrast, at an early combustion stage nearer the burner lip, a slight enhancement of soot observed with ferrocene seeding.

  14. 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...

  15. Releasing-addition method for the flame-photometric determination of calcium in thermal waters

    USGS Publications Warehouse

    Rowe, J.J.

    1963-01-01

    Study of the interferences of silica and sulfate in the flame-photometric determination of calcium in thermal waters has led to the development of a method requiring no prior chemical separations. The interference effects of silica, sulfate, potassium, sodium, aluminum, and phosphate are overcome by an addition technique coupled with the use of magnesium as a releasing agent. ?? 1963.

  16. Estimated intakes of brominated flame retardants via diet and dust compared to internal concentrations in a Swedish mother-toddler cohort.

    PubMed

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

    2015-06-01

    Tri-decabrominated diphenyl ethers (tri-decaBDEs), isomer-specific hexabromocyclododecanes (HBCDs) and 14 emerging brominated flame retardants (EBFRs) were determined in Swedish market basket samples, two pooled breast milk samples and house dust collected in homes of first-time mothers. Daily dietary and dust intakes were estimated for the mothers and their toddlers and compared to previously reported levels in serum of both the mothers and toddlers and in feces of the toddlers (n=20). Diet was the main contributor for intake of ΣpentaBDE and α-tetrabromoethylcyclohexane (DBE-DBCH) for both mothers and toddlers. For ΣoctaBDE, ΣHBCD and pentabromobenzene (PBBz), dietary intake was more important for mothers while house dust ingestion was more important for toddlers. House dust was the main exposure route for ΣdecaBDE, decabromodiphenyl ethane (DBDPE), 2-ethylhexyl-2,3,4,5-tetrabromobenzoate (EH-TBB), bis(2-ethylhexyl)tetrabromophthalate (BEH-TEBP), bis(2,4,6-tribromophenoxy) ethane (BTBPE) and pentabromotoluene (PBT) for both mothers and toddlers. Significant correlations (Spearmans, α<0.05) were found between the mothers' BDE serum concentrations and their consumption of meat and fish while no correlations were found between BFR dietary intake and serum or feces concentrations in toddlers. Octa-decaBDE congener concentrations in serum and feces of toddlers were significantly correlated to those in house dust. BDE-207 and -208 concentrations in serum of mothers were significantly correlated with the nonaBDEs in house dust. The correlations between house dust and internal concentrations and comparison of the house dust and dietary contributions to the estimated daily intakes suggest that dust exposure plays a larger role for the octa-decaBDE body burden in toddlers than in their mothers.

  17. Pollution profiles and risk assessment of PBDEs and phenolic brominated flame retardants in water environments within a typical electronic waste dismantling region.

    PubMed

    Xiong, Jukun; An, Taicheng; Zhang, Chaosheng; Li, Guiying

    2015-06-01

    The aim of this study was to assess the pollution profiles of various typical brominated flame retardants in water and surface sediment near a typical electronic waste dismantling region in southern China. We found that polybrominated diphenyl ethers (PBDEs), 2,4,6-tribromophenol (TBP), pentabromophenol (PeBP), tetrabromobisphenol A (TBBPA), and bisphenol A (BPA) were ubiquitous in the water and sediment samples collected in the study region. In water, Σ19PBDEs (sum of all 20 PBDE congeners studied except BDE-209, which was below the detection limit) levels ranged from 0.31 to 8.9 × 10(2) ng L(-1). TBP, PeBP, TBBPA, and BPA concentrations in the water samples ranged from not being detectable (nd-under the detection limit) to 3.2 × 10(2) (TBP), from nd to 37 (PeBP), from nd to 9.2 × 10(2) (TBBPA) and from nd-8.6 × 10(2) ng L(-1) (BPA). In sediment, Σ19PBDEs ranged from nd to 5.6 × 10(3) ng g(-1), while BDE-209 was the predominant congener, with a range of nd to 3.5 × 10(3) ng g(-1). Tri- to hepta-BDE concentrations were significantly (p < 0.01) correlated with each other, except for BDE-71 and BDE-183, and octa- to nona-BDEs concentrations were significantly (p < 0.05) correlated with each other, except for BDE-208. BDE-209 was not significantly correlated with tri- to nona-BDEs. Risk assessments indicated that the water and sediment across the sampling sites posed no estrogenic risk. However, different eco-toxicity risk degrees at three trophic levels did exist at most sampling sites.

  18. In silico and biological analysis of anti-androgen activity of the brominated flame retardants ATE, BATE and DPTE in zebrafish.

    PubMed

    Pradhan, Ajay; Asnake, Solomon; Kharlyngdoh, Joubert Banjop; Modig, Carina; Olsson, Per-Erik

    2015-05-25

    The brominated flame retardants (BFRs) 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH or DBE-DCBH) and allyl 2,4,6-tribromophenyl ether (ATE or TBP-AE) are alternative BFRs that have been introduced to replace banned BFRs. TBECH is a potential endocrine disrupter in human, chicken and zebrafish and in a recent study we showed that ATE, along with the structurally similar BFR 2,3-dibromopropyl 2,4,6-tribromophenyl ether (DPTE or TBP-DBPE) and its metabolite 2-bromoallyl 2,4,6-tribromophenyl ether (BATE or TBP-BAE) are potential endocrine and neuronal disrupters in human. In this study we analyzed ATE, BATE and DPTE for zebrafish androgen receptor (zAR) modulating properties. In silico analysis with two softwares, Molecular Operating Environment (MOE) and Internal Coordinate Mechanics (ICM), showed that ATE, BATE and DPTE bind to zAR. In vitro AR activation assay revealed that these three BFRs down-regulate 11-ketotestosterone (KT) mediated zAR activation. Exposure to 10 μM DPTE resulted in reduced hatching success and like TBECH, BATE and DPTE at 10 μM also had teratogenic properties with 20% and 50% back-bone curvature respectively. Gene transcription analysis in zebrafish embryos as well as in juveniles showed down-regulation of the androgen receptor and androgen response genes, which further support that these BFRs are androgen antagonists and potential endocrine disrupting compounds. Genes involved in steroidogenesis were also down-regulated by these BFRs. In view of this, the impact of these BFRs on humans and wildlife needs further analysis.

  19. In silico and biological analysis of anti-androgen activity of the brominated flame retardants ATE, BATE and DPTE in zebrafish.

    PubMed

    Pradhan, Ajay; Asnake, Solomon; Kharlyngdoh, Joubert Banjop; Modig, Carina; Olsson, Per-Erik

    2015-05-25

    The brominated flame retardants (BFRs) 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH or DBE-DCBH) and allyl 2,4,6-tribromophenyl ether (ATE or TBP-AE) are alternative BFRs that have been introduced to replace banned BFRs. TBECH is a potential endocrine disrupter in human, chicken and zebrafish and in a recent study we showed that ATE, along with the structurally similar BFR 2,3-dibromopropyl 2,4,6-tribromophenyl ether (DPTE or TBP-DBPE) and its metabolite 2-bromoallyl 2,4,6-tribromophenyl ether (BATE or TBP-BAE) are potential endocrine and neuronal disrupters in human. In this study we analyzed ATE, BATE and DPTE for zebrafish androgen receptor (zAR) modulating properties. In silico analysis with two softwares, Molecular Operating Environment (MOE) and Internal Coordinate Mechanics (ICM), showed that ATE, BATE and DPTE bind to zAR. In vitro AR activation assay revealed that these three BFRs down-regulate 11-ketotestosterone (KT) mediated zAR activation. Exposure to 10 μM DPTE resulted in reduced hatching success and like TBECH, BATE and DPTE at 10 μM also had teratogenic properties with 20% and 50% back-bone curvature respectively. Gene transcription analysis in zebrafish embryos as well as in juveniles showed down-regulation of the androgen receptor and androgen response genes, which further support that these BFRs are androgen antagonists and potential endocrine disrupting compounds. Genes involved in steroidogenesis were also down-regulated by these BFRs. In view of this, the impact of these BFRs on humans and wildlife needs further analysis. PMID:25818047

  20. Optimization and Simultaneous Determination of Alkyl Phenol Ethoxylates and Brominated Flame Retardants in Water after SPE and Heptafluorobutyric Anhydride Derivatization followed by GC/MS.

    PubMed

    Chokwe, Tlou B; Okonkwo, Jonathan O; Sibali, Linda L; Ncube, Esper J

    2012-10-01

    A gas chromatography-mass spectrometry (GC-MS) method was investigated for the simultaneous analysis of two types of endocrine disrupting compounds (EDCs), i.e., alkylphenol ethoxylates and brominated flame retardants (BFRs), by extraction and derivatization followed by GC-MS. Different solid phase extraction (SPE) cartridges (Cleanert PestiCarb, C18, Cleanert-SAX and Florosil), solvents (toluene, tetrahydrofuran, acetone, acetonitrile and ethyl acetate) and bases (NaHCO3, triethylamine and pyridine) were tested and the best chromatographic analysis was achieved by extraction with Strata-X (33 μm, Reverse Phase) cartridge and derivatization with heptafluorobutyric anhydride at 55 °C under Na2CO3 base in hexane. It was observed that APE together with lower substituted PBBs (PBB1, PBB10, PBB18 and PBB49), HBCD and TBBPA can be determined simultaneously under the same GC conditions. This simple and reliable analytical method was applied to determining trace amounts of these compounds from wastewater treatment plant samples. The recoveries of the target compounds from simulated water were above 60 %. The limit of detection ranged from 0.01 to 0.15 μg L(-1) and the limit of quantification ranged from 0.05 to 0.66 μg L(-1). There were no appreciable differences between filtered and unfiltered wastewater samples from Leeuwkil treatment plant although concentration of target analytes in filtered influent was slightly lower than the concentration of target analytes in unfiltered influent water. The concentrations of the target compounds from the wastewater treatment were determined from LOQ upwards. PMID:23864736

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

    PubMed

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

    2014-01-01

    Because of the reduction in the use of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD), novel brominated flame retardants (NBFRs), including 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), decabromodiphenyl ethane (DBDPE), hexabromobenzene (HBB), and pentabromoethylbenzene (PBEB), started to be marketed as alternatives to the banned formulations. In this study, the spatial distribution and accumulation of NBFRs, PBDEs, and HBCD in the biota have been investigated in the littoral compartment of a large and deep subalpine lake (Lake Maggiore, Northern Italy), using zebra mussel Dreissena polymorpha and roach (Rutilus rutilus) as bioindicators. To our knowledge, this is the first study reporting the contamination of NBFRs in the freshwater invertebrate D. polymorpha. Contamination of zebra mussel due to PBEB, HBB, and BTBPE was low, ranging from 0.9 to 2.9 ng/g lipid weight, from 1.1 to 2.9 ng/g l.w., and from 3.5 to 9.5 ng/g l.w., respectively. PBEB and BTBPE in roach were always below the detection limit, while the contamination of HBB ranged from < limits of detection (LOD) to 1.74 ng/g l.w., indicating a weak contamination. DBDPE was < LOD in all the considered biological samples. Finally, HBCD was detected in all organic tissues with mean concentrations up to 74.4 ng/g l.w. PBDE results, supported by principal component analysis elaboration, suggested a possible contamination due to the congeners composing the penta- and deca-BDE technical formulations, which are present in the Lake Maggiore basin. The biomagnification factor values showed that tetra- and penta-BDE biomagnified, while octa-, nona-, and deca-BDE were still bioavailable and detectable in the fish muscles, but they do not biomagnified. Considering the other BFRs, only HBCD showed a moderate biomagnification potential. PMID:24756669

  2. 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.

  3. Brominated flame retardants in house dust from e-waste recycling and urban areas in South China: implications on human exposure.

    PubMed

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

    2010-08-01

    Brominated flame retardants (BFRs) were examined in house dust from the electronic waste (e-waste) recycling and urban areas of South China. The concentrations of polybrominated diphenyl ethers (PBDEs) were in the range of 227-160,000 ng/g in the e-waste recycling area and 530-44,000 ng/g in the urban area. These values were much higher than other BFRs, except for novel decabromodiphenyl ethane (DBDPE) whose value of 100-47,000 ng/g was dominant in approximately 1/4 of the samples from the urban area. Urban dust PBDE levels were generally higher than those in many European and Asian countries and comparable to the values found in North America. Urban dust DBDPE levels were higher than those of other areas in the world. The distinct dust BFR profiles observed in the two studied areas were reflective of activities in these areas (electronics industry vs. e-waste recycling). The presence of BDE202, as well as the BDE197 to BDE201 and the nona-BDEs to deca-BDE ratios in the dust samples from the studied areas were probably indicative of environmental degradation of deca-BDE. The estimated daily intakes (EDIs) of average adult and toddler via house dust ranged from 37.0 to 304 ng/day for PBDEs and from 3.01 to 87.6 ng/day for all other BFRs in the studied areas. The EDIs via house dust were much higher than those via other indoor pathways (air, fish, human milk, and toys). Despite the potentially low deleterious risk of PBDE exposure via house dust as suggested by the hazard quotients, this exposure pathway should be of great concern because of the higher BFR exposures for children and the presence of other BFRs (such as DBDPE) which have not yet been fully investigated. PMID:20452672

  4. Changes in spontaneous behaviour and altered response to nicotine in the adult rat, after neonatal exposure to the brominated flame retardant, decabrominated diphenyl ether (PBDE 209).

    PubMed

    Viberg, Henrik; Fredriksson, Anders; Eriksson, Per

    2007-01-01

    Polybrominated diphenyl ethers (PBDEs), which are used as flame retardants, have recently been shown to increase in the environment and in human milk, which is also true for the decabrominated congener, 2,2',3,3',4,4',5,5',6,6'-decaBDE (PBDE 209). We have recently reported that neonatal exposure to PBDE 209 can induce persistent aberrations in spontaneous behaviour, in mice, effects that get worse with age. Other PBDE congeners affect learning and memory functions and the cholinergic system in adult mice and rats. The present study indicates that spontaneous behaviour, along with the cholinergic system during its developing stage, can be targets for PBDE 209 in the rat. Neonatal oral exposure of male Sprague-Dawley rats, on postnatal day 3, to 6.7, and 20.1 mg PBDE 209/kg body weight, was shown to disrupt normal spontaneous behaviour at 2 months of age. Also, rats exposed to the high dose of PBDE 209 showed a different response to adult nicotine treatment, compared to control rats. These findings show similarities to observations made from neonatal exposure of rats or mice to 2,2',4,4',5-pentaBDE (PBDE 99), 2,2',4,4',5,5'-hexaBDE (PBDE 153) and certain PCBs, compounds shown to affect both spontaneous behaviour and the cholinergic system. It is also clear from the present study and from recent studies from our research group that both lower and higher brominated diphenyl ethers can cause similar developmental neurotoxic effects in both mice and rats. PMID:17030062

  5. Brominated flame retardants in house dust from e-waste recycling and urban areas in South China: implications on human exposure.

    PubMed

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

    2010-08-01

    Brominated flame retardants (BFRs) were examined in house dust from the electronic waste (e-waste) recycling and urban areas of South China. The concentrations of polybrominated diphenyl ethers (PBDEs) were in the range of 227-160,000 ng/g in the e-waste recycling area and 530-44,000 ng/g in the urban area. These values were much higher than other BFRs, except for novel decabromodiphenyl ethane (DBDPE) whose value of 100-47,000 ng/g was dominant in approximately 1/4 of the samples from the urban area. Urban dust PBDE levels were generally higher than those in many European and Asian countries and comparable to the values found in North America. Urban dust DBDPE levels were higher than those of other areas in the world. The distinct dust BFR profiles observed in the two studied areas were reflective of activities in these areas (electronics industry vs. e-waste recycling). The presence of BDE202, as well as the BDE197 to BDE201 and the nona-BDEs to deca-BDE ratios in the dust samples from the studied areas were probably indicative of environmental degradation of deca-BDE. The estimated daily intakes (EDIs) of average adult and toddler via house dust ranged from 37.0 to 304 ng/day for PBDEs and from 3.01 to 87.6 ng/day for all other BFRs in the studied areas. The EDIs via house dust were much higher than those via other indoor pathways (air, fish, human milk, and toys). Despite the potentially low deleterious risk of PBDE exposure via house dust as suggested by the hazard quotients, this exposure pathway should be of great concern because of the higher BFR exposures for children and the presence of other BFRs (such as DBDPE) which have not yet been fully investigated.

  6. 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. PMID:27281541

  7. Transcriptional and epigenetic mechanisms underlying enhanced in vitro adipocyte differentiation by the brominated flame retardant BDE-47.

    PubMed

    Kamstra, Jorke H; Hruba, Eva; Blumberg, Bruce; Janesick, Amanda; Mandrup, Susanne; Hamers, Timo; Legler, Juliette

    2014-04-01

    Recent studies suggest that exposure to endocrine-disrupting compounds (EDCs) may play a role in the development of obesity. EDCs such as the flame retardant 2,2',4,4'-tetrabrominated diphenyl ether (BDE-47) have been shown to enhance adipocyte differentiation in the murine 3T3-L1 model. The mechanisms by which EDCs direct preadipocytes to form adipocytes are poorly understood. Here, we examined transcriptional and epigenetic mechanisms underlying the induction of in vitro adipocyte differentiation by BDE-47. Quantitative high content microscopy revealed concentration-dependent enhanced adipocyte differentiation following exposure to BDE-47 or the antidiabetic drug troglitazone (TROG). BDE-47 modestly activated the key adipogenic transcription factor peroxisome proliferator-activated receptor gamma (PPARγ) in COS7 cells, transiently transfected with a GAL4 reporter construct. Increased gene expression was observed for Pparγ2, leptin (Lep), and glucose-6-phophatase catalytic subunit (G6pc) in differentiated 3T3-L1 cells after BDE-47 exposure compared to TROG. Methylation-sensitive high resolution melting (MS-HRM) revealed significant demethylation of three CpG sites in the Pparγ2 promoter after exposure to both BDE-47 and TROG in differentiated 3T3-L1 cells. This study shows the potential of BDE-47 to induce adipocyte differentiation through various mechanisms that include Pparγ2 gene induction and promoter demethylation accompanied by activation of PPARγ, and possible disruption of glucose homeostasis and IGF1 signaling. PMID:24559133

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

    PubMed

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

    2014-12-01

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

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

    PubMed

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

    2014-12-01

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

  10. Transcriptional and Epigenetic Mechanisms Underlying Enhanced in Vitro Adipocyte Differentiation by the Brominated Flame Retardant BDE-47

    PubMed Central

    2015-01-01

    Recent studies suggest that exposure to endocrine-disrupting compounds (EDCs) may play a role in the development of obesity. EDCs such as the flame retardant 2,2′,4,4′-tetrabrominated diphenyl ether (BDE-47) have been shown to enhance adipocyte differentiation in the murine 3T3-L1 model. The mechanisms by which EDCs direct preadipocytes to form adipocytes are poorly understood. Here, we examined transcriptional and epigenetic mechanisms underlying the induction of in vitro adipocyte differentiation by BDE-47. Quantitative high content microscopy revealed concentration-dependent enhanced adipocyte differentiation following exposure to BDE-47 or the antidiabetic drug troglitazone (TROG). BDE-47 modestly activated the key adipogenic transcription factor peroxisome proliferator-activated receptor gamma (PPARγ) in COS7 cells, transiently transfected with a GAL4 reporter construct. Increased gene expression was observed for Pparγ2, leptin (Lep), and glucose-6-phophatase catalytic subunit (G6pc) in differentiated 3T3-L1 cells after BDE-47 exposure compared to TROG. Methylation-sensitive high resolution melting (MS-HRM) revealed significant demethylation of three CpG sites in the Pparγ2 promoter after exposure to both BDE-47 and TROG in differentiated 3T3-L1 cells. This study shows the potential of BDE-47 to induce adipocyte differentiation through various mechanisms that include Pparγ2 gene induction and promoter demethylation accompanied by activation of PPARγ, and possible disruption of glucose homeostasis and IGF1 signaling. PMID:24559133

  11. 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.

  12. Variation, levels and profiles of organochlorines and brominated flame retardants in great tit (Parus major) eggs from different types of sampling locations in Flanders (Belgium).

    PubMed

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

    2008-02-01

    Small-scale geographical variation in the occurrence of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) was investigated using the eggs of a terrestrial residential songbird species, the great tit (Parus major). In addition, we investigated the influence of the type of sampling location on the presence of these pollutants. To achieve this, 10 different sampling locations in Flanders (Belgium) were classified into 3 groups based on the extent of urbanisation, industrialisation and agriculture. The higher variance among sampling locations for the levels and profiles of PCBs and OCPs, suggests that local contamination sources are more important for the PCBs and OCPs compared to the PBDEs. Levels of PCBs and PBDEs were significantly higher in the industrialised sampling locations compared to the other locations. Sum PCB and sum PBDE levels reached up to 6050 and 79 ng/g lipid weight, respectively. PCBs and PBDEs were highly positively correlated for all groups, suggesting similar exposure pathways and/or mechanisms of accumulation. Significantly higher levels of OCPs (sum OCPs up to 2683 ng/g lipid weight) were detected in the rural sampling locations situated in a residential area. This suggests that local historical usage of OCPs by inhabitants may be an important source of contamination in Flanders. Contamination profiles differed also among the sampling locations. The rural sampling locations had a higher contribution of lower brominated BDE congeners, whereas the industrialised locations had a higher contribution of higher brominated congeners. The differences in contamination profiles among the sampling locations are probably due to differences in exposure. In conclusion, our results showed that the characteristics of a sampling location influence both the levels and profiles of PCBs, OCPs and PBDEs. PMID:17765970

  13. Diphenyloctyl phosphate as a flame-retardant additive in electrolyte for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Shim, Eun-Gi; Nam, Tae-Heum; Kim, Jung-Gu; Kim, Hyun-Soo; Moon, Seong-In

    The use of diphenyloctyl phosphate (DPOF) as a flame-retardant additive in liquid electrolyte for Li-ion batteries is investigated. Mesocarbon microbeads (MCMB) and LiCoO 2 are used as the anode and cathode materials, respectively. Cyclic voltammetry (CV), differential scanning calorimetry (DSC), electrochemical impedance spectroscopy (EIS), and scanning electron microscopy (SEM) are used for the analyses. The cell with DPOF shows better electrochemical cell performance than that without DPOF in initial charge/discharge and rate performance tests. In cycling tests, a cell with DPOF-containing electrolyte exhibited better discharge capacity and capacity retention than that of the DPOF-free electrolyte after cycling. These results confirm the viability of using DPOF as a flame-retardant additive for improving the cell performance and thermal stability of electrolytes for Li-ion batteries.

  14. Distribution pattern of legacy and "novel" brominated flame retardants in different particle size fractions of indoor dust in Birmingham, United Kingdom.

    PubMed

    Al-Omran, Layla Salih; Harrad, Stuart

    2016-08-01

    This study investigates the particle size distribution of eight polybrominated diphenyl ethers (PBDEs) and five "novel" brominated flame retardants (NBFRs) in settled house dust. Elevated surface dust (ESD) and floor dust (FD) were collected from 5 homes in Birmingham, UK, yielding a total of 10 samples. Each sample was fractionated into three different particle sizes: 125-250 μm (P1), 63-125 μm (P2) and 25-63 μm (P3). Non-fractionated bulk dust samples (BD) were also analysed. BDE-209 predominated, comprising an average 74.3%, 77.3%, 69.2%, and 62.7% ΣBFRs of BD, P1, P2 and P3 respectively. Σ5NBFRs contributed 24.2%, 21.5%, 29.0% and 35.3% ΣBFRs, while Σ7tri-hepta-BDEs represented 1.5%, 1.2%, 1.7%, and 2.0% ΣBFRs. BEH-TEBP was the predominant NBFR contributing 76.9%, 75.1%, 83.1%, and 83.9% ΣNBFRs in BD, P1, P2 and P3 respectively; followed by DBDPE which contributed 20.1%, 21.9%, 14.1% and 13.9% ΣNBFRs. EH-TBB, BTBPE and PBEB were the least abundant NBFRs. Concentrations of Σ7tri-hepta-BDEs and BEH-TEBP in P3 exceeded significantly (P < 0.05) those in P2, with those in P2 exceeding significantly those in P1. In contrast, no significant differences were found between concentrations of BDE-209, EH-TBB, BTBPE, and DBDPE in different particle size fractions. Concentrations of Σ7tri-hepta-BDEs, BDE-209, and BEH-TEBP in ESD exceeded significantly those in FD (P < 0.05). Normalising BFR concentrations to organic carbon content, did not alter these findings. This suggests that differences in BFR concentrations between different particle size fractions are caused by variations in particle surface area to volume ratio, rather than by variations in organic carbon content.

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

    PubMed

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

    2014-11-01

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

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

    PubMed

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

    2014-11-01

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

  17. Dioxins, PCBs, chlorinated pesticides and brominated flame retardants in free-range chicken eggs from peri-urban areas in Arusha, Tanzania: Levels and implications for human health.

    PubMed

    Polder, A; Müller, M B; Brynildsrud, O B; de Boer, J; Hamers, T; Kamstra, J H; Lie, E; Mdegela, R H; Moberg, H; Nonga, H E; Sandvik, M; Skaare, J U; Lyche, J L

    2016-05-01

    The environment in the northern part of Tanzania is influenced by rapid population growth, and increased urbanization. Urban agriculture is common and of economic value for low income families. In Arusha, many households sell eggs from free-ranging backyard chicken. In 2011, 159 eggs from different households in five different locations in Arusha were collected, homogenized, pooled into 28 composite samples and analyzed for a wide selection of POPs. Levels of POPs varied widely within and between the locations. The levels of dieldrin and ΣDDT ranged between 2 and 98,791 and 2 and 324ng/g lipid weight (lw), respectively. EU MRLs of 0.02mg/kg dieldrin for eggs were exceeded in 4/28 samples. PCBs, HCHs, chlordanes, toxaphenes and endosulfanes were found at lower frequency and levels. Brominated flame retardants (BFRs), e.g polybrominated diphenylethers (PBDEs), hexabromocyclododecane (HBCD) and 1,2-bis(2,4,6-tribromphenoxy)ethane (BTBPE) were present in 100%, 60% and 46% of the composite samples, respectively. Octa-and deca-BDEs were the dominating PBDEs and BDE 209 levels ranged between

  18. Distribution pattern of legacy and "novel" brominated flame retardants in different particle size fractions of indoor dust in Birmingham, United Kingdom.

    PubMed

    Al-Omran, Layla Salih; Harrad, Stuart

    2016-08-01

    This study investigates the particle size distribution of eight polybrominated diphenyl ethers (PBDEs) and five "novel" brominated flame retardants (NBFRs) in settled house dust. Elevated surface dust (ESD) and floor dust (FD) were collected from 5 homes in Birmingham, UK, yielding a total of 10 samples. Each sample was fractionated into three different particle sizes: 125-250 μm (P1), 63-125 μm (P2) and 25-63 μm (P3). Non-fractionated bulk dust samples (BD) were also analysed. BDE-209 predominated, comprising an average 74.3%, 77.3%, 69.2%, and 62.7% ΣBFRs of BD, P1, P2 and P3 respectively. Σ5NBFRs contributed 24.2%, 21.5%, 29.0% and 35.3% ΣBFRs, while Σ7tri-hepta-BDEs represented 1.5%, 1.2%, 1.7%, and 2.0% ΣBFRs. BEH-TEBP was the predominant NBFR contributing 76.9%, 75.1%, 83.1%, and 83.9% ΣNBFRs in BD, P1, P2 and P3 respectively; followed by DBDPE which contributed 20.1%, 21.9%, 14.1% and 13.9% ΣNBFRs. EH-TBB, BTBPE and PBEB were the least abundant NBFRs. Concentrations of Σ7tri-hepta-BDEs and BEH-TEBP in P3 exceeded significantly (P < 0.05) those in P2, with those in P2 exceeding significantly those in P1. In contrast, no significant differences were found between concentrations of BDE-209, EH-TBB, BTBPE, and DBDPE in different particle size fractions. Concentrations of Σ7tri-hepta-BDEs, BDE-209, and BEH-TEBP in ESD exceeded significantly those in FD (P < 0.05). Normalising BFR concentrations to organic carbon content, did not alter these findings. This suggests that differences in BFR concentrations between different particle size fractions are caused by variations in particle surface area to volume ratio, rather than by variations in organic carbon content. PMID:27213241

  19. Dioxins, PCBs, chlorinated pesticides and brominated flame retardants in free-range chicken eggs from peri-urban areas in Arusha, Tanzania: Levels and implications for human health.

    PubMed

    Polder, A; Müller, M B; Brynildsrud, O B; de Boer, J; Hamers, T; Kamstra, J H; Lie, E; Mdegela, R H; Moberg, H; Nonga, H E; Sandvik, M; Skaare, J U; Lyche, J L

    2016-05-01

    The environment in the northern part of Tanzania is influenced by rapid population growth, and increased urbanization. Urban agriculture is common and of economic value for low income families. In Arusha, many households sell eggs from free-ranging backyard chicken. In 2011, 159 eggs from different households in five different locations in Arusha were collected, homogenized, pooled into 28 composite samples and analyzed for a wide selection of POPs. Levels of POPs varied widely within and between the locations. The levels of dieldrin and ΣDDT ranged between 2 and 98,791 and 2 and 324ng/g lipid weight (lw), respectively. EU MRLs of 0.02mg/kg dieldrin for eggs were exceeded in 4/28 samples. PCBs, HCHs, chlordanes, toxaphenes and endosulfanes were found at lower frequency and levels. Brominated flame retardants (BFRs), e.g polybrominated diphenylethers (PBDEs), hexabromocyclododecane (HBCD) and 1,2-bis(2,4,6-tribromphenoxy)ethane (BTBPE) were present in 100%, 60% and 46% of the composite samples, respectively. Octa-and deca-BDEs were the dominating PBDEs and BDE 209 levels ranged between

  20. 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

  1. 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.

  2. 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)

  3. Persistent organic pollutants, brominated flame retardants and synthetic musks in fish from remote alpine lakes in Switzerland.

    PubMed

    Schmid, Peter; Kohler, Martin; Gujer, Erika; Zennegg, Markus; Lanfranchi, Marco

    2007-04-01

    Remote alpine lakes do not receive any direct aquatic inputs from anthropogenic activities. Therefore, these ecosystems may receive persistent organic compounds (POPs) by direct atmospheric deposition, only. Consequently, fish dwelling in these ecosystems represent an excellent indicator for the long-term atmospheric input of bioaccumulating and persistent contaminants. In the present study, fish from seven remote alpine lakes, located between 2062 and 2637 m above sea level in south eastern Switzerland (Grisons), were investigated. Lipid-based fish tissue concentrations of pesticides including dichlorodiphenyltrichloroethane (DDT) and its transformation products (2,4'-DDT, 4,4'-DDT, 2,4'-dichlorodiphenyldichloroethane (DDD), 4,4'-DDD, 2,4'-dichlorodiphenyldichloroethene (DDE), 4,4'-DDE), as well as dieldrin, heptachlor exo-epoxide (HPEX), hexachlorobenzene (HCB), hexachlorocyclohexanes (HCH), polychlorinated biphenyls (PCB), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and polybrominated diphenyl ethers (PBDE) were measured. In addition, seven synthetic musk compounds (Crysolide (ADBI), Phantolide (AHMI), Fixolide (AHTN), Traseolide (ATII), Galaxolide (HHCB), musk ketone (MK), and musk xylene (MX)) were determined. Concentrations of PCB, PCDD/F, and PBDE were in the same range as in fish from the major lakes situated in the Swiss plateau, indicating mainly atmospheric input of these persistent compounds. In contrast, concentrations of synthetic musks which are used as fragrances in laundry detergents and cosmetic products were distinctly lower than concentrations in fish from Swiss plateau lakes which receive inputs from waste water treatment plants.

  4. 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.

  5. The Influence of the Distribution State of Flame-retardants and Talc on the Flammability of Polypropylene

    NASA Astrophysics Data System (ADS)

    Seino, Makoto; Nomura, Manabu; Matsubara, Shigeyoshi; Kotaki, Masaya; Hamada, Hiroyuki

    Flammability of polymer is a phenomenon of oxidation reaction at near surface of products. Distribution of filler and flame-retardant at surface of products is thought to influence the flammability. So model samples that have various distributions of flame-retardant and filler, were made by using high-speed sandwich injection moldings. In this study, two types of flame-retardant, bromine type and phosphorous type, were used. The model sample which had high flame-retardant content in surface layer and high filler content in core layer, had good flammability and mechanical properties. Especially, phosphorous flame-retardant showed superior effect in that small amount of flame-retardant achieved same flammability as flame-retardant PP without filler. Control of distribution of flame-retardant and filler by using high-speed sandwich injection molding is cost-effective method with low flame-retardant addition.

  6. 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

  7. Halogenated flame retardants in the Great Lakes environment.

    PubMed

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

    2015-07-21

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

  8. Developmental exposure to a brominated flame retardant: an assessment of effects on physiology, growth, and reproduction in a songbird, the zebra finch.

    PubMed

    Eng, Margaret L; Williams, Tony D; Elliott, John E

    2013-07-01

    Mixtures of polybrominated diphenyl ethers (PBDEs) have been widely used as additive flame retardants, and BDE-99 is one of the most predominant congeners found in the environment. BDE-99 has been reported in avian samples worldwide, yet knowledge of its toxicity to birds is minimal. We assessed the short- and long-term effects of nestling exposure to environmentally relevant levels of BDE-99 in a model passerine, the zebra finch. Early exposure to BDE-99 did not affect hematocrit, oxidative stress, or thyroid hormones in either the juvenile or adult stages, and there were no effects on chick growth or survival. BDE-99 exposure caused a dose-dependent delay in timing of reproduction, but there were no other effects on reproductive success. In zebra finches, endpoints related to reproductive behavior appear to be the most sensitive to BDE-99. However, passerines overall appear to be less sensitive than birds of prey or mammals to PBDE exposure. PMID:23603472

  9. 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)

  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

    2015-04-01

    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. Investigation of fuel-additive effects on sooting flames. Final report, 1 June 1986-31 May 1989

    SciTech Connect

    Bonczyk, P.A.

    1989-07-28

    Research was conducted to clarify the mechanisms responsible for the suppression of soot in flames by selected fuel additives. Measurements were limited to well-defined prevaporized liquid- and gaseous-fueled hydrocarbon/air flames. Emphasis was given to ferrocene in a diffusion flame fueled by prevaporized iso-octane, as well as to alkali and alkaline-earth additives in premixed ethylene/air flames. Nonperturbing laser optical diagnostic techniques were used to measure flame temperature, as well as to relate changes in soot particulate size, number density, and volume fraction to additive type and concentration. Quartz probe sampling and gas chromatography were used to determine the additive's effect on soot precursor hydrocarbon and other species. For the diffusion flame, the time of the first appearance of soot is shortened when ferrocene is present. Following its appearance, the particulate's size and number density are perturbed by ferrocene. Ferrocene accelerates acetylene oxidation. Ferrocene is very effective at late stages, appearing to enhance soot burnout. Attempts were not successful to find iron occluded by soot as a possible mechanism of enhanced soot oxidation. Alkali metals were effective.

  12. Investigation of fuel-additive effects on sooting flames. Annual technical report, 1 June 1987-31 May 1988

    SciTech Connect

    Bonczyk, P.A.

    1988-06-30

    The objective of this research is to clarify the mechanisms responsible for the suppression of soot in flames by fuel additives. Measurements are limited to well-defined hydrocarbon air prevaporized liquid- and gaseous-fueled flames. Gas-phase hydrocarbon species measurements were made in an axisymmetric prevaporized iso-octane/air diffusion flame with and without ferrocene present as a fuel additive. The concentrations have been determined using quartz probe sampling and chromatographic analysis. Of the roughly twenty species detected, most were unaffected by the ferrocene. Expections were C2H2 and H2 which showed a decrease and increase, respectively, with ferrocene seeding. Solid effluent was collected and analyzed by ESCA (Electron Scattering for Chemical Analysis) for the seeded flame. For seeding levels sufficient to suppress a soot plume, the effluent was hematite.

  13. 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.

  14. 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.

  15. Melamine Polyphosphate - the Reactive and Additive Flame Retardant for Polyurethane Foams.

    PubMed

    Lubczak, Jacek; Lubczak, Renata

    2016-01-01

    Melamine polyphosphate, MPP was applied as reactive and additive flame retardant for thermally resistant polyurethane foams. MPP was hydroxyalkylated with ethylene and propylene carbonates to get oligoetherols with 1,3,5-triazine ring and phosphorus. The structure and physical properties of the products were studied. The polyurethane foams, PUFs obtained from this oligoetherols were self-distinguishing. The addition of powdered MPP into foaming mixture resulted in further decrease of flammability modified PUFs. The MPP-modified PUFs were characterized by physical methods adequate to thermal resistance and flammability of the PUFs. The best MPP-modified PUF showed oxygen index 24.6. All the modified PUFs were remarkably thermally resistant; they could stand long lasting thermal exposure even at 200 °C. PMID:26970791

  16. 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

  17. 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

  18. Determination, correlation, and mechanistic interpretation of effects of hydrogen addition on laminar flame speeds of hydrocarbon–air mixtures

    SciTech Connect

    Tang, C. L.; Huang, Z. H.; Law, C. K.

    2010-08-30

    The stretch-affected propagation speeds of expanding spherical flames of n-butane–air mixtures with hydrogen addition were measured at atmospheric pressure and subsequently processed through a nonlinear regression analysis to yield the stretch-free laminar flame speeds. Based on a hydrogen addition parameter (RH) and an effective fuel equivalence ratio (ΦF), these laminar flame speeds were found to increase almost linearly with RH, for ΦF between 0.6 and 1.4 and RHRH from 0 to 0.5, with the slope of the variation assuming a minimum around stoichiometry. These experimental results also agree well with computed values using a detailed reaction mechanism. Furthermore, a mechanistic investigation aided by sensitivity analysis identified that kinetic effects through the global activation energy, followed by thermal effects through the adiabatic flame temperature, have the most influence on the increase in the flame speeds and the associated linear variation with RH due to hydrogen addition. Nonequidiffusion effects due to the high mobility of hydrogen, through the global Lewis number, have the least influence. Further calculations for methane, ethene, and propane as the fuel showed similar behavior, leading to possible generalization of the phenomena and correlation.

  19. 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).

  20. 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

  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. Applicability of Gas Chromatography (GC) Coupled to Triple-Quadrupole (QqQ) Tandem Mass Spectrometry (MS/MS) for Polybrominated Diphenyl Ether (PBDE) and Emerging Brominated Flame Retardant (BFR) Determinations in Functional Foods Enriched in Omega-3.

    PubMed

    García-Bermejo, Ángel; Mohr, Susana; Herrero, Laura; González, María-José; Gómara, Belén

    2016-09-28

    This paper reports on the optimization, characterization, and applicability of gas chromatography coupled to triple-quadrupole tandem mass spectrometry (GC-QqQ(MS/MS)) for the determination of 14 polybrominated diphenylethers (PBDEs) and 2 emerging brominated flame retardants, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), in functional food samples. The method showed satisfactory precision and linearity with instrumental limits of detection (iLODs) ranging from 0.12 to 7.1 pg, for tri- to octa-BDEs and BTBPE, and equal to 51 and 20 pg for BDE-209 and DBDPE, respectively. The highest ΣBFR concentrations were found in fish oil supplements (924 pg/g fresh weight, fw), followed by biscuits (90 pg/g fw), vegetable oil supplements (46 pg/g fw), chicken eggs (45 pg/g fw), cow's milk (7.7 pg/g fw), and soy products (1.6 pg/g fw). BDE-47, BDE-99, and DBDPE were the most abundant compounds. Foodstuffs enriched with omega-3 presented concentrations similar to or even lower than those of conventional foods commercialized in Spain since 2000. PMID:27600263

  3. Applicability of Gas Chromatography (GC) Coupled to Triple-Quadrupole (QqQ) Tandem Mass Spectrometry (MS/MS) for Polybrominated Diphenyl Ether (PBDE) and Emerging Brominated Flame Retardant (BFR) Determinations in Functional Foods Enriched in Omega-3.

    PubMed

    García-Bermejo, Ángel; Mohr, Susana; Herrero, Laura; González, María-José; Gómara, Belén

    2016-09-28

    This paper reports on the optimization, characterization, and applicability of gas chromatography coupled to triple-quadrupole tandem mass spectrometry (GC-QqQ(MS/MS)) for the determination of 14 polybrominated diphenylethers (PBDEs) and 2 emerging brominated flame retardants, 1,2-bis(2,4,6-tribromophenoxy)ethane (BTBPE) and decabromodiphenylethane (DBDPE), in functional food samples. The method showed satisfactory precision and linearity with instrumental limits of detection (iLODs) ranging from 0.12 to 7.1 pg, for tri- to octa-BDEs and BTBPE, and equal to 51 and 20 pg for BDE-209 and DBDPE, respectively. The highest ΣBFR concentrations were found in fish oil supplements (924 pg/g fresh weight, fw), followed by biscuits (90 pg/g fw), vegetable oil supplements (46 pg/g fw), chicken eggs (45 pg/g fw), cow's milk (7.7 pg/g fw), and soy products (1.6 pg/g fw). BDE-47, BDE-99, and DBDPE were the most abundant compounds. Foodstuffs enriched with omega-3 presented concentrations similar to or even lower than those of conventional foods commercialized in Spain since 2000.

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

    PubMed

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

    2016-01-15

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

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

    PubMed

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

    2016-01-15

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

  6. 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

  7. 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.

  8. 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…

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

    SciTech Connect

    Alsabbagh, A.M.

    1990-01-01

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

  10. 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...

  11. 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.

  12. 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...

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

    PubMed

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

    2010-11-01

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

  14. 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.

  15. Brominated-chlorinated diphenyl ethers formed by thermolysis of polybrominated diphenyl ethers at low temperatures.

    PubMed

    Rupp, Silke; Metzger, Jörg W

    2005-09-01

    Polybrominated diphenyl ethers (PBDEs) are a group of brominated flame retardants (BFRs) used mainly as additives in different kinds of plastic material. Various PBDEs are found in all environmental compartments as well as in tissue and blood serum of animals and humans due to their persistence and tendency to bioaccumulate. Emission of PBDEs into the environment can occur during recycling of PBDE-containing plastic material or during their uncontrolled or insufficient combustion as e.g. in accidental fires or landfill fires. Under these circumstances, PBDEs can also function as precursor molecules for the formation of polybrominated dibenzodioxins (PBDDs) and dibenzofurans (PBDFs). In this study, we qualitatively investigated the reaction of two PBDE congeners, 2,2',4,4'-tetrabromo diphenyl ether (BDE 47) and 2,2',4,4',5,5'-hexabromo diphenyl ether (BDE 153), as well as hexabromobenzene (HBB), a flame retardant used in the past, when exposed to temperatures between 250 degrees C and 500 degrees C. The formed reaction products were analysed by high resolution gas chromatography-low resolution mass spectrometry (HRGC-LRMS). Among others brominated-chlorinated diphenyl ethers were formed by chlorodebromination of the PBDEs. In addition, thermolysis of BDE 47 and BDE 153 in the presence of tetrachloromethane as model substance for an organic chlorine source was studied. Thermal treatment of HBB resulted in the formation of brominated-chlorinated benzenes. PMID:16083771

  16. Photolytic degradation products of two highly brominated flame retardants cause cytotoxicity and mRNA expression alterations in chicken embryonic hepatocytes.

    PubMed

    Su, Guanyong; Letcher, Robert J; Crump, Doug; Farmahin, Reza; Giesy, John P; Kennedy, Sean W

    2014-10-21

    Tetradecabromo-1,4-diphenoxybenzene (TeDB-DiPhOBz) and 2,2',3,3',4,4',5,5',6,6'-decabromodiphenyl ether (BDE-209) are photolytically unstable flame retarding chemicals. Here, photocatalyzed byproducts of TeDB-DiPhOBz and BDE-209 (i.e Br(8)- to Br(11)-PB-DiPhOBz congeners from TeDB-DiPhOBz, and Br(6)- to Br(8)-BDE congeners from BDE-209), formed after 21 days of natural sunlight irradiation (SI), were assessed for exposure effects on cytotoxicity and mRNA expression levels of selected genes in chicken embryonic hepatocytes (CEH). CEHs were exposed for 36 h to concentrations of SI- and nonirradiated (NI)-TeDB-DiPhOBz and BDE-209. Cytotoxic effects were observed only in CEH exposed to 50 μM SI-BDE-209. Results from a custom-designed Avian ToxChip polymerase chain reaction array showed that NI-TeDB-DiPhOBz and NI-BDE-209, up to maximum concentrations of 1.9 and 9 μM, respectively, caused limited changes in mRNA levels of 27 genes from toxicologically relevant pathways, including phase I/II metabolism, the thyroid hormone pathway, lipid/cholesterol metabolism, oxidative stress, immune response, and cell death. In contrast, 12 and 14 of the 27 genes were altered after exposure to 25 μM SI-TeDB-DiPhOBz or 10 μM SI-BDE-209, respectively. Aryl hydrocarbon receptor (AhR)-related CYP1A4 mRNA levels were the most altered on the PCR array with an induction of 560- and 5200-fold after exposure to 1 or 25 μM SI-TeDB-DiPhOBz, respectively, and 2500- and 2300-fold after exposure to 1 or 10 μM SI-BDE-209, respectively. A dioxin-responsive luciferase reporter gene assay confirmed that the CYP1A4 inductions were independent of the dissolution solvents used (tetrahydrofuran/n-hexane, n-hexane, or methanol) during photolysis. Overall, degradation of TeDB-DiPhOBz and BDE-209 by natural sunlight generates byproducts that affect in vitro expression of genes, especially the AhR-mediated CYP1A4. PMID:25222814

  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. 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,...

  19. 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,...

  20. 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,...

  1. 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,...

  2. 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,...

  3. 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.

  4. 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...

  5. 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...

  6. 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...

  7. 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...

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

    PubMed

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

    2011-06-15

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

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

    PubMed

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

    2011-06-15

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

  10. 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

  11. 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.

  12. Secondary functionalization of allyl-terminated GaP(111)A surfaces via heck cross-coupling metathesis, hydrosilylation, and electrophilic addition of bromine.

    PubMed

    Peczonczyk, Sabrina L; Brown, Elizabeth S; Maldonado, Stephen

    2014-01-14

    The functionalization of single crystalline gallium phosphide (GaP) (111)A surfaces with allyl groups has been performed using a sequential chlorine-activation/Grignard reaction process. Increased hydrophobicity following reaction of a GaP(111)A surface with C3H5MgCl was observed through water contact angle measurements. Infrared spectra of GaP(111)A samples after reaction with C3H5MgCl showed the asymmetric C═C and C═C-H modes diagnostic of surface-attached allyl groups. The stability of allyl-terminated GaP(111)A surfaces under ambient and aqueous conditions was investigated. XP spectra of allyl-terminated GaP(111)A highlighted a significant resistance against interfacial oxidation both in air and in water relative to the native interface. Electrochemical impedance spectroscopy indicated a change in the flat-band potential of allyl-terminated GaP(111)A electrodes immersed in water relative to native GaP(111)A surfaces. Further, the flat-band potentials for allyl-terminated electrodes were insensitive to changes in solution pH. The utility of surface-bound allyl groups for covalent secondary functionalization of GaP(111)A interfaces was assessed through three separate reactions: Heck cross-coupling metathesis, hydrosilylation, and electrophilic addition of bromine reactions. Addition of aryl groups across the olefins on allyl-terminated GaP(111)A via Heck cross coupling was performed and confirmed through high-resolution F 1s and C 1s XP spectra and IR spectra. Control experiments with GaP(111)A surfaces functionalized with short alkanes indicated no evidence for metathesis. Hydrosilylation reactions were separately performed. Si 2s XP spectra, in conjunction with infrared spectra, similarly showed secondary evidence of surface functionalization for allyl-terminated GaP(111)A but not for CH3-terminated GaP(111)A surfaces. Similar analyses showed electrophilic addition of Br2 across the terminal olefin on an allyl-terminated GaP(111)A surface after exposure to

  13. Plastics additives in the indoor environment--flame retardants and plasticizers.

    PubMed

    Wensing, M; Uhde, E; Salthammer, T

    2005-03-01

    Phthalic acid esters and phosphororganic compounds (POC) are generally known as semivolatile organic compounds (SVOCs) and are frequently utilized as plasticizers and flame retardants in commercial products. In the indoor environment, both compound groups are released from a number of sources under normal living conditions and accumulate in air and dust. Therefore, inhalation of air and ingestion of house dust have to be considered as important pathways for the assessment of exposure in living habitats. Especially in the case of very young children, the oral and dermal uptake from house dust might be of relevance for risk assessment. A critical evaluation of indoor exposure to phthalates and POC requires the determination of the target compounds in indoor air and house dust as well as emission studies. The latter are usually carried out under controlled conditions in emission test chambers or cells. Furthermore, chamber testing enables the determination of condensable compounds by fogging sampling. In the case of automobiles, specific scenarios have been developed to study material emissions on a test stand or to evaluate the exposure of users while the vehicle is driving. In this review, results from several studies are summarized and compared for seven phthalic esters and eight POC. The available data for room air and dust differ widely depending on investigated compound and compartment. Room air studies mostly include only a limited number of measurements, which makes a statistical evaluation difficult. The situation is much better for house dust measurements. However, the composition of house dust is very inhomogeneous and the result is strongly dependent on the particle size distribution used for analysis. Results of emission studies are presented for building products, electronic equipment, and automobiles. Daily rates for inhalation and dust ingestion of phthalic esters and POC were calculated from 95-percentiles or maximum values. A comparison of the data

  14. 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...

  15. Catalytic and electrocatalytic hydrogenolysis of brominated diphenyl ethers.

    PubMed

    Bonin, Pascale M L; Edwards, Patrick; Bejan, Dorin; Lo, Chun Chi; Bunce, Nigel J; Konstantinov, Alexandre D

    2005-02-01

    Polybrominated diphenyl ethers (PBDEs) are ubiquitous environmental contaminants due to their use as additive flame-retardants. Conventional catalytic hydrogenolysis in methanol solution and electrocatalytic hydrogenolysis in aqueous methanol were examined as methods for debrominating mono- and di-bromodiphenyl ethers, as well as a commercial penta-PBDE mixture, in each case using palladium on alumina as the catalyst. Electrocatalytic hydrogenolysis employed a divided flow-through batch cell, with reticulated vitreous carbon cathodes and IrO2/Ti dimensionally stable anodes. Both methods gave efficient sequential debromination, with essentially complete removal of bromine from the PBDEs, but the electrocatalytic method was limited by the poor solubility of PBDEs in aqueous methanol. PMID:15639268

  16. Analysis of zinc in biological samples by flame atomic absorption spectrometry: use of addition calibration technique.

    PubMed

    Dutra, Rosilene L; Cantos, Geny A; Carasek, Eduardo

    2006-01-01

    The quantification of target analytes in complex matrices requires special calibration approaches to compensate for additional capacity or activity in the matrix samples. The standard addition is one of the most important calibration procedures for quantification of analytes in such matrices. However, this technique requires a great number of reagents and material, and it consumes a considerable amount of time throughout the analysis. In this work, a new calibration procedure to analyze biological samples is proposed. The proposed calibration, called the addition calibration technique, was used for the determination of zinc (Zn) in blood serum and erythrocyte samples. The results obtained were compared with those obtained using conventional calibration techniques (standard addition and standard calibration). The proposed addition calibration was validated by recovery tests using blood samples spiked with Zn. The range of recovery for blood serum and erythrocyte samples were 90-132% and 76-112%, respectively. Statistical studies among results obtained by the addition technique and conventional techniques, using a paired two-tailed Student's t-test and linear regression, demonstrated good agreement among them. PMID:16943611

  17. 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.

  18. 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 ...

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. Candle Flames in Microgravity

    NASA Technical Reports Server (NTRS)

    Dietrich, Daniel L.; Ross, Howard D.; Frate, David T.; Tien, James S.; Shu, Yong

    1997-01-01

    This work is a study of a candle flame in a microgravity environment. The purpose of the work is to determine if a steady (or quasi-steady) flame can exist in a microgravity environment, study the characteristics of the steady flame, investigate the pre-extinction flame oscillations observed in a previous experiment in more detail, and finally, determine the nature of the interactions between two closely spaced candle flames. The candle flame is used as a model combustion system, in that in microgravity it is one of the only examples of a non-propagating, steady-state, pure diffusion flame. Others have used the candle to study a number of combustion phenomena including flame flicker, flame oscillations, electric field effects and enhanced and reduced gravitational effects in flames. The present work is a continuation of a small-scale Shuttle experiment on candle flames. That study showed that the candle flame lifetimes were on the order of 40 seconds, the flames were dim blue after a transient ignition period, and that just prior to extinction the flames oscillated spontaneously for about five seconds at a frequency of 1 Hz. The authors postulated that the gas phase in the immediate vicinity of the flame was quasi-steady. Further away from the flame, however, the assertion of a quasi-steady flame was less certain, thus the authors did not prove that a steady flame could exist. They also speculated that the short lifetime of the candle flame was due to the presence of the small, weakly perforated box that surrounded the candle. The Candle Flames in Microgravity (CFM) experiment, with revised hardware, was recently flown aboard the Mir orbiting station, and conducted inside the glovebox facility by Dr. Shannon Lucid. In addition to the purposes described above, the experiments were NASA's first ability to ascertain the merits of the Mir environment for combustion science studies. In this article, we present the results of that experiment. We are also in the process

  5. 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.

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

    PubMed

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

    2016-03-10

    Underwriters Laboratories 94 test bars have been imaged with X-ray K-edge tomography between 12 and 32 keV to assess the bromine and antimony concentration gradient across char layers of partially burnt samples. Phase contrast tomography on partially burnt samples showed gas bubbles and dark-field scattering ascribed to residual blend inhomogeneity. In addition, single-shot grating interferometry was used to record X-ray movies of test samples during heating (IR and flame) intended to mimic the UL 94 plastics flammability test. The UL 94 test bars were formulated with varying concentrations of a brominated flame retardant, Saytex 8010, and a synergist, Sb2O3, blended into high-impact polystyrene (HIPS). Depending on the sample composition, samples will pass or fail the UL 94 plastics flammability test. Tomography and interferometry imaging show differences that correlate with UL 94 performance. Key features such as char layer, gas bubble formation, microcracks, and dissolution of the flame retardant in the char layer regions are used in understanding the efficiency of the flame retardant and synergist. The samples that pass the UL 94 test have a thick, highly visible char layer as well as an interior rich in gas bubbles. Growth of gas bubbles from flame-retardant thermal decomposition is noted in the X-ray phase contrast movies. Also noteworthy is an absence of bubbles near the burning surface of the polymer; dark-field images after burning suggest a microcrack structure between interior bubbles and the surface. The accepted mechanism for flame retardant activity includes free radical quenching in the flame by bromine and antimony species. The imaging supports this as well as provides a fast inspection of other parameters, such as viscosity and surface tension. PMID:26846254

  7. 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

  8. 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...

  9. 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...

  10. 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...

  11. 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...

  12. Development of Flame Retardants for Engineering Polymers and Polyurethanes

    NASA Astrophysics Data System (ADS)

    Desikan, Anantha

    2013-03-01

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

  13. Flame resistant elastic elastomeric fibers

    NASA Technical Reports Server (NTRS)

    Howarth, J. T.; Massucco, A. A.

    1972-01-01

    Development of materials to improve flame resistance of elastic elastomeric fibers is discussed. Two approaches, synthesis of polyether based urethanes and modification of synthesized urethanes with flame ratardant additives, are described. Specific applications of both techniques are presented.

  14. 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.

  15. Laser-induced fluorescence of CF{sub 2} from a CH{sub 4} flame and an H{sub 2} flame with addition of HCFC-22 and HFC-134a

    SciTech Connect

    Su, Y.; Gu, Y.; Reck, G.P.; Rothe, E.W.; Francisco, J.S.

    1998-04-01

    Laser-induced fluorescence (LIF) of CF{sub 2} radicals in atmospheric diffusion flames is reported for the first time. When a CH{sub 4} flame is premixed with HCFC-22 (CCIF{sub 2}H) or HFC-134a (CF{sub 3}CFH{sub 2}), fluorescence spectra between 250 and 314 nm of the {tilde A}{sup 1}B{sub 1}-{tilde X}{sup 1}A{sub 1} transition from CF{sub 2} are observed when the flame is probed by a KrF laser. When these two halocarbons are added to an atmospheric H{sub 2} flame, similar LIF spectra of CF{sub 2} are also observed. Two-dimensional LIF images from the flames show that the CF{sub 2} radicals are localized between the flame center and the flame front.

  16. Flame retardant spandex type polyurethanes

    NASA Technical Reports Server (NTRS)

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

    1978-01-01

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

  17. 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.

  18. 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,…

  19. Impact of the flame retardant additive triphenyl phosphate (TPP) on the performance of graphite/LiFePO4 cells in high power applications

    NASA Astrophysics Data System (ADS)

    Ciosek Högström, Katarzyna; Lundgren, Henrik; Wilken, Susanne; Zavalis, Tommy G.; Behm, Mårten; Edström, Kristina; Jacobsson, Per; Johansson, Patrik; Lindbergh, Göran

    2014-06-01

    This study presents an extensive characterization of a standard Li-ion battery (LiB) electrolyte containing different concentrations of the flame retardant triphenyl phosphate (TPP) in the context of high power applications. Electrolyte characterization shows only a minor decrease in the electrolyte flammability for low TPP concentrations. The addition of TPP to the electrolyte leads to increased viscosity and decreased conductivity. The solvation of the lithium ion charge carriers seem to be directly affected by the TPP addition - as evidenced by Raman spectroscopy and increased mass-transport resistivity. Graphite/LiFePO4 full cell tests show the energy efficiency to decrease with the addition of TPP. Specifically, diffusion resistivity is observed to be the main source of increased losses. Furthermore, TPP influences the interface chemistry on both the positive and the negative electrode. Higher concentrations of TPP lead to thicker interface layers on LiFePO4. Even though TPP is not electrochemically reduced on graphite, it does participate in SEI formation. TPP cannot be considered a suitable flame retardant for high power applications as there is only a minor impact of TPP on the flammability of the electrolyte for low concentrations of TPP, and a significant increase in polarization is observed for higher concentrations of TPP.

  20. Triple flames and flame stabilization

    NASA Technical Reports Server (NTRS)

    Broadwell, James E.

    1994-01-01

    It is now well established that when turbulent jet flames are lifted, combustion begins, i.e., the flame is stabilized, at an axial station where the fuel and air are partially premixed. One might expect, therefore, that the beginning of the combustion zone would be a triple flame. Such flames have been described; however, other experiments provide data that are difficult to reconcile with the presence of triple flames. In particular, laser images of CH and OH, marking combustion zones, do not exhibit shapes typical of triple flames, and, more significantly, the lifted flame appears to have a propagation speed that is an order of magnitude higher than the laminar flame speed. The speed of triple flames studied thus far exceeds the laminar value by a factor less than two. The objective of the present task is the resolution of the apparent conflict between the experiments and the triple flame characteristics, and the clarification of the mechanisms controlling flame stability. Being investigated are the resolution achieved in the experiments, the flow field in the neighborhood of the stabilization point, propagation speeds of triple flames, laboratory flame unsteadiness, and the importance of flame ignition limits in the calculation of triple flames that resemble lifted flames.

  1. Diphenyloctyl phosphate and tris(2,2,2-trifluoroethyl) phosphite as flame-retardant additives for Li-ion cell electrolytes at elevated temperature

    NASA Astrophysics Data System (ADS)

    Nam, Tae-Heum; Shim, Eun-Gi; Kim, Jung-Gu; Kim, Hyun-Soo; Moon, Seong-In

    The effect of diphenyloctyl phosphate (DPOF) and tris(2,2,2-trifluoroethyl) phosphite (TTFP) as flame-retardant (FR) additives in the liquid electrolyte of Li-ion cells is evaluated at both elevated temperature (40 °C) and room temperature (RT, 25 °C). The tested cells use mesocarbon microbeads (MCMB) and LiCoO 2 as the anode and cathode materials, respectively. Cell characteristics are investigated by means of electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The results of the cycle performance tests demonstrate the superior discharge capacity and capacity retention of the DPOF-containing cell compared will TTFP after cycling at both RT and 40 °C. Therefore, these results confirm the promising potential of DPOF as an FR additive for improving the electrochemical performance of Li-ion batteries.

  2. 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.

  3. 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...

  4. Preliminary study on the occurrence of brominated organic compounds in Dutch marine organisms.

    PubMed

    Kotterman, Michiel; van der Veen, Ike; van Hesselingen, Judith; Leonards, Pim; Osinga, Ronald; de Boer, Jacob

    2003-07-01

    The extracts of three marine organisms; the ascidian Ciona intestinalis, the brown seaweed Sargassum muticum and the sponge Halichondria panicea, all elicited a number of brominated compounds, some of which were tentatively identified. Tribromophenol was observed in all species. This compound, also industrially produced as flame retardant and fungicide, was likely due to endogenous production. PMID:12919829

  5. 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.

  6. 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.

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

    PubMed

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

    2015-01-01

    Polybrominated diphenyl ethers (PBDEs) increased in many matrices during the 1990s and early 2000s. Since voluntary restrictions and regulations on PBDEs were implemented in North America circa early 2000s, decreases in PBDEs have occurred in many of these same matrices. To examine temporal trends in the North Pacific, we retrospectively analysed PBDEs and eight non-PBDE flame retardants (FR) in eggs of two aquatic bird species, great blue herons, Ardea herodias, and double-crested cormorants, Phalacrocorax auritus, collected along the British Columbia coast, Canada from 1979 to 2012. Increasing PBDE concentrations were observed in both species followed by significant decreases post-2000 for all dominant congeners and ΣPBDE. Non-PBDE FRs were generally undetected in cormorant eggs, or detected at very low levels in heron eggs, except for hexabromocyclododecane (HBCDD). HBCDD, currently unregulated in North America, was not detected in early sampling years; however low concentrations were observed in both species in recent sampling years (2003-2012). Dietary tracers (δ(13)C and δ(15)N) did not change significantly over time, indicating that temporal changes in PBDEs are likely caused by implemented regulations. A comparison with recently published temporal trends of ΣPBDE in marine birds from North America and Europe is given. PMID:25241209

  8. 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)

  9. 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.

  10. 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.

  11. 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...

  12. 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.

  13. Contributions of BrCl, Br2, BrOCl, Br2O, and HOBr to regiospecific bromination rates of anisole and bromoanisoles in aqueous solution.

    PubMed

    Sivey, John D; Bickley, Mark A; Victor, Daniel A

    2015-04-21

    When bromide-containing waters are chlorinated, conventional wisdom typically assumes HOBr is the only active brominating agent. Several additional and often-overlooked brominating agents (including BrCl, Br2, BrOCl, Br2O) can form in chlorinated waters, albeit at generally lower concentrations than HOBr. The extent to which these additional brominating agents influence bromination rates of disinfection byproduct precursors is, however, poorly understood. Herein, the influence of BrCl, Br2, BrOCl, Br2O, and HOBr toward rates of sequential bromination of anisole was quantified. Conditions affecting bromine speciation (e.g., pH, concentrations of chloride, bromide, and chlorine) were varied, and regiospecific second-order rate constants were calculated for reactions of each brominating agent with anisole, 2-bromoanisole, and 4-bromoanisole. The regioselectivity of anisole bromination changed with pH, consistent with the participation of more than one brominating agent. Under conditions representative of chlorinated drinking water, contributions to bromination rates decreased as BrCl > BrOCl > HOBr > Br2O (Br2 negligible). The second-order rate constant determined for net bromination of anisole by HOBr is up to 3000-times less than reported in previous studies (which assumed HOBr was the only active brominating agent). Accordingly, models that assume HOBr is the only kinetically relevant brominating agent in solutions of free bromine may be insufficient for reactions involving modestly nucleophilic organic compounds.

  14. 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.

  15. 40 CFR 180.519 - Bromide ion and residual bromine; tolerances for residues.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... additives, bromide ion and residual bromine, may be present in water, potable in accordance with the following conditions: (1) The food additives are present as a result of treating water aboard ships with a...) Residual bromine levels are controlled to not exceed 1.0 part per million (ppm) in the final treated...

  16. Bromine function in halite geochemistry

    SciTech Connect

    Billo, S.M. )

    1991-06-01

    Of the halogens or salt formers, bromine is the only nonmetal which occurs naturally as a poisonous liquid much denser than water. The power of its atoms, expressed by a valence of 1 and 5, makes it unite directly with a large number of metallic elements to form salts. As a rare and strongly electronegative element of group VII in the periodic table, bromine exists in seawater and evaporitic brines as bromide with a ratio to chlorinity of 0.00348. Most water detains only about 1 ppm bromide for each 300 ppm of chloride. The most abundant source of bromine is ocean water (65 ppm Br), but richer peps occur in salt deposits and primarily in mineral brines. Atomic absorption spectrophotometric resolutions of Permian Castile halites exposed low values of bromine compared with its higher quantities in modern oceans like the Mediterranean. Bromine analyses of the two petrographically distinct forms of halite that characterize many ancient evaporite deposits, as in the Elk Point basin fields of Alberta, imply they crystallized from brines of noticeably different concentrations. Bromine in halite has been used as a paleosalinity indicator and a stratigraphic marker. Bromine liquid, with an atomic weight of 79.904 and atomic number 35, is used in producing gasoline antiknock mixtures, fumigants, photographic chemicals, drilling fluids, and fire retardants. It is also highly toxic and corrosive as bromine gas. Bromine contents greater than 1 ppm may be unsafe in the atmosphere, and a dose of 500 ppm can lead to death in less than an hour.

  17. 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

  18. 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.

  19. 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.

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

    PubMed

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

    2016-06-01

    In response to concerns regarding the widespread use of flame retardants, the California Legislature passed a law (SB1019) requiring labels on furniture products to indicate whether they do or do not contain flame retardants. To support the enforcement of the new law, our laboratory developed a step-wise, screening approach to test for brominated (BFR) and phosphorus-based flame retardants (OPFRs) in several types of furniture components (foam, fabric, batting, plumage, etc.). We used X-Ray Fluorescence (XRF) to screen for the presence of Br (and other elements) and Inductively Coupled Plasma - Optical Emission Spectrometry (ICP-OES) to identify and measure the concentration of P (and other elements). The same samples were also extracted by dichloromethane using sonication and analyzed by a single injection into a Gas Chromatograph - Tandem Mass Spectrometer to obtain concentrations of specific BFRs and OPFRs. Our approach showed excellent screening potential for Br and Sb by XRF and for P by ICP-OES, with both tests having predictive values of a negative equal to 1. To explore and screen for flame retardants in products not included in our current list of target chemicals, we used Liquid Chromatography/Time-of-Flight Mass Spectrometry operated with electrospray ionization, to identify additional flame retardants to be incorporated in quantitative methods. We are making all our methodologies public to facilitate simple and low cost methods that can help manufacturers and suppliers have their products tested and correctly labeled, ultimately benefitting the consumer. PMID:26991383

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

    NASA Astrophysics Data System (ADS)

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

    2012-02-01

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

  2. 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)

  3. Candle Flames in Microgravity Video

    NASA Technical Reports Server (NTRS)

    1997-01-01

    This video of a candle flame burning in space was taken by the Candle Flames in Microgravity (CFM) experiment on the Russian Mir space station. It is actually a composite of still photos from a 35mm camera since the video images were too dim. The images show a hemispherically shaped flame, primarily blue in color, with some yellow early int the flame lifetime. The actual flame is quite dim and difficult to see with the naked eye. Nearly 80 candles were burned in this experiment aboard Mir. NASA scientists have also studied how flames spread in space and how to detect fire in microgravity. Researchers hope that what they learn about fire and combustion from the flame ball experiments will help out here on Earth. Their research could help create things such as better engines for cars and airplanes. Since they use very weak flames, flame balls require little fuel. By studying how this works, engineers may be able to design engines that use far less fuel. In addition, microgravity flame research is an important step in creating new safety precautions for astronauts living in space. By understanding how fire works in space, the astronauts can be better prepared to fight it.

  4. An evaluation of different contributions to flame stretch for stationary premixed flames

    SciTech Connect

    Goey, L.P.H. de; Mallens, R.M.M.; Thije Boonkkamp, J.H.M. ten

    1997-07-01

    The concept of flame stretch is extended to study stationary premixed flames with a finite thickness. It is shown that the analysis results in additional contributions to the stretch rate due to changes in the flame thickness and due to density variations along the flame. Extended expressions are derived that describe the effect of stretch on variations in scalar quantities, such as the enthalpy. These expressions are used to determine local variations in the flame temperature, and it is shown that known results are recovered when a number of approximations are introduced. The extended stretch formalism might be useful to analyze and quantify the different flame stretch contributions and their effects in numerical flame studies. Finally, the different contributions to the total stretch rate and the effects thereof on the flame stabilization are numerically computed for the flame tip of a two-dimensional Bunsen flame as illustration.

  5. Substrate Directed Regioselective Monobromination of Aralkyl Ketones Using N-Bromosuccinimide Catalysed by Active Aluminium Oxide: α-Bromination versus Ring Bromination

    PubMed Central

    Mohan, Reddy Bodireddy; Reddy, G. Trivikram; Gangi Reddy, N. C.

    2014-01-01

    Bromination of aralkyl ketones using N-bromosuccinimide in presence of active Al2O3 provided either α-monobrominated products in methanol at reflux or mononuclear brominated products in acetonitrile at reflux temperature with excellent isolated yields depending on the nature of substrate employed. The α-bromination was an exclusive process when aralkyl ketones containing moderate activating/deactivating groups were subjected to bromination under acidic Al2O3 conditions in methanol at reflux while nuclear functionalization was predominant when aralkyl ketones containing high activating groups were utilized for bromination in presence of neutral Al2O3 conditions in acetonitrile at reflux temperature. In addition, easy isolation of products, use of inexpensive catalyst, short reaction time (10–20 min), and safe operational practice are the major benefits in the present protocol. PMID:24955257

  6. 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…

  7. 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.

  8. 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.

  9. Flame Hair

    PubMed Central

    Miteva, Mariya; Tosti, Antonella

    2015-01-01

    Background ‘Flame hairs’ is a trichoscopic feature described as hair residue from pulling anagen hairs in trichotillomania. Objective: To detect whether flame hairs are present in other hair loss disorders. Methods We retrospectively, independently and blindly reviewed the trichoscopic images of 454 consecutive patients with alopecia areata (99 cases), trichotillomania (n = 20), acute chemotherapy-induced alopecia (n = 6), acute radiotherapy-induced alopecia (n = 2), tinea capitis (n = 13), lichen planopilaris (n = 33), frontal fibrosing alopecia (n = 60), discoid lupus erythematosus (n = 30), dissecting cellulitis (n = 11), central centrifugal cicatricial alopecia (n = 94) and traction alopecia (n = 86) for the presence of flame hairs. We prospectively obtained trichoscopy-guided scalp biopsies from flame hairs in trichotillomania, alopecia areata, traction alopecia and central centrifugal cicatricial alopecia (1 case each). Results Flame hairs were detected in 100% of the acute chemotherapy- and radiotherapy-induced alopecias, where they were the predominant hair abnormality. They were also found in trichotillomania (55%), alopecia areata (21%), traction alopecia (4%) and central centrifugal cicatricial alopecia (3%). On pathology, they corresponded to distorted hair shafts. Conclusion The flame hair is a type of broken hair which can be seen in various hair loss disorders. It results from traumatic pulling of anagen hairs or from anagen arrest due to inflammation or drugs. © 2015 S. Karger AG, Basel PMID:27171360

  10. Bromine heterogenous chemistry in the troposhere

    SciTech Connect

    Abbatt, J.P.D.

    1996-10-01

    Motivated by the observations of boundary layer ozone loss which is correlated with high levels of bromine in the Arctic springtime, we have studied a number of heterogeneous interactions of tropospheric bromine species. The goal of this work is both to better define the source of inorganic bromine during this time of year and to determine the primary mechanism which keeps bromine in a photochemically active form.

  11. 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.

  12. Computational Studies of Flame Structures

    NASA Astrophysics Data System (ADS)

    Amin, Vaishali

    This thesis is concerned with computational studies of laminar flame structures using detailed and skeletal chemical kinetic mechanisms. Elementary reactions in these mechanisms control the observable combustion properties such as flame speed, autoignition temperature, ignition delay time, and extinction characteristics in nonpremixed and premixed flame phenomena. First part of thesis deals with computational investigations of influence of carbon monoxide and hydrogen addition on methane flames stabilized in counterflow configuration. Computations were performed employing detailed chemical kinetic mechanism---the San Diego mechanism. In case of nonpremixed flames, effect of carbon xvi monoxide addition on structure and critical condition of extinction were examined. Differences between addition on fuel and oxidizer sides were investigated and plausible explanation given for the differences. For premixed flames, effect of addition of hydrogen and carbon monoxide to reactant mixture was studied. Critical conditions of extinction were predicted using computations for various compositions. Rates of production and consumption of various species were calculated and flame structure was analyzed for nonpremixed and premixed flames. It was found that moderate amount of carbon monoxide addition to methane enhances flame reactivity. However, with large amount of carbon monoxide addition, additive chemistry dominates. Addition of increasing amounts of hydrogen in premixed reactant stream enhances methane flame reactivity. In second part of thesis, kinetic modeling was performed to elucidate the structure and mechanism of extinction and autoignition of nonpremixed toluene flames in counterflow configuration. Computations were performed using detailed chemistry to determine flame structure and to obtain values for critical conditions of extinction and autoignition. Sensitivity analysis of rate parameters, reaction pathway analysis, and spatial reaction rate profiles were used to

  13. 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...

  14. 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

  15. 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

  16. 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

  17. 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.

  18. The chemistry of atmospheric bromine. [catalyst for ozone destruction

    NASA Technical Reports Server (NTRS)

    Wofsy, S. C.; Mcelroy, M. B.; Yung, Y. L.

    1975-01-01

    Bromine may act as a catalyst for recombination of ozone and could be more efficient than either nitric oxide or chlorine. The lower atmosphere contains small concentrations of gaseous bromine produced in part by marine activity and volatilization of particulate material released during the combustion of leaded gasoline, with an additional contribution due to the use of methyl bromide as an agricultural fumigant. Observations by Lazrus et al., (1975) indicate small concentrations of bromine, about 10 to the -11th power (v/v), in the contemporary stratosphere and appear to imply a reduction of approximately 0.3% in the global budget of O3. Estimates are given for future reductions in O3 which might occur if the use of CH3Br as an agricultural fumigant were to continue to grow at present rates.

  19. 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.

  20. 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.

  1. 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.

  2. Flame retardants

    NASA Technical Reports Server (NTRS)

    Troitzsch, J.

    1988-01-01

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

  3. Rayleigh-Taylor Unstable Flames -- Fast or Faster?

    NASA Astrophysics Data System (ADS)

    Hicks, E. P.

    2015-04-01

    Rayleigh-Taylor (RT) unstable flames play a key role in the explosions of supernovae Ia. However, the dynamics of these flames are still not well understood. RT unstable flames are affected by both the RT instability of the flame front and by RT-generated turbulence. The coexistence of these factors complicates the choice of flame speed subgrid models for full-star Type Ia simulations. Both processes can stretch and wrinkle the flame surface, increasing its area and, therefore, the burning rate. In past research, subgrid models have been based on either the RT instability or turbulence setting the flame speed. We evaluate both models, checking their assumptions and their ability to correctly predict the turbulent flame speed. Specifically, we analyze a large parameter study of 3D direct numerical simulations of RT unstable model flames. This study varies both the simulation domain width and the gravity in order to probe a wide range of flame behaviors. We show that RT unstable flames are different from traditional turbulent flames: they are thinner rather than thicker when turbulence is stronger. We also show that none of the several different types of turbulent flame speed models accurately predicts measured flame speeds. In addition, we find that the RT flame speed model only correctly predicts the measured flame speed in a certain parameter regime. Finally, we propose that the formation of cusps may be the factor causing the flame to propagate more quickly than predicted by the RT model.

  4. Brominated and fluorinated organic pollutants in the breast milk of first-time Irish mothers: is there a relationship to levels in food?

    PubMed

    Pratt, Iona; Anderson, Wayne; Crowley, Dominique; Daly, Sean; Evans, Rhodri; Fernandes, Alwyn; Fitzgerald, Margaret; Geary, Michael; Keane, Declan; Morrison, John J; Reilly, Alan; Tlustos, Christina

    2013-01-01

    Brominated flame retardants - polybrominated diphenyl ethers (PBDEs), polybrominated biphenyls (PBBs), hexabromocyclododecane (HBCD) and others - have been measured in 11 pooled breast milk samples from 109 first-time mothers in Ireland. Additionally, the study has measured levels of polybrominated dibenzo-p-dioxins and furans (PBDD/Fs), mixed halogenated dioxins (PXCC/Fs) and biphenyls (PXBs), polychlorinated naphthalenes (PCNs) and perfluoroalkylated substances (PFAS) in these samples. The mean sum of 19 PBDEs including BDE-209 was 4.85 ng g(-1) fat, which is comparable with that found in other European countries. BDE-47, BDE-153, BDE-209, BDE-99 and BDE-100 were found at the highest concentrations. The only PBBs detected consistently were BB-77, BB-126 and BB-153, with highest concentrations being found for BB-153 (mean = 0.13 ng g(-1) fat). The mean sum of HBCD enantiomers was 3.52 ng g(-1) fat, with α-HBCD representing over 70% of the total. Of the other brominated flame retardants - tetrabromobisphenol-A (TBBP-A), hexabromobenzene (HBB), decabromodiphenylethane (DBDPE) and bis(2,4,6-tribromophenoxyethane) (BTBPE) - examined, only TBBP-A was detected above the limit of detection (LOD), in two of the 11 pools analysed. All measured PBDF congeners were observed (at 0.02-0.91 pg g(-1) fat), but 2,3,7,8-tetrabromo-dibenzodioxin (TeBDD) was the only PBDD detected, with a mean concentration of 0.09 pg g(-1) fat. The occurrence of the mixed chlorinated/brominated dibenzodioxins, dibenzofurans and biphenyls, 2-B-3,7,8-CDD, 2,3-B-7,8-CDF, 4-B-2,3,7,8-CDF, PXB 105, PXB 118, PXB 126 and PCB 156 in breast milk in the current study may indicate that levels of these contaminants are increasing in the environment. Polychlorinated naphthalenes were detected in all samples, but not perfluorooctane sulfonate (PFOS) and other PFAS. The pattern of occurrence of these brominated and fluorinated persistent organic pollutants (POPs) in Irish breast milk shows a general relationship

  5. 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.

  6. 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. PMID:26343755

  7. 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.

  8. 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.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  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. 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.

  13. Cool flame quench distances

    NASA Technical Reports Server (NTRS)

    Ryason, P. R.; Hirsch, E.

    1974-01-01

    The results of a brief experimental investigation are presented which confirm the expectation that cool flame quenching distances should be larger than hot flame quenching distances. It is also discovered that whereas quenching distances for hot flames reach their minimum values near stoichiometric conditions, cool flame quenching distances are least under rich conditions. Rich conditions are well known to favor cool flame formation.

  14. Hydrogen-Bromine Secondary Battery

    NASA Technical Reports Server (NTRS)

    England, C. (Inventor)

    1975-01-01

    A secondary battery is described utilizing hydrogen and halogen as primary reactants. It comprises inert anode and cathode initially contacting an aqueous solution of an acid and an alkali metal bromide. The hydrogen generated during charging of the cell is stored as gas, while the bromine becomes dissolved predominantly in the lower layers of the acid electrolyte. Preferred components are phosphoric acid and lithium bromide.

  15. Pulsed Turbulent Diffusion Flames in a Coflow

    NASA Astrophysics Data System (ADS)

    Usowicz, James E.; Hermanson, James C.; Johari, Hamid

    2000-11-01

    Fully modulated diffusion flames were studied experimentally in a co-flow combustor using unheated ethylene fuel at atmospheric pressure. A fast solenoid valve was used to fully modulate (completely shut-off) the fuel flow. The fuel was released from a 2 mm diameter nozzle with injection times ranging from 2 to 750 ms. The jet exit Reynolds number was 2000 to 10,000 with a co-flow air velocity of up to 0.02 times the jet exit velocity. Establishing the effects of co-flow for the small nozzle and short injection times is required for future tests of pulsed flames under microgravity conditions. The very short injection times resulted in compact, burning puffs. The compact puffs had a mean flame length as little as 20flame for the same Reynolds number. As the injection time and fuel volume increased, elongated flames resembling starting jets resulted with a flame length comparable to that of a steady flame. For short injection times, the addition of an air co-flow resulted in an increase in flame length of nearly 50flames with longer injection times was correspondingly smaller. The effects of interaction of successive pulses on the flame length were most pronounced for the compact puffs. The emissions of unburned hydrocarbon and NOx from the pulsed flames were examined.

  16. 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.

  17. 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.

  18. 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 ...

  19. 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.

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

    PubMed

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

    2013-01-01

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

  1. 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.

  2. 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.

  3. Lifted turbulent jet flames

    NASA Astrophysics Data System (ADS)

    Hammer, Jay A.

    Experiments were conducted on lifted, turbulent jet diffusion flames. An automated technique using a linear photodiode array was implemented to measure the temporal history of the liftoff height h. The measurements enabled accurate determination of the mean liftoff height [...] under a wide range of flow conditions, including several fuels, nozzle diameters, and exit velocities [...]. The results showed an approximately linear relationship between [...] and [...], with a slight dependence on Reynolds number. A strain-rate model for liftoff, based on far-field scaling of turbulent jets, provides an explanation for the linear dependence of [...] on [...]. Measurements were also made in which the nozzle fluid contained varying amounts of air, where it was found that the slope of the [...] vs. [...] line increases faster than predicted by far-field scaling of turbulent jets. The discrepancy is attributed to near-field effects.The amplitudes of the fluctuations in h were found to be of the order of the local large scale of the jet. There is a slight increase in normalized fluctuation level [...] with [...], and there is some variation of [...] with fuel type. The time scales of the fluctuations of h were found to be considerably longer than the local large-scale time of the turbulence [...]. By using fuels of different chemical times to vary [...], the measured correlation time [...] normalized by [...] was found to collapse with Richardson number [...]. Experiments in which the nozzles were oriented horizontally showed no change in [...], however. Additional experiments were conducted to investigate alternative explanations for the variation of [...] with [...]. These experiments included measuring the flame length L simultaneously with h, and measuring the visible radiation I simultaneously with h. L(t) was found to be nearly uncorrelated with h(t), dismissing the possibility that a feedback mechanism from L to h controls the fluctuations of h. Although I(t) is highly

  4. 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

  5. Oxidation of lactose with bromine.

    PubMed

    Yang, Byung Y; Montgomery, Rex

    2005-12-12

    Oxidation of lactose by bromine in an aqueous buffered solution was conducted as a model experiment to examine the glycosidic linkage cleavage occurring during the oxidation of oligosaccharides and polysaccharides. The resulting oxidation products, after reduction with sodium borodeuteride, were characterized by GLC-MS analyses of the per-O-methyl or per-O-Me3Si derivatives. Most of the products were carboxylic acids, of which lactobionic acid was major. Minor products, identified after partial fractionation on a BioGel P-2 column, comprised oxalic acid; glyceric acid; threonic and erythronic acids; tartaric acid; lyxonic, arabinonic, and xylonic acids; galactonic and gluconic acids; galactosylerythronic acid; galactosylarabinonic acid; galactosylarabinaric acid; galacturonosylarabinonic acid; and galactosylglucaric acid. No keto acids were identified. Galactose was detected as 1-deuteriogalactitol, the presence of which, together with the C6 aldonic acids, supported a galactosidic bond cleavage. Galactosylarabinonic acid was the major constituent (7.5%) among minors, and others constituted 0.2-3.7% of the principal lactobionic acid. These products together comprised 29% of the lactobionic acid, more than half (17%) of which were accounted for by the galactosidic linkage cleavage, supporting the significant decrease in molecular weight seen earlier in the bromine-oxidized polysaccharides by glycosidic cleavage.

  6. 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.

  7. Stratified turbulent Bunsen flames: flame surface analysis and flame surface density modelling

    NASA Astrophysics Data System (ADS)

    Ramaekers, W. J. S.; van Oijen, J. A.; de Goey, L. P. H.

    2012-12-01

    In this paper it is investigated whether the Flame Surface Density (FSD) model, developed for turbulent premixed combustion, is also applicable to stratified flames. Direct Numerical Simulations (DNS) of turbulent stratified Bunsen flames have been carried out, using the Flamelet Generated Manifold (FGM) reduction method for reaction kinetics. Before examining the suitability of the FSD model, flame surfaces are characterized in terms of thickness, curvature and stratification. All flames are in the Thin Reaction Zones regime, and the maximum equivalence ratio range covers 0.1⩽φ⩽1.3. For all flames, local flame thicknesses correspond very well to those observed in stretchless, steady premixed flamelets. Extracted curvature radii and mixing length scales are significantly larger than the flame thickness, implying that the stratified flames all burn in a premixed mode. The remaining challenge is accounting for the large variation in (subfilter) mass burning rate. In this contribution, the FSD model is proven to be applicable for Large Eddy Simulations (LES) of stratified flames for the equivalence ratio range 0.1⩽φ⩽1.3. Subfilter mass burning rate variations are taken into account by a subfilter Probability Density Function (PDF) for the mixture fraction, on which the mass burning rate directly depends. A priori analysis point out that for small stratifications (0.4⩽φ⩽1.0), the replacement of the subfilter PDF (obtained from DNS data) by the corresponding Dirac function is appropriate. Integration of the Dirac function with the mass burning rate m=m(φ), can then adequately model the filtered mass burning rate obtained from filtered DNS data. For a larger stratification (0.1⩽φ⩽1.3), and filter widths up to ten flame thicknesses, a β-function for the subfilter PDF yields substantially better predictions than a Dirac function. Finally, inclusion of a simple algebraic model for the FSD resulted only in small additional deviations from DNS data

  8. Aerodynamics of Laminar Flames

    NASA Astrophysics Data System (ADS)

    Law, Chung K.

    2000-11-01

    The presentation will review recent advances in the understanding of the structure, dynamics, and geometry of stretched, nonequidiffusive, laminar premixed flames, as exemplified by the unsteady propagation of wrinkled flames in nonuniform flow fields. It is first shown that by considering the effects of aerodynamic stretch on the flame structure, and by allowing for mixture nonequidiffusion, the flame responses, especially the flame propagation speed, can be quantitatively as well as qualitatively modified from the idealized planar limit. Subsequently, by treating the flame as a level surface propagating with the stretch-affected flame speed, problems of increasing complexity are presented to illustrate various features of flame propagation. The illustration first treats the flame as a structureless surface propagating into a constant-density combustible with a constant velocity * the laminar flame speed, and demonstrates the phenomena of cusp formation and volumetric burning rate augmentation through flame wrinkling. By using the stretch-affected flame speed, we then describe the phenomena of cusp broadening as well as tip opening of the Bunsen flame. Finally, by allowing for the density jump across the flame surface, a unified dispersion relation is derived for the intrinsic hydrodynamic, body-force, and nonequidiffusive modes of flame

  9. 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.

  10. Isoselenazolones as catalysts for the activation of bromine: bromolactonization of alkenoic acids and oxidation of alcohols.

    PubMed

    Balkrishna, Shah Jaimin; Prasad, Ch Durga; Panini, Piyush; Detty, Michael R; Chopra, Deepak; Kumar, Sangit

    2012-11-01

    Isoselenazolones were synthesized by a copper-catalyzed Se-N bond forming reaction between 2-halobenzamides and selenium powder. The catalytic activity of the various isoselenazolones was studied in the bromolactonization of pent-4-enoic acid. Isoselenazolone 9 was studied as a catalyst in several reactions: the bromolactonization of a series of alkenoic acids with bromine or N-bromosuccinimide (NBS) in the presence of potassium carbonate as base, the bromoesterification of a series of alkenes using NBS and a variety of carboxylic acids, and the oxidation of secondary alcohols to ketones using bromine as an oxidizing reagent. Mechanistic details of the isoselenazolone-catalyzed bromination reaction were revealed by (77)Se NMR spectroscopic and ES-MS studies. The oxidative addition of bromine to the isoselenazolone gives the isoselenazolone(IV) dibromide, which could be responsible for the activation of bromine under the reaction conditions. Steric effects from an N-phenylethyl group on the amide of the isoselenazolone and electron-withdrawing fluoro substituents on the benzo fused-ring of the isoselenazolone appear to enhance the stability of the isoselenazolone as a catalyst for the bromination reaction. PMID:23046286

  11. Stability and metastability of bromine clathrate polymorphs.

    PubMed

    Nguyen, Andrew H; Molinero, Valeria

    2013-05-23

    Clathrate hydrates are crystals in which water forms a network of fully hydrogen-bonded polyhedral cages that contain small guests. Clathrate hydrates occur mostly in two cubic crystal polymorphs, sI and sII. Bromine is one of two guests that yield a hydrate with the tetragonal structure (TS), the topological dual of the Frank-Kasper σ phase. There has been a long-standing disagreement on whether bromine hydrate also forms metastable sI and sII crystals. To date there are no data on the thermodynamic range of stability (e.g., the melting temperatures) of the metastable polymorphs. Here we use molecular dynamics simulations with the coarse-grained model of water mW to (i) investigate the thermodynamic stability of the empty and guest-filled the sI, sII, TS, and HS-I hydrate polymorphs, (ii) develop a coarse-grained model of bromine compatible with mW water, and (iii) evaluate the stability of the bromine hydrate polymorphs. The mW model predicts the same relative energy of the empty clathrate polymorphs and the same phase diagram as a function of water-guest interaction than the fully atomistic TIP4P water model. There is a narrow region in water-guest parameter space for which TS is marginally more stable than sI or sII. We parametrize a coarse-grained model of bromine compatible with mW water and use it to determine the order of stability of the bromine hydrate polymorphs. The melting temperatures of the bromine hydrate polymorphs predicted by the coarse-grained model are 281 ± 1 K for TS, 279 ± 1 K for sII, and 276 ± 1 K for sI. The closeness of the melting temperatures supports the plausibility of formation of metastable sII and sI bromine hydrates.

  12. 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.

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

    NASA Technical Reports Server (NTRS)

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

    1976-01-01

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

  14. Understanding flame rods

    SciTech Connect

    McAuley, J.A. Jr.

    1995-11-01

    The flame rod is probably the least understood method of flame detection. Although it is not recommended for oilfired equipment, it is very common on atmospheric, or {open_quotes}in-shot,{close_quotes} gas burners. It is also possible, although not common, to have an application with a constant gas pilot, monitored by a flame rod, and maintaining an oil main flame. Regardless of the application, chances are that flame rods will be encountered during the course of servicing. The technician today must be versatile and able to work on many different types of equipment. One must understand the basic principles of flame rods, and how to correct potential problems. The purpose of a flame detection system is two-fold: (1) to prove there is no flame when there shouldn`t be one, and (2) to prove there is a flame when there should be one. Flame failure response time is very important. This is the amount of time it takes to realize there is a loss of flame, two to four seconds is typical today. Prior to flame rods, either bi-metal or thermocouple type flame detectors were common. The response time for these detectors was up to three minutes, seldom less than one minute.

  15. 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.

  16. 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...

  17. 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.

  18. 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.

  19. 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)

  20. Saline Snow Surfaces and Arctic Bromine Activation

    NASA Astrophysics Data System (ADS)

    Pratt, K. A.; Custard, K. D.; Shepson, P.; Douglas, T. A.; Pöhler, D.; General, S.; Zielcke, J.; Platt, U.; Carlsen, M. S.; Tanner, D.; Huey, L. G.; Stirm, B.

    2012-12-01

    Following polar sunrise, tropospheric ozone levels often decrease rapidly to near zero, concurrent with mercury depletion and deposition. Despite our increasing understanding of the spatial variability of BrO and possible mechanisms based on laboratory studies, important questions remain regarding the most efficient sources of and mechanisms for Arctic halogen activation, leading to tropospheric ozone depletion. Rapid sea ice decline in the Arctic is expected to influence halogen activation and corresponding ozone and mercury depletion events. Therefore, an improved understanding of halogen activation is necessary to predict future changes in atmospheric chemical composition. During the March-April 2012 BRomine, Ozone, and Mercury EXperiment (BROMEX) in Barrow, Alaska, outdoor chamber experiments with snow and ice samples were conducted. Ozone was added as the precursor oxidant, and the samples were investigated with and without ambient sunlight. Samples included first-year sea ice, brine icicles, several layers of snow above first-year sea ice, and seasonal snow above the tundra. Chemical ionization mass spectrometry was utilized to monitor Br2 production, and ion chromatography was utilized to measure the bromide, chloride, nitrate, and sulfate content of the melted snow/ice samples. Surprisingly, tundra snow and drifting snow above sea ice produced the most Br2, with no production resulting from sea ice and basal snow directly above sea ice, suggesting more efficient production from samples characterized by greater acidity and lower chloride/bromide ratios. In addition, Br2 was only observed in the presence of sunlight, indicating the role of snowpack photolysis and the hydroxyl radical in its production. The observed trends in Br2 production may also help explain observations of inland hotspots in measured BrO by aircraft-based nadir MAX-DOAS (Multi Axis-Differential Optical Absorption Spectroscopy) measurements, conducted during the same field campaign. The

  1. An old flame

    NASA Astrophysics Data System (ADS)

    Thompson, Frank

    2014-07-01

    Flames are seen more often in chemistry than in physics laboratories. However, as a continuation of the previous colourful demonstration of a levitating Bunsen flame described recently in this journal (De Carvalho 2012 Phys Educ. 47 517), two short experiments are reported. Firstly, flame rectification is investigated and secondly, the electrical potential around a charged object is measured.

  2. 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

  3. Flame front configuration of turbulent premixed flames

    SciTech Connect

    Furukawa, Junichi; Maruta, Kaoru; Hirano, Toshisuke

    1998-02-01

    The present study is performed to explore dependence of the wrinkle scale of propane-air turbulent premixed flames on the characteristics of turbulence in the nonreacting flow, burner size, and mixture ratio. The wrinkle scales are examined and expressed in the frequency distribution of the radii of flame front curvatures. The average wrinkle scale depends not only on the characteristics of turbulence in the nonreacting flow but also on burner diameter and mixture ratio. The average wrinkle scale of a lean propane-air flame is larger than those of the near stoichiometric and rich flames. The smallest wrinkle scale of turbulent premixed flame is in the range of 0.75--1.0 mm, which is much larger than the Kolmogorov scale of turbulence in the nonreacting flow.

  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. Toxicity of new generation flame retardants to Daphnia magna.

    PubMed

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

    2013-10-01

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

  6. Analytical Study of Gravity Effects on Laminar Diffusion Flames

    NASA Technical Reports Server (NTRS)

    Edelman, R. B.; Fortune, O.; Weilerstein, G.

    1972-01-01

    A mathematical model is presented for the description of axisymmetric laminar-jet diffusion flames. The analysis includes the effects of inertia, viscosity, diffusion, gravity and combustion. These mechanisms are coupled in a boundary layer type formulation and solutions are obtained by an explicit finite difference technique. A dimensional analysis shows that the maximum flame width radius, velocity and thermodynamic state characterize the flame structure. Comparisons with experimental data showed excellent agreement for normal gravity flames and fair agreement for steady state low Reynolds number zero gravity flames. Kinetics effects and radiation are shown to be the primary mechanisms responsible for this discrepancy. Additional factors are discussed including elipticity and transient effects.